合成条件对磷钨酸负载的金属有机框架催化剂氧化脱硫性能的影响

张东旭; 宋华; 苑丹丹

合成条件对磷钨酸负载的金属有机框架催化剂氧化脱硫性能的影响

张东旭¹,
宋华^{1, 2, ,},
苑丹丹^{1, 2}

1.
东北石油大学化学化工学院, 黑龙江大庆 163318
2.
东北石油大学石油与天然气化工省重点实验室, 黑龙江大庆 163318

基金项目:

中国石油和化学工业联合会科技指导项目 2016-09-02

详细信息

中图分类号: O643;TQ53
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- 被引次数: 0
出版历程
- 收稿日期: 2018-11-26
- 修回日期: 2018-12-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-02-10

Effect of synthesis conditions on the catalytic performance of phosphotungstic acid encapsulated metal-organic framework in the oxidative desulfurization

ZHANG Dong-xu¹,
SONG Hua^{1, 2
, ,},
YUAN Dan-dan^{1, 2}

1.
College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
2.
Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, China

Funds:

the Mentoring Project of China Petroleum and Chemical Industry Federation 2016-09-02

More Information

Corresponding author: SONG Hua, Tel: 0459-6503167, E-mail: songhua2004@sina.com

摘要

摘要: 通过一步水热合成法制备了大比表面积、高脱硫活性的磷钨酸（HPW）负载的金属有机框架HPW@MIL-101（Cr）催化剂，对其进行了FT-IR、XRD和氮吸附等表征，并研究了合成时间、合成温度、酸碱度及HPW负载量等参数对催化剂脱硫性能的影响。结果表明，随着合成时间的延长、合成温度的提高，HPW@MIL-101（Cr）孔道有序度提高；合成温度低于等于140℃时，不能形成MIL-101（Cr）晶体结构；酸性合成条件合成的HPW@MIL-101（Cr）的孔道有序度降低；随着HPW负载量的增加，HPW@MIL-101（Cr）的催化性能呈现先升高后降低的趋势。在12 h、220℃和中性条件下制备得到的负载量为3.5 g的HPW@MIL-101（Cr）催化剂具有最佳脱硫活性；在模拟油20 mL、催化剂用量0.24 g、氧硫比为8和50℃条件下反应120 min，对苯并噻吩、二苯并噻吩和4，6-二甲基二苯并噻吩脱硫率分别为99%、100%和99%；与HPW相比，苯并噻吩脱硫率提高了2.4倍。
- 磷钨酸 /
- 金属有机框架 /
- 氧化脱硫 /
- 苯并噻吩(BT)
Abstract: A series of phosphotungstic acid (HPW) encapsulated metal-organic HPW@MIL-101(Cr) catalysts, with high surface area and high activity in the oxidative desulfurization (ODS), were synthesized by one-step hydrothermal method and characterized by FT-IR, XRD and nitrogen physisorption. The influences of synthesis time, temperature, HPW loading, and acidity/alkalinity on the catalytic performance of HPW@MIL-101(Cr) in ODS were then investigated. The results indicated that the order degree of channels in HPW@MIL-101(Cr) is improved with the increase of synthesis time and temperature. The crystal structure of MIL-101(Cr) cannot be formed at a synthetic temperature below 140℃ and the channel order of HPW@MIL-101(Cr) decreases under an acidic synthetic environment. The catalytic activity of HPW@MIL-101(Cr) displays a trend of first increasing and then decreasing with the increase of HPW loading. The HPW@MIL-101(Cr) catalyst with a HPW loading of 3.5 g, synthesized at 220℃ under neutral environment for 12 h, exhibits the highest activity in ODS. At 50℃, with a catalyst dosage of 0.24 g, an model oil of 20 mL, and an O/S molar ratio of 8, the desulfurization rates over the HPW@MIL-101(Cr) catalyst towards benzothiophene, dibenzothiophene, and 4, 6-dimethyl dibenzothiophene after reaction for 120 min reach 99%, 100% and 99%, respectively; in particular, the desulfurization rate for benzothiophene is 2.4 times higher than that obtained over HPW.
- phosphotungstic acid /
- metal-organic framework /
- oxidative desulfurization performance /
- benzothiophene (BT)

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图 1 不同合成时间制备的催化剂的XRD谱图

Figure 1 XRD patterns of catalysts with different synthesis time

a: HPW(3.5)@MIL-101(Cr)-2-220-zh; b: HPW(3.5)@MIL-101(Cr)-4-220-zh; c: HPW(3.5)@MIL-101(Cr)-8-220-zh; d: HPW(3.5)@MIL-101(Cr)-12-220-zh

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图 2 不同合成温度制备的催化剂XRD谱图

Figure 2 XRD patterns of catalysts at different synthesis temperatures

a: HPW(3.5)@MIL-101(Cr)-12-100-zh; b: HPW(3.5)@MIL-101(Cr)-12-140-zh; c: HPW(3.5)@MIL-101(Cr)-12-180-zh; d: HPW(3.5)@MIL-101(Cr)-12-220-zh

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图 3 不同酸碱度催化剂的XRD谱图

Figure 3 XRD patterns of catalysts with different acidity/alkalinity

a: HPW(3.5)@MIL-101(Cr)-12-220-s; b: HPW(3.5)@MIL-101(Cr)-12-220-zh; c: HPW(3.5)@MIL-101(Cr)-12-220-j

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图 4 不同合成时间制备的催化剂的FT-IR谱图

Figure 4 FT-IR spectra of catalysts with different synthesis time

a: HPW(3.5)@MIL-101(Cr)-2-220-zh; b: HPW(3.5)@MIL-101(Cr)-4-220-zh; c: HPW(3.5)@MIL-101(Cr)-8-220-zh; d: HPW(3.5)@MIL-101(Cr)-12-220-zh

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图 5 不同合成温度制备的催化剂的FT-IR谱图

Figure 5 FT-IR spectra of catalysts at different synthesis temperatures

a: HPW(3.5)@MIL-101(Cr)-12-100-zh; b: HPW(3.5)@MIL-101(Cr)-12-140-zh; c: HPW(3.5)@MIL-101(Cr)-12-180-zh; d: HPW(3.5)@MIL-101(Cr)-12-220-zh

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图 6 不同酸碱度催化剂的FT-IR谱图

Figure 6 FT-IR spectra of catalysts with different acidity/alkalinity

a: HPW(3.5)@MIL-101(Cr)-12-220-s; b: HPW(3.5)@MIL-101(Cr)-12-220-zh; c: HPW(3.5)@MIL-101(Cr)-12-220-j

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图 7 合成时间对HPW(3.5)@MIL-101(Cr)-x-220-zh催化剂BT催化氧化脱硫性能的影响

Figure 7 Effect of synthesis time on the ODS performance of HPW(3.5)@MIL-101(Cr)-x-220-zh

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图 8 合成温度对HPW(3.5)@MIL-101(Cr)-12-y-zh催化剂BT催化氧化脱硫性能的影响

Figure 8 Effect of synthesis temperature on the ODS performance of HPW(3.5)@MIL-101(Cr)-12-y-zh

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图 9 HPW负载量对HPW(a)@MIL-101 (Cr)-12-220-zh催化剂BT催化氧化脱硫性能的影响

Figure 9 Effect of the HPW loading on the ODS performance of the HPW(a)@MIL-101(Cr)-12-220-zh catalyst

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图 10 HPW(3.5)@MIL-101(Cr)-12- 220-zh与HPW脱硫性能比较

Figure 10 A comparison of HPW(3.5)@MIL-101(Cr)-12-220-zh and HPW in their catalytic performance in ODS

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表 1 催化剂的N₂吸附数据

Table 1 N₂ adsorption data of various catalysts

Sample	A_BET /(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore size d/nm
HPW	13	10.46	17.9
MIL-101(Cr)	2465	0.93	3.1
HPW(3.5)@MIL-101(Cr)-2-220-zh	798	0.49	5.3
HPW(3.5)@MIL-101(Cr)-4-220-zh	871	0.43	4.7
HPW(3.5)@MIL-101(Cr)-8-220-zh	984	0.32	2.9
HPW(3.5)@MIL-101(Cr)-12-220-zh	1054	0.31	2.7
HPW(3.5)@MIL-101(Cr)-12-100-zh	156	7.48	9.1
HPW(3.5)@MIL-101(Cr)-12-140-zh	214	7.56	8.6
HPW(3.5)@MIL-101(Cr)-12-180-zh	899	0.39	3.5
HPW(3.5)@MIL-101(Cr)-12-220-s	813	0.37	3.3
HPW(3.5)@MIL-101(Cr)-12-220-j	1182	0.31	2.8
HPW(0.5)@MIL-101(Cr)-12-220-zh	1475	0.51	3.0
HPW(2.0)@MIL-101(Cr)-12-220-zh	1213	0.39	2.8
HPW(5.0)@MIL-101(Cr)-12-220-zh	916	0.29	2.6

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表 2 HPW(3.5)@MIL-101(Cr)-12-220-z催化剂BT催化氧化脱硫性能的影响

Table 2 Effect of synthesis environment on the ODS performance of HPW(3.5)@MIL-101(Cr)-12-220-z catalysts

Catalyst	HPW(3.5)@MIL-101 (Cr)-12-220-s (acidic)	HPW(3.5)@MIL-101 (Cr)-12-220-zh (neutral)	HPW(3.5)@MIL-101 (Cr)-12-220-j (alkalic)
BT removal η/%	68	99	85

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表 3 其他油品的氧化脱硫性能

Table 3 Oxidative desulfurization results

Sulfur removal η/%	TP	BT	DBT	4, 6-DMDBT
Sulfur removal η/%	58	99	100	99

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