Preparation of Ag and Y loaded metal-organic framework Ag-Y/MIL-101 and its adsorption desulfurization performance
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摘要: 通过银、钇双金属改性制备了Ag-Y/MIL-101吸附剂，并对Ag-Y/MIL-101进行了X射线衍射（XRD）、电镜（SEM-EDS）、比表面积（BET）和热重（TG-DTG）表征。考察了Ag-Y/MIL-101金属负载顺序、金属负载浓度、金属溶液用量、负载时间对脱硫性能的影响，优化了吸附脱硫条件。结果表明，金属改性得到的Ag-Y/MIL-101保持了MIL-101的晶格结构。与MIL-101相比，Ag-Y/MIL-101的比表面积和孔容均有所下降。适宜Ag-Y/MIL-101的制备条件为：先负载银后负载钇，银离子和钇离子的负载浓度均为30 mmol/L，金属溶液用量均为1 mL，负载时间为8 h。适宜Ag-Y/MIL-101的吸附脱硫条件为：吸附剂用量0.05 g，模拟油为10 mL，吸附温度为60℃，吸附时间为8 h。在此条件下，Ag-Y/MIL-101对噻吩的吸附量达到21.7 mg/g。Ag能显著提高MIL-101的吸附硫容，Y能显著提高MIL-101的吸附选择性，因此，Ag-Y/MIL-101吸附剂中Ag和Y的协同作用使其拥有比MIL-101更高的硫容和噻吩脱硫选择性。
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关键词:
- 吸附脱硫 /
- 金属改性 /
- Ag-Y/MIL-101 /
- 噻吩
Abstract: The Ag-Y/MIL-101 adsorbents were successfully prepared via loading Ag and Y onto MIL-101. The adsorbents were characterized by XRD, SEM-EDS, BET and TG-DTG methods. The effects of the loading order and concentrations of metals, the amount of AgNO3 solution and Y(NO3)3 solution, and the loading residence time on adsorptive removal performance of thiophene were studied. The conditions of adsorptive desufurization were also optimized. The results show that the lattice structure of MIL-101 remains after the introduction of metals. Compared with MIL-101, the specific surface area and pore volume of Ag-Y/MIL-101 decrease. The optimal preparation conditions of Ag-Y/MIL-101 adsorbent are to load Ag first and then Y with 30 mmol/L of both the loading concentrations of Ag and Y ion, 1 mL of both the dosages of AgNO3 solution and Y(NO3)3 solution, and 8 h of the loading residence time. The optimal desulfurization conditions are 10 mL of model oil, 0.05 g of Ag-Y/MIL-101 dosage, the adsorption temperature of 60℃, and the adsorption time of 8 h. At these conditions, the thiophene desulfurization capacity over Ag-Y/MIL-101 reaches 21.7 mg/g. The Ag can significantly improve the adsorption sulfur capacity of MIL-101, and Y can significantly improve the adsorption selectivity of MIL-101. Therefore, the synergistic effect of Ag and Y in Ag-Y/MIL-101 adsorbent makes it have higher sulfur capacity and thiophene desulfurization selectivity than MIL-101.-
Key words:
- adsorptive desulfurization /
- metals modification /
- Ag-Y/MIL-101 /
- thiophene (TP)
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图 1 MIL-101和Ag-Y/MIL-101的XRD谱图
Figure 1 XRD patterns of MIL-101 and Ag-Y/MIL-101
(a): 2°-10°; (b): 10°-80°
图 2 MIL-101和Ag-Y/MIL-101的SEM照片
Figure 2 SEM images of MIL-101 (a) and Ag-Y/MIL-101 (b)
图 3 MIL-101和Ag-Y/MIL-101的孔径分布图
Figure 3 Distribution of pore size of MIL-101 and Ag-Y/MIL-101
图 4 MIL-101和Ag-Y/MIL-101的EDS谱图
Figure 4 EDS patterns of MIL-101 (a) and Ag-Y/MIL-101 (b)
图 6 金属负载顺序对Ag-Y/MIL-101吸附脱硫活性的影响
Figure 6 Effect of the order of metal loading on the desulfurization performance of Ag-Y/MIL-101
图 7 Ag+负载浓度对Ag-Y/MIL-101吸附脱硫活性的影响
Figure 7 Effect of Ag+ loading concentration on adsorptive desulfurization activity of Ag-Y/MIL-101
图 8 Y3+负载浓度对Ag-Y/MIL-101吸附脱硫活性的影响
Figure 8 Effect of Y3+ loading concentration on adsorptive desulfurization activity of Ag-Y/MIL-101
图 9 金属用量对Ag-Y/MIL-101吸附脱硫活性的影响
Figure 9 Effect of the content of metal on adsorptive desulfurization of Ag-Y/MIL-101
图 10 金属负载时间对Ag-Y/MIL-101吸附脱硫活性的影响
Figure 10 Effect of the residence time of metals loading on adsorptive desulfurization of Ag-Y/MIL-101
图 11 吸附温度对吸附脱硫性能的影响
Figure 11 Effect of adsorption temperature on adsorptive desulfurization performance
图 12 吸附时间对吸附脱硫性能的影响
Figure 12 Effect of adsorption time on adsorptive desulfurization performance
表 1 吸附剂的BET比表面积、孔隙体积和孔径
Table 1 BET area, pore volume and average pore size of the adsorbents
Adsorbent BET area A/(m2·g-1) Pore volume v/(cm3·g-1) Average pore size d/nm MIL-101 2238 1.43 2.55 Ag-Y/MIL-101 1759 1.14 2.58 
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表 2 金属溶液用量对Ag-Y/MIL-101吸附脱硫性能的影响
Table 2 Effect of the amount of AgNO3 solution and Y(NO3)3 solution on adsorptive desulfurization activity of Ag-Y/MIL-101
30 mmol/L AgNO3 solution/mL 30 mmol/L Y(NO3)3 solution/mL Case1 0.5 0.5 Case2 1 1 Case3 2 2 Case4 3 3
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