磷钨酸负载锆基金属有机骨架PTA@MOF-808的制备及其吸附脱硫性能

doi:10.11949/0438-1157.20200692

摘要/Abstract

摘要：

利用原位合成法将磷钨酸（PTA）负载于锆基金属有机骨架材料（MOFs）上，通过X射线衍射（XRD）、红外（FT-IR）、氮气吸附-脱附、扫描电镜（SEM）以及热重（TG）等表征证实了PTA@MOF-808复合材料的成功制备。通过制备的PTA@MOF-808吸附剂在模型油中对苯并噻吩（BT）的静态吸附脱硫实验，考察了PTA负载量、温度、油剂比、模型油硫含量以及不同有机硫对复合材料吸附脱硫性能的影响。实验结果表明：PTA的引入致使MOF-808对正辛烷中BT的吸附量提高了约2倍。PTA@MOF-808吸附速率快、在300 s时基本吸附完全，并且其第6次循环使用吸附BT的吸附量为首次吸附量的86%。最后，通过PTA@MOF-808对BT吸附的动力学和热力学研究表明该吸附过程符合准二级动力学模型，吸附过程包含物理吸附与化学吸附。

关键词: 吸附, 脱硫, 磷钨酸, MOF-808, 复合材料, 动力学模型

Abstract:

The phosphotungstic acid (PTA) was loaded on the zirconium-based metal organic framework materials (MOFs) by in-situ synthesis, and X-ray diffraction (XRD), infrared (FT-IR), nitrogen adsorption-desorption, scanning electron microscope (SEM) and thermogravimetric (TG) confirmed the successful preparation of PTA@MOF-808 composite material. The effects of PTA amounts, temperature, oil-adsorbent ratio, model oil sulfur content and type of sulfide on the adsorption desulfurization performance of PTA@MOF-808 adsorbents were investigated by the static adsorption desulfurization experiments. The results showed that the introduction of PTA increased the adsorption capacity of MOF-808 for benzothiophene (BT) by 2 times. PTA@MOF-808 has a fast adsorption rate and basically reaches adsorption equilibrium at 300 s. After 6 cycles of removal of BT, the adsorption capacity was still 86% of the first adsorption capacity. Finally, the kinetic and thermodynamic of BT adsorption onto PTA@MOF-808 were studied. The results showed that the adsorption process followed a quasi-second-order kinetics model and included physical adsorption and chemical adsorption.

Key words: adsorption, desulfurization, phosphotungstic acid, MOF-808, composites, kinetic modeling

中图分类号:

杨诗, 蔡阳, 李长平, 李雪辉. 磷钨酸负载锆基金属有机骨架PTA@MOF-808的制备及其吸附脱硫性能[J]. 化工学报, 2021, 72(3): 1722-1731.

YANG Shi, CAI Yang, LI Changping, LI Xuehui. Preparation of phosphotungstic acid loaded Zr-based metal-organic framework PTA@MOF-808 and its adsorption desulfurization performance[J]. CIESC Journal, 2021, 72(3): 1722-1731.

图/表 17

图1 PTA@MOF-808的氮气吸附-脱附等温线（a）及相应的NL-DFT孔径分布图（b）

Fig.1 N2 adsorption/desorption isotherms (a) and NL-DFT pore size distributions (b) for PTA@MOF-808

表1 复合材料PTA@MOF-808的BET比表面积和孔体积

Table 1 BET surface areas and pore volumes of PTA@MOF-808 samples

样品	BET比表面积/ (m²·g^-1)	孔体积/ (cm³·g^-1)
MOF-808	1186.6	0.52
10%(质量) PTA@MOF-808	653.4	0.39
20%(质量) PTA@MOF-808	563.4	0.36
30%(质量) PTA@MOF-808	388.3	0.28
40%(质量) PTA@MOF-808	369.1	0.21
50%(质量) PTA@MOF-808	166.7	0.15

图2 PTA@MOF-808的红外光谱图

Fig.2 IR spectra of PTA@MOF-808 samples

图3 PTA@MOF-808的XRD谱图

Fig.3 XRD patterns for PTA@MOF-808 samples

图4 PTA@MOF-808的TG曲线

Fig.4 TG curves of PTA@MOF-808

图5 MOF-808(a)和20%（质量）PTA@MOF-808(b)的SEM图

Fig.5 SEM images of MOF-808 (a) and 20%(mass) PTA@MOF-808 (b)

图6 PTA负载量对PTA@MOF-808吸附量的影响

Fig.6 Influence of loaded amounts of PTA on desulfurization capacity of PTA@MOF-808

图7 温度对PTA@MOF-808吸附量的影响

Fig.7 Influence of temperature on desulfurization capacity of PTA@MOF-808

图8 油剂比对PTA@MOF-808吸附量的影响

Fig.8 Influence of ratio of oil to adsorbent on desulfurization capacity of PTA@MOF-808

图9 硫含量对PTA@MOF-808吸附量的影响

Fig.9 Influence of sulfur concentration on desulfurization capacity of PTA@MOF-808

表2 20%(质量) PTA@MOF-808对不同模型油的吸附量

Table 2 The adsorption capacity of 20%(mass) PTA@MOF-808 for different sulfur compound

Sulfur compound	Q₀/(mg·g^-1)	Sulfur removal/%
TP	18.5	46.7
BT	25.4	63.4
DBT	34.9	87.2

图10 PTA@MOF-808吸附脱硫循环性能

Fig.10 The recycling performance of PTA@MOF-808 for the adsorption desulfurization

图11 PTA@MOF-808六次循环后的红外光谱图

Fig.11 IR spectra of PTA@MOF-808 sample after six cycles

图12 吸附动力学：(a) 准一级动力学模型拟合和(b) 准二级动力学模型拟合

Fig.12 Adsorption kinetics of the pseudo-first-order plots (a) and the pseudo-second-order plots (b)

表3 吸附动力学拟合参数R2值

Table 3 The fitting parameters R2 of adsorption kinetics

浓度/(μg·g^-1)	R²
浓度/(μg·g^-1)	准一级	准二级
100	0.98796	0.99909
200	0.90400	0.99978
300	0.92852	0.99959
400	0.83953	0.99985
500	0.93483	0.99987

图13 Langmuir 吸附等温线(a)和Freundlich吸附等温线(b)

Fig.13 Adsorption isotherms of the linear fitted curve of Langmuir model (a) and the linear fitted curve of Freundlich model (b)

表4 吸附等温线拟合参数

Table 4 The fitting parameters of adsorption isotherms

等温吸附线模型	等温吸附方程	Q_m/(mg·g^-1)	b/(g·μg^-1)	R²
Langmuir	y=0.74812x+0.02832	35.3107	47.1993	0.98225
等温吸附线模型	等温吸附方程	k_F/((mg·g^-1)(g·μg^-1)^1/^a)	a	R²
Freundlich	y=0.28376x+0.83893	6.9013	3.5241	0.96744

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