改性固体超强酸S2O82-/ZrO2-CoO用于FCC汽油氧化脱硫的研究

李昊; 闫锋; 杨少斌

改性固体超强酸S₂O₈^2-/ZrO₂-CoO用于FCC汽油氧化脱硫的研究

李昊¹,
闫锋^1, ,,
杨少斌²

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
中国石油天然气股份有限公司抚顺石化分公司催化剂厂, 辽宁抚顺 113001

基金项目:

国家科技重大专项课题任务 2016ZX05010-004-005

详细信息

中图分类号: TQ423.93
计量
- 文章访问数: 120
- HTML全文浏览量: 65
- PDF下载量: 13
- 被引次数: 0
出版历程
- 收稿日期: 2018-12-05
- 修回日期: 2019-01-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Modified solid superacid S₂O₈^2-/ZrO₂-CoO for oxidative desulfurization of FCC gasoline

LI Hao¹,
YAN Feng^{1
, ,},
YANG Shao-bin²

1.
College of Petrochemical Technology, Liaoning University of Petroleum & Chemical Technology, Fushun 113001, China
2.
China National Petroleum Corporation Fushun Petrochemical Company Catalyst Factory, Fushun 113001, China

Funds:

the National Science and Technology Major Project Tasks 2016ZX05010-004-005

More Information

Corresponding author: YAN Feng, E-mail: yfstar65@126.com

摘要

摘要: 以硝酸锆、硝酸铜和硝酸钴为金属源，过硫酸铵作为浸渍液，采用共沉淀浸渍法合成出固体超强酸催化剂S₂O₈^2-/ZrO₂、S₂O₈^2-/ZrO₂-CuO和S₂O₈^2-/ZrO₂-CoO，通过XRD、FT-IR、NH₃-TPD、BET对催化剂进行表征。结果表明，Co（钴）改性催化剂S₂O₈^2-/ZrO₂-CoO在三种催化剂中超强酸位最多。将其作为催化剂，过氧化氢作为氧化剂用于FCC汽油氧化脱硫反应，研究不同反应温度、催化剂用量、反应时间、氧化剂用量对FCC汽油脱硫效果的影响。结果表明，FCC汽油氧化脱硫的最佳条件为：反应温度70 ℃，反应1.5 h，FCC汽油加入量与氧化剂体积比7.5：1，催化剂用量0.02 g/mL。反应产物利用N，N-二甲基甲酰胺进行萃取分离，萃取剂/汽油体积比为1：1时，FCC汽油脱硫率最高可达85.34%，回收率为94.45%，并且催化剂表现出较为稳定的催化活性。
- 固体超强酸 /
- 氧化脱硫 /
- 浸渍法 /
- FCC汽油
Abstract: A series of solid super acid catalysts, S₂O₈^2-/ZrO₂, S₂O₈^2-/ZrO₂-CuO and S₂O₈^2-/ZrO₂-CoO, were synthesized by coprecipitation impregnation method with zirconium nitrate, copper nitrate and cobalt nitrate as the metal sources and with ammonium persulfate as the impregnation solution. The catalysts were characterized by XRD, FT-IR and NH₃-TPD. The characterization shows that the S₂O₈^2-/ZrO₂-CoO catalyst has the most super acid sites among the three catalysts. S₂O₈^2-/ZrO₂-CoO as the catalyst and hydrogen peroxide as the oxidant were used for oxidative desulfurization of FCC gasoline, and the effects of reaction temperature, catalyst dosage, reaction time and oxidant dosage on the desulfurization of FCC gasoline were studied. The optimal conditions were determined as:FCC gasoline of 15 mL, reaction temperature of 70℃, reaction time of 1.5 h, oxidant dosage of V(H₂O₂):V(oil)=7.5:1, and catalyst dosage of 0.02 g/mL. Moreover, the reaction product was extracted with N, N-dimethylformamide. When the volume ratio of extractant to gasoline is 1:1, the sulfur removal efficiency and recovery of FCC gasoline reach to 85.34% and 94.45%, respectively. The catalyst exhibits a relatively stable catalytic activity.
- solid super acid /
- oxidative desulfurization /
- impregnation method /
- FCC gasoline

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图 1 S₂O₈^2-/M_xO_y酸中心结构模型

Figure 1 Acid center structure model of S₂O₈^2-/M_xO_y

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图 2 不同催化剂的XRD谱图

Figure 2 XRD patterns of different catalysts

a: S₂O₈^2-/ZrO₂; b: S₂O₈^2-/ZrO₂-CuO; c: S₂O₈^2-/ZrO₂-CoO

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图 3 不同催化剂的FT-IR谱图

Figure 3 FT-IR spectra of different catalysts

a: S₂O₈^2-/ZrO₂-CoO; b: S₂O₈^2-/ZrO₂; c: S₂O₈^2-/ZrO₂-CuO

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图 4 不同催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD spectra of different catalysts

a: S₂O₈^2-/ZrO₂-CoO; b: S₂O₈^2-/ZrO₂-CuO; c: S₂O₈^2-/ZrO₂

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图 5 不同催化剂的脱硫率

Figure 5 Desulfurization efficiency with different catalysts

a: S₂O₈^2-/ZrO₂-CoO; b: S₂O₈^2-/ZrO₂-CuO; c: S₂O₈^2-/ZrO₂

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图 6 反应温度(a)、催化剂用量(b)、反应时间(c)和氧化剂用量(d)对脱硫效率的影响

Figure 6 Effect of reaction temperature (a), amount of catalyst (b), reaction time (c) and oxidant dosage (d) on desulfurization efficiency

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图 7 不同萃取剂对脱硫率和回收率的影响

Figure 7 Effect of different extractants on desulfurization efficiency and recovery

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图 8 催化剂循环使用次数对脱硫率的影响

Figure 8 Effect of recycling numbers of catalyst on desulfurization efficiency

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表 1 不同催化剂的BET数据

Table 1 BET data of different catalysts

Catalyst	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm
S₂O₈^2-/ZrO₂	102.2	0.129	1.83
S₂O₈^2-/ZrO₂-CuO	114.1	0.098	0.96
S₂O₈^2-/ZrO₂-CoO	130.9	0.071	0.55

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表 2 直接萃取与反应后再萃取对脱硫率的影响

Table 2 Effect of direct extraction and extraction after reaction on the desulfurization efficiency

Extraction	Desulfurization efficiency η/%	Recovery /%
Direct extraction	49.85	95.33
Extraction after reaction	85.34	94.45

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表 3 FCC汽油氧化脱硫反应前后的硫形态分布

Table 3 Distribution of sulfur form before and after oxidative desulfurization of FCC gasoline

Apex RT	Species of sulfide	Distribution w/%
Apex RT	Species of sulfide	s_before	s_after
1.27	hydrothion	35.32	-
1.33	methanthiol	36.19	8.92
1.47	ethanethiol	136.83	33.93
1.65	isopropyl mercaptan	32.89	8.14
1.94	n-propyl mercaptan	50.37	12.60
2.48	thiophene	166.31	41.30
3.14	n-butyl mercaptan	10.83	2.71
4.62	2-methylthiophene	94.12	23.46
4.84	3-methylthiophene	125.76	-
5.69	tetrahydrothiophene	57.05	-
6.93	C6-thioether	15.12	3.68
7.51	2-methyltetrahydrothiophene	15.89	-
8.69	2-ethylthiophene	61.67	-
9.35	2、4-dimethylthiophene	77.92	19.2
9.83	2、3-dimethylthiophene	55.92	-
10.64	3、5-dimethylthiophene	31.86	-
15.23	C3-thiophene	34.18	-
15.4	C3-thiophene	12.50	-
15.86	C3-thiophene	36.53	9.11
17.05	C3-thiophene	8.47	-
17.84	C3-thiophene	31.61	-
21.88	C4-thiophene	19.31	4.85
23.65	C4-thiophene	6.54	-
24.51	C4-thiophene	6.76	-
25.38	C4-thiophene	9.22	-
30.06	benzothiophene	76.84	19.00
34.26	C4-thiophene	6.80	-
36.38	methylbenzothiophene	11.6	-
36.95	methylbenzothiophene	11.05	-
37.44	methylbenzothiophene	8.17	-
37.8	methylbenzothiophene	12.32	3.10
Total		1295.96	190.02

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