Adsorption and removal of organochloride from plastic oil by MOF⁃808⁃modified material

doi:10.19491/j.issn.1001-9278.2024.06.013

Abstract

Abstract:

The removal effectiveness of the MOF⁃808 material for organic chloride in a plastic cracking oil was studied in light of its excellent adsorption properties. The MOF⁃808 materials was prepared， and then the Zr_x∶Fe_y@MOF⁃808 materials with different doping ratios were prepared by using a hydrothermal synthesis method. Four typical organic chlorides in the plastic cracking oil were selected to prepare a model oil， and the optimal x/y ratio was determined to be 1∶0.67 according to the removal rate of organic chlorides in the model oil. The optimal reaction conditions and reuse performance of adsorption dechlorination experiments were determined， and the corresponding adsorption mechanism was investigated. The results indicated that the as⁃prepared Zr₁∶Fe_0.67@MOF⁃08 adsorption material exhibited has good structure and stability. The removal rate of chloride in the model oil was as high as 97.66 % at an adsorption temperature of 50 ℃， an adsorption time of 2 h， and an agent/oil mass ratio of 1/40. The dechlorination rate remained to be above 85 % after repeatedly using the adsorbent for 6 times. The adsorption process conformed to a pseudo⁃second⁃order kinetic model， belonging to a spontaneous chemisorption process.

Key words: plastic cracking oil, chloride, adsorption dechlorination, MOF?808, adsorption kinetics

CLC Number:

TQ320.9

JI Yaru, LI Ruili, ZHAI Yongyi, ZHANG Shibo. Adsorption and removal of organochloride from plastic oil by MOF⁃808⁃modified material[J]. China Plastics, 2024, 38(6): 82-89.

Figures/Tables 20

Fig.1. Comparison of adsorption effect of Zr∶Fe（x∶y）@MOF⁃808

Fig.2. XRD patterns of different adsorbents

Fig.3. FTIR spectrum of different adsorbents

Fig.4. N2 adsorption⁃desorption curve of different adsorbents

Fig.5. Pore size distribution curves of different adsorbents

吸附剂	比表面积/ $m 2 · g - 1$	总孔体积/ $c m 3 · g - 1$	孔径/ $n m$
MOF⁃808	1 124.52	0.59	2.19
Zr∶Fe（1∶0.67）@MOF⁃808	866.38	0.75	3.39

吸附剂	比表面积/ $m 2 · g - 1$	总孔体积/ $c m 3 · g - 1$	孔径/ $n m$
MOF⁃808	1 124.52	0.59	2.19
Zr∶Fe（1∶0.67）@MOF⁃808	866.38	0.75	3.39

Tab.1. Specific surface area， total pore volume and pore diameter of different adsorbents

Fig.6. SEM and TEM of different adsorbents

Fig.7. TG curves of different adsorbents

Fig.8. Effect of adsorption temperature on the dechlorination effect

Fig.9. Effect of adsorption time on the dechlorination effect

Fig.10. Effect of ratio of adsorbent to oil on the dechlorination effect

Fig.11. Reuse performance of Zr∶Fe（1∶0.67）@MOF⁃808

Fig.12. Pseudo⁃first⁃order kinetic equation fitting curve

Fig.13. Pseudo⁃second⁃order kinetic equation fitting curve

Fig.14. The in⁃particle diffusion model fitting curve

样品	拟一级动力学方程			拟二级动力学方程
样品	$K 1 / m i n - 1$	$Q e, e x p$	$R 2$	$K 2 / g · (m g · m i n) - 1$	$Q e, e x p$	$R 2$
Zr∶Fe（1∶0.67）@MOF⁃808	0.025	5.76	0.843	0.008	11.36	0.998

样品	拟一级动力学方程			拟二级动力学方程
样品	$K 1 / m i n - 1$	$Q e, e x p$	$R 2$	$K 2 / g · (m g · m i n) - 1$	$Q e, e x p$	$R 2$
Zr∶Fe（1∶0.67）@MOF⁃808	0.025	5.76	0.843	0.008	11.36	0.998

Tab.2. Pseudo⁃kinetic parameters of removal of organic chlorides by Zr：Fe（1：0.67）@MOF⁃808 adsorption

样品	$K 1 d / m g · g · m i n 1 / 2$ ^-1	$R 12$	$K 2 d / m g · g · m i n 1 / 2$ ^-1	$R 22$	$K 3 d / m g · g · m i n 1 / 2$ ^-1	$R 32$
Zr：Fe（1：0.67）@MOF⁃808	0.949	0.946	0.070	0.987	0.002	0.992

样品	$K 1 d / m g · g · m i n 1 / 2$ ^-1	$R 12$	$K 2 d / m g · g · m i n 1 / 2$ ^-1	$R 22$	$K 3 d / m g · g · m i n 1 / 2$ ^-1	$R 32$
Zr：Fe（1：0.67）@MOF⁃808	0.949	0.946	0.070	0.987	0.002	0.992

Tab.3. Parameters of in⁃particle diffusion model for removal of organic chlorides by Zr：Fe（1：0.67）@MOF⁃808 adsorption

T/K	$∆ G$ / $k J · m o l - 1$	$∆ H$ / $k J · m o l - 1$	$∆ S$ / $k J · (m o l · K - 1) - 1$
293.15	-0.823	3.575	0.015
303.15	-0.973
313.15	-1.123
323.15	-1.273
333.15	-1.423
343.15	-1.573

T/K	$∆ G$ / $k J · m o l - 1$	$∆ H$ / $k J · m o l - 1$	$∆ S$ / $k J · (m o l · K - 1) - 1$
293.15	-0.823	3.575	0.015
303.15	-0.973
313.15	-1.123
323.15	-1.273
333.15	-1.423
343.15	-1.573

Tab.4. Fitting parameters of thermodynamic curves for removal of organic chlorides by Zr：Fe（1：0.67）@MOF⁃808 adsorption

Fig.15. Fitting curve of thermodynamic equation

Fig.16. Adsorption and dechlorination effect of Zr∶Fe（1∶0.67）@MOF⁃808 on actual oil

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