Preparation of ionic liquid supported metal-organic framework Py/MOF-199 and its adsorption desulfurization performance
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摘要: 制备了金属框架MOF-199(Cu-BTC),并将[Hnmp][H2PO4]离子液体负载到MOF-199上合成了离子液体负载的金属框架Py/MOF-199。对吸附剂进行了X射线衍射、红外光谱、扫描电镜、比表面积表征。考察了MOF-199预处理条件、离子液体负载方式、负载量、负载温度、负载时间对噻吩吸附脱除性能的影响,通过正交实验优化了吸附剂的制备条件和吸附脱硫条件。结果表明,离子液体改性得到的Py/MOF-199保持了MOF-199的规则的八面体结构。Py/MOF-199的适宜制备条件为:采用二氯甲烷索氏提取并真空干燥法进行预处理MOF-199后,再用溶剂热法负载[Hnmp][H2PO4],负载温度为50 ℃,负载时间为8 h,负载量为7%。各因素对吸附剂脱硫性能影响大小顺序为:负载温度>负载时间>离子液体负载量。适宜Py/MOF-199吸附脱硫条件为:模拟油为10 mL,吸附剂用量0.2 g,吸附温度70 ℃,吸附时间1 h。在此条件下,噻吩脱除率可达到96.7%。
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关键词:
- 吸附脱硫 /
- 离子液体 /
- Py/MOF-199 /
- 噻吩(TP)
Abstract: MOF-199(Cu-BTC) was prepared and the ionic liquid supported MOF-199 adsorbents (Py/MOF-199) were successfully obtained via fixing ionic liquid[Hnmp] [H2PO4] onto the MOF-199. Adsorbents were characterized via XRD, FT-IR, SEM, and BET methods. The effects of pretreatment conditions of MOF-199, ionic liquid loading method, ionic liquid content, loading temperature and time on adsorptive removal performance of thiophene were studied. The preparation conditions of Py/MOF-199 adsorbent were optimized via orthogonal experiment, and the desulfurization conditions were also optimized. The results show that after the introduction of[Hnmp] [H2PO4] the regular octahedron structure of MOF-199 of Py/MOF-199 was maintained unchanged and the average pore diameter was increased. The optimal preparation conditions of Py/MOF-199 adsorbent are pretreating MOF-199 with Soxhlet extraction and drying in vacuum, then loading[Hnmp] [H2PO4] using solvothermal method, loading temperature of 50 ℃, loading time of 8 h, ionic liquid content of 7%. The influence of preparation factors on the desulfurization performance of adsorbent is in order:loading temperature > loading time > ionic liquid content. The optimal desulfurization conditions are model oil of 10 mL, Py/MOF-199 dosage of 0.2 g, adsorption under 70 ℃ for 1 h. Under these conditions, the thiophene desulfurization rate over Py/MOF-199 reached 96.7%.-
Key words:
- adsorptive desulfurization /
- ionic liquids /
- Py/MOF-199 /
- thiophene (TP)
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表 1 MOF-199和Py/MOF-199吸附剂的BET比表面积、孔隙体积和孔径
Table 1 BET surface area pore volume and pore size of the adsorbents
Adsorbent BET area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore size d/nm MOF-199 1362 0.71 2.13 7%Py/MOF-199 1074 0.62 2.35 表 2 正交试验因素水平
Table 2 Level of the factors of orthogonal test
Level Factor temperature t/℃ time t/h ionic liquid content w/% A B C 1 40 6 6 2 50 8 7 3 60 10 8 表 3 离子液体负载条件影响因素正交试验直观分析表
Table 3 Visual analysis table of orthogonal test for influencing factors of ionic liquid loading condition
Test Temperature t/℃ Time t/h Ionic liquid content Rate of thiophene removal A B C 1 40 6 6% 64.6% 2 40 8 7% 67.7% 3 40 10 8% 73.5% 4 50 6 7% 73.8% 5 50 8 8% 69.7% 6 50 10 6% 66.2% 7 60 6 8% 58.7% 8 60 8 6% 69.0% 9 60 10 7% 61.1% K1 205.9% 197.2% 199.8% K2 209.8% 206.5% 202.7% K3 188.8% 200.8% 202.0% Average k1 68.6% 65.7% 66.6% Average k2 69.9% 68.8% 67.6% Average k3 62.9% 66.9% 67.3% Range R 5.7% 3.1% 0.9% Primary order A>B>C Superior level A2 B2 C2 Superior combination A2B2C2 Kn is the comprehensive removal rate of thiophene at different levels of the same influence factor; kn is the average removal rate of thiophene at different levels of the same influence factor; R=kmax-kmin is the difference between the maximum removal rate and the minimum removal rate of thiophene for the same influence factor -
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