C9H10O2-0.5ZnCl2/Al2O3的制备及其氧化脱硫性能

李秀萍; 赵荣祥; 宫晓杰; 李萍

C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃的制备及其氧化脱硫性能

辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001

基金项目:

辽宁省教育厅服务地方项目 L2017LFW004

详细信息

通讯作者:
ZHAO Rong-xiang, E-mail: zylhzrx@126.com

中图分类号: TE624
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- 文章访问数: 122
- HTML全文浏览量: 38
- PDF下载量: 17
- 被引次数: 0
出版历程
- 收稿日期: 2019-05-23
- 修回日期: 2019-08-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-10-10

Preparation of C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ and its oxidative desulfurization performance

College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China

Funds:

the Local Service Projects from Liaoning Education Department L2017LFW004

摘要

摘要: 通过将C₉H₁₀O₂-0.5ZnCl₂双酸型低共熔溶剂固载到Al₂O₃上制备了C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃催化剂。该催化剂采用XRD、FT-IR、SEM、EDS、N₂吸附-脱附技术进行了分析。以C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃为催化剂，过氧化氢为氧化剂研究模拟油中芳香族硫化物的脱除性能。考察反应参数如温度、催化剂加入量、O/S物质的量比、硫化物类型等对催化剂脱硫活性的影响。实验结果表明，在模拟油为5 mL、催化剂量为0.2 g、O/S比为8、反应温度为60 ℃、反应时间为180 min的条件下，模拟油中二苯并噻吩（DBT）脱硫率为99.2%。此外，在模拟油氧化脱硫中催化剂循环使用六次，其氧化脱硫活性略有降低。研究了C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃催化氧化脱硫的反应机理。
- 氯化锌 /
- 氧化铝 /
- 氧化脱硫 /
- 低共熔溶剂
Abstract: A C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ catalyst was successfully prepared by immobilizing phenylpropionic acid-zinc chloride(C₉H₁₀O₂-0.5ZnCl₂) double acid deep eutectic solvent on Al₂O₃, and analyzed by XRD, FT-IR, SEM, EDS and N₂ adsorption-desorption. The removal activity for aromatic sulfides in model oil using C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ as catalysis and H₂O₂ as oxidant and the effect of some reaction parameters such as temperature, catalyst dosage, O/S molar ratio and different sulfide types on the desulfurization activity of catalyst were investigated. The experimental results show that with the model oil of 5 mL, the catalyst dosage of 0.2 g and the O/S molar ratio of 8, at temperature of 60℃and reaction time of 180 min, the removal rate of DBT can reach to 99.2%. In addition, the catalyst can be recycled up to 6 times with a little decrease in catalytic activity for the ODS process. The catalysis-oxidation desulfurization mechanism of C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ was also explored.
- zinc chloride /
- alumina /
- oxidation desulfurization /
- deep eutectic solvents

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图 1 Al₂O₃和C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃的XRD谱图

Figure 1 XRD patterns of Al₂O₃ and C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃

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图 2 Al₂O₃, C₉H₁₀O₂-0.5ZnCl₂和C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃的FT-IR谱图

Figure 2 FT-IR spectra of Al₂O₃, C₉H₁₀O₂-0.5 ZnCl₂ and C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃

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图 3 氧化铝和催化剂的形貌

Figure 3 Morphology of Al₂O₃ and C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ catalyst

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图 4 氧化铝和催化剂的EDS谱图

Figure 4 EDS of Al₂O₃ and C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ catalyst

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图 5 氧化铝和催化剂N₂吸附-脱附曲线和孔径分布

Figure 5 N₂-adsorptive desorption curves and pore size distribution of Al₂O₃ and C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃ catalyst

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图 6 反应温度对脱硫率的影响

Figure 6 Effect of reaction temperature on desulfurization rate (5 mL model oil, O/S= 8, 0.2 g C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃, t=180 min)

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图 7 反应时间对脱硫率的影响

Figure 7 Effect of reaction time on desulfurization rate 5 mL model oil, 60 ℃, O/S= 8, 0.2 g C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃

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图 8 O/S物质的量比对脱硫率的影响

Figure 8 Effect of O/S mol ratio on desulfurization rate

5 mL model oil, 60 ℃, 0.2 g C₉H₁₀O₂- 0.5ZnCl₂/Al₂O₃, t=180 min

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图 9 催化剂加入量对脱硫率的影响

5 mL model oil, 60 ℃, O/S=8, t=180 min

Figure 9 Effect of catalyst dosage on desulfurization rate

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图 10 不同硫化物对脱硫率的影响

5 mL model oil, 60 ℃, O/S=8, 0.2 g C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃, t=180 min

Figure 10 Effect of sulfide types on desulfurization rate

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图 11 回收催化剂与新鲜催化剂的XRD谱图

Figure 11 XRD patterns of recyced catalyst and fresh catalyst

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图 12 DBT和氧化产物的红外光谱谱图

Figure 12 Infrared spectra of DBT and oxidation products

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图 13 C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃催化氧化脱硫反应机理

Figure 13 Catalysis-oxidation desulfurization mechanism of C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃

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表 1 样品的表面结构表征

Table 1 Surface structural characteristics of samples

Sample	Surface A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore size d/nm
Al₂O₃	346.5	1.164	0.5086
C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃	171.4	0.5684	0.9976

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表 2 不同脱硫体系脱硫活性对比

Table 2 Comparison of desulfurization performance of different desulfurization systems

Desulfurization systems	Removal rate of DBT η/%
H₂O₂/Al₂O₃^[a]	20
H₂O₂/C₉H₁₀O₂-0.5ZnCl₂^[b]	38
H₂O₂/C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃^[c]	99.2
reaction condition: ^a: 5 mL model oil, 60 ℃, O/S= 8, 0.133 g Al₂O₃, t=180 min; ^b: 5 mL model oil, 60 ℃, O/S= 8, 0.067 g C₉H₁₀O₂-0.5ZnCl₂, t=180 min; ^c: 5 mL model oil, 60 ℃, O/S= 8, 0.2 g C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃, t=180 min

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表 3 C₉H₁₀O₂-0.5ZnCl₂/Al₂O₃的重复使用性能

Table 3 Recycling performance of C₉H₁₀O₂-0.5ZnCl₂ /Al₂O₃

Recycle times	1	2	3	4	5	6
Sulfur removal η/%	99.2	96.2	95.4	92.3	88.3	85.1

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