Preparation and desulfurization performance of molecularly imprinted composite with dibenzothiophene as template
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摘要: 聚丙烯中空纤维膜经多巴胺氧化、硅烷化两步表面改性处理后，以甲基丙烯酸为功能单体进行表面分子印迹聚合，制备了中空纤维膜支撑-二苯并噻吩分子印迹复合膜（MIP-PP膜）。利用红外光谱、扫描电镜对印迹复合膜形态结构进行表征，测定了MIP-PP膜的脱硫性能。结果表明，在298 K时，MIP-PP膜对DBT的吸附在180 min达到平衡，最大吸附容量为133.32 mg/g；MIP-PP膜对DBT的吸附符合Lagergren准一级动力学模型及Langmuir吸附等温线，是可自发进行的放热过程。Abstract: The polypropylene hollow fiber membrane was subjected to dopamine oxidation and silanization two-step surface modification treatment, and then the surface molecular molecularly imprinted polymerization was carried out using methacrylic acid as a functional monomer to prepare a hollow fiber membrane supported-dibenzothiophene molecularly imprinted composite membrane (MIP-PP membrane).The morphology of the imprinted composite membrane was characterized by infrared spectroscopy and scanning electron microscopy, and the desulfurization performance of MIP-PP membrane was measured. The results show that at 298 K, the adsorption of DBT by MIP-PP membrane reaches equilibrium at 180 min, and the maximum adsorption capacity is 133.32 mg/g. The adsorption of DBT by MIP-PP membrane conforms to the Lagergren quasi-first-order kinetic model and the Langmuir adsorption isotherm, which is a spontaneous exothermic process.
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图 2 PP中空纤维膜(a), PDA-PP膜(b), PDA-KH570-PP膜(c), MIP-PP膜(d)的红外光谱谱图
Figure 2 FT-IR spectra of PP hollow fiber membrane (a), PDA-PP membrane(b), PDA-KH570-PP membrane (c), and MIP-PP membrane (d)
图 3 膜的表面及断面扫描电镜照片
Figure 3 SEM photographs of cross section and external surface of membrane
(a: PP hollow fiber membrane; b: MIP-PP membrane)
图 4 不同聚合条件下制备的MIP-PP膜对DBT的吸附性能
Figure 4 Adsorption of DBT by MIP-PP membranes prepared under different polymerization conditions
(a): polymerization conditions is DBT:EGDMA=1:10, polymerization pemperature at 65 ℃ (b): polymerization conditions is DBT:MAA=1:4, polymerization pemperature at 65 ℃ (c): polymerization conditions is DBT:MAA:EGDMA=1:4:10 (d): polymerization conditions is DBT:functional monomer:EGDMA=1:4:10 and polymerization pemperature at 65 ℃
图 6 ln(qe-qt)与t及t/qt与t的线性图
Figure 6 Linear plot of ln(qe-qt) versus t(a) and t/qt versus t(b)
图 7 不同温度下MIP-PP膜(a)和NIP-PP膜(b)对DBT的吸附等温线
Figure 7 Adsorption isotherms of MIP-PP membrane and NIP-PP membrane to DBT at different temperatures
图 8 MIP-PP膜及NIP-PP膜的选择性吸附性能
Figure 8 Selective adsorption property of MIP-PP membrane and NIP-PP membrane
表 1 MIP-PP膜和NIP-PP膜对DBT吸附等温线参数
Table 1 Adsorption isotherm parameters of MIP-PP membrane and NIP-PP membrane to DBT
Isotherm model Parameter MIP-PP membrane NIP-PP membrane 298 K 308 K 318 K 298 K 308 K 318 K Langmuir model kL 0.68 0.73 0.57 0.86 0.77 0.65 qm 133.32 114.74 116.86 62.89 60.24 57.81 R2 0.991 0.999 0.993 0.996 0.999 0.997 Freundlich model kF 1.48 1.49 1.41 1.46 1.45 1.37 n 48.87 44.06 38.85 24.82 24.27 21.57 R2 0.973 0.961 0.966 0.989 0.986 0.986 
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表 2 MIP-PP膜对DBT的吸附热力学参数
Table 2 Thermodynamic parameters for the adsorption of MIP-PP membrane to DBT
T/K kc ΔG0 ΔH0 ΔS0 298 56.09 -9.97 -11.96 -6.75 308 47.76 -9.90 318 41.38 -9.84
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表 3 MIP-PP膜及NIP-PP膜选择性吸附参数
Table 3 Selective recognition parameters of MIP-PP membrane and NIP-PP membrane
Compounds MIP-PP membrane NIP-PP membrane k' kd k kd k DBT 0.0553 - 0.0293 - - BT 0.0384 1.44 0.0282 1.03 1.39 T 0.0327 1.69 0.0273 1.07 1.57
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