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摘要: 以钨酸和氧化石墨烯为原料，利用浸渍法将钨酸负载到氧化石墨烯上制得H2WO4/GO。采用XRD、FT-IR、SEM、BET表征确定H2WO4/GO的形态及其结构。以H2WO4/GO作为催化剂，H2O2作为氧化剂，乙腈作为萃取剂超声氧化脱除模拟油中的二苯并噻吩（DBT）。实验表明，在模拟油为5 mL，钨酸的负载量为30%（质量分数），催化剂为0.02 g，乙腈为1 mL，H2O2/S（mol ratio）为8，反应温度为50℃，超声功率为150 W的最佳反应条件下，二苯并噻吩（DBT）、4，6-二甲基二苯并噻吩（4，6-DMDBT）、苯并噻吩（BT）的脱除率分别达到96.6%、81.2%、72.8%。同时，考察了催化剂的循环使用性能，并对超声氧化脱硫机理进行了研究。Abstract: H2WO4/GO was prepared by dipping method using tungstic acid and graphene oxide as raw materials. The morphology and structure of H2WO4/GO were characterized by XRD, FT-IR, SEM and BET. The ultrasonic-oxidation desulfurization of model oil containing DBT was carried out with H2WO4/GO as catalyst, H2O2 as oxidant agent and acetonitrile as extractant. Under the optimum conditions with 5 mL of model oil, 30% of tungstic acid loading(mass ratio), 0.02 g of catalyst, 1 mL of acetonitrile, H2O2/S mol ratio of 8, ultrasonic power of 150 W and at 50℃, the removal rate of DBT, 4, 6-DMDBT and BT can reach 96.6%, 81.2%, 72.8%, respectively. Besides, the recycling use of catalyst and the mechanism of ultrasonic-oxidation desulfurization were investigated.
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Key words:
- tungstic acid /
- graphene oxide /
- ultrasound /
- oxidative desulfurization /
- dibenzothiophene
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图 1 H2WO4、GO和30%-H2WO4/GO的XRD谱图
a: H2WO4; b: 30%-H2WO4/GO; c: GO
Figure 1 XRD patterns of H2WO4, GO and 30%-H2WO4/GO
图 3 H2WO4、GO和30%-H2WO4/GO的SEM照片
Figure 3 SEM images of H2WO4(a), GO(b) and 30%-H2WO4/GO(c)
图 4 GO和30%-H2WO4/GO的吸附-脱附等温线
Figure 4 N2 adsorption and desorption isotherms of GO and 30%-H2WO4/GO
图 5 钨酸负载量对脱硫率的影响
reaction conditions: V(model oil)=5 mL; m(catalyst)=0.02 g; 50 ℃; H2O2/S(mol ratio)=8; V(acetonitrile)=2.0 mL; P=150 W
Figure 5 Effect of loading of H2WO4 on the desulfurization rate
图 6 反应温度对脱硫率的影响
reaction conditions: V(model oil)=5 mL; m(catalyst)=0.02 g; loading(H2WO4)=30%; H2O2/S(mol ratio)=8; V(acetonitrile)=2.0 mL; P=150 W
Figure 6 Effect of reaction temperature on the desulfurization rate
图 7 H2O2/S物质的量比对脱硫率的影响
reaction conditions: V(model oil)=5 mL；m(catalyst)=0.02 g；loading(H2WO4)=30%；50 ℃; V(acetonitrile)=2.0 mL; P=150 W
Figure 7 Effect of H2O2/S (mol ratio) on the desulfurization rate
图 8 催化剂用量对脱硫率的影响
reaction conditions: V(model oil)=5 mL; H2O2/S (mol ratio)=8; loading(H2WO4)=30%；50 ℃; V(acetonitrile)=2.0 mL; P=150 W
Figure 8 Effect of catalyst dosage on the desulfurization rate
图 9 萃取剂加入量对脱硫率的影响
reaction conditions: V(model oil)=5 mL；m(catalyst)=0.02 g; loading(H2WO4)=30%；50 ℃; H2O2/S (mol ratio)=8; P=150 W
Figure 9 Effect of amount of extraction agent on the desulfurization rate
图 10 超声功率对脱硫率的影响
reaction conditions: V(model oil)=5 mL；m(catalyst)=0.02 g；loading(H2WO4)=30%；50 ℃；H2O2/S (mol ratio)=8; V(acetonitrile)=1.0 mL
Figure 10 Effect of ultrasonic power on the desulfurization rate
图 11 不同硫化物对脱硫率的影响
reaction conditions: V(model oil)=5 mL；m(catalyst)=0.02 g；loading(H2WO4)=30%；50 ℃；H2O2/S (mol ratio)=8；V(acetonitrile)=1.0 mL; P=150 W
Figure 11 Effect of different sulfur compounds on the desulfurization rate
图 12 氧化脱硫反应中不同硫化物脱除的动力学分析
reaction conditions: V(model oil)=5 mL；m(catalyst)=0.02 g; loading(H2WO4)=30%；50 ℃；H2O2/S (mol ratio)=8；V(acetonitrile)=1.0 mL; P=150 W
Figure 12 Kinetic analysis of the sulfur removal for different sulfur compounds in oxidative desulfurization reaction
图 14 H2WO4/GO氧化脱硫机理示意图
Figure 14 Oxidative desulfurization mechanism of DBT by H2WO4/GO
表 1 GO和30%-H2WO4/GO的孔结构参数
Table 1 Pore structure parameters of GO and 30%-H2WO4/GO
Sample Specific surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pole diameter d/nm GO 24.70 0.03747 6.069 30%-H2WO4 /GO 22.13 0.07442 13.450 
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表 2 30%-H2WO4/ GO的循环使用性能
Table 2 Recycling performance of 30%-H2WO4/ GO
Cycle 1 2 3 4 5 Desulfurization rate 96.6 95.8 93.2 92.7 90.4 reaction conditions: V(model oil)=5 mL; m(catalyst)=0.02 g; loading(H2WO4)=30%; 50 ℃; H2O2/S (mol ratio)=8; V(acetonitrile)=1.0 mL; P=150 W
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