Preparation and dechlorination performance of Mg⁃doped UiO⁃66 for plastic oil

doi:10.19491/j.issn.1001-9278.2023.02.010

Abstract

Abstract:

The octahedral UiO⁃66 was prepared by means of a solvothermal method， followed by modification through doping an Mg metal. To explore the optimal doping concentration， the Mg⁃UiO⁃66⁃n （n is molar ratio of magnesium to zirconium） adsorbent was prepared， and their morphology and surface properties were characterized using X⁃ray diffractometer， infrared spectrometer， and scanning electron microscope. The adsorption and dechlorination properties and adsorption mechanism of Mg⁃UiO⁃66⁃0.07 were investigated. The results demonstrated the successful fabrication of the Mg⁃doped UiO⁃66 adsorbent. The Mg⁃UiO⁃66⁃0.07 achieved the best adsorption effect at an adsorption time of 4 h and an adsorption temperature of 40 ºC. The Mg⁃UiO⁃66⁃0.07 gained a removal rate of 95.03 % at a solvent⁃to⁃oil ratio of 1/40 and could be recycled for reutilization 5 times. This adsorption process is a spontaneous chemical adsorption process， which conforms to a pseudo second order kinetic model.

Key words: plastic cracking oil, UiO?66, adsorption, organic chloride, adsorption kinetics, adsorption thermodynamics

CLC Number:

TQ320.9

ZHAI Yongyi, LI Ruili, BU Yuhao, JI Yaru. Preparation and dechlorination performance of Mg⁃doped UiO⁃66 for plastic oil[J]. China Plastics, 2023, 37(2): 62-70.

Figures/Tables 19

Fig.1. Comparison of adsorption effects of adsorbents doped with different molar ratio of magnesium to zirconium

Fig.2. XRD patterns of different adsorbents

Fig.3. FTIR spectra of different adsorbents

Fig.4. SEM images of different adsorbents and EDS images of Mg⁃UiO⁃66⁃0.07

Fig.5. Effect of initial concentration of organic chloride

Fig.6. Effect of adsorption time

Fig.7. Effect of adsorption temperature

Fig.8. Effect of agent oil ratio

Fig.9. Regencration adsorption performance of Mg⁃UiO⁃66⁃0.07 for organic chlorides

Fig.10. Comparison of XRD patterns of Mg⁃UiO⁃66⁃0.07 before adsorption and after desorption

Fig.11. Dynamic equation fitting curves

样品	拟一级动力学方程			拟二级动力学方程
样品	k₁/min^-1	q_e，exp	R²	k₂/mg·（g·min）^-1	q_e，exp	R²
Mg⁃UiO⁃66⁃0.07	0.002	5.77	0.849	15.109	7.34	0.999

Tab.1. Pseudo primary and pseudo secondary kinetic parameters of Mg⁃UiO⁃66⁃0.07 adsorption of organic chlorides

Fig.12. Fitting diagram of particle internal diffusion model

样品	k_1d/g∙mg^-1∙min^-1/2	R₁²	k_2d/g∙mg^-1∙min^-1/2	R₂²	k_3d/g∙mg^-1∙min^-1/2	R₃²
Mg⁃UiO⁃66⁃0.07	0.916	0.997	0.211	0.987	0.016 9	0.958

Tab.2. Parameters of particle internal diffusion model for Mg⁃UiO⁃66⁃0.07 adsorption of organic chloride

Fig.13. Fitting curves of Langmuir and Freundlich adsorption isotherms

样品	Langmuir			Freundlich
样品	K_L	q_max	R²	K_F	n	R²
Mg⁃UiO⁃66⁃0.07	0.225	22.36	0.997	1.913	1.33	0.987

Tab.3. Fitting parameters of adsorption isotherm of Mg⁃UiO⁃66⁃0.07 adsorbing organic chloride at 40 ℃

Fig.14. Thermodynamic equation fitting curve

T/K

△G/ kJ·mol^-1

△H/kJ·mol^-1

△S/

J·（mol·K^-1）^-1

Tab.4. Thermodynamic curve fitting parameters of Mg⁃UiO⁃66⁃0.07 adsorption of organic chloride at 40 ℃

Fig.15. Possible mechanism of chloride removal by adsorption

References 39

1	孙艺蕾，马跃，李术元，等. 聚烯烃塑料的热解和催化热解研究进展［J］. 化工进展， 2021， 40（5）： 2 784⁃2 801.
	SUN Y L， MA Y， LI S Y，et al. Research progress in the pyrolysis and catalytic pyrolysis of waste polyolefin plastics［J］. Chemical Industry and Engineering Progress， 2021， 40（5）： 2 784⁃2 801.
2	钟艳辉，张莹莹，刘晓文. 废塑料裂解能制燃料油［J］. 中国石油和化工产业观察， 2021，4： 46⁃47.
3	全淑苗，张彦军，宋小飞，等. 废塑料脱氯技术现状及产业化进展［J］. 中国塑料， 2022， 36（9）： 122⁃130.
	QUAN S M， ZHANG Y Y， SONG X F，et al. Status and industrialization progress in dechlorination technologies for waste plastics［J］. China Plastics， 2022， 36（9）： 122⁃130.
4	钟艳辉，张莹莹，刘晓文. 废塑料裂解制取燃料油技术的研究进展［J］. 低碳世界， 2020， 10（4）： 7⁃8.
5	郝清泉，刘宗鹏，朱建华. 废塑料热解油中有机氯化物鉴定及加氢脱氯的热力学和反应机理［J］. 石油化工， 2020， 49（1）： 48⁃55.
	HAO Q Q， LIU Z P， ZHU J H. Identification of organic chlorides in pyrolysis oil from waste plastics and thermodynamic and reaction mechanism of hydrodechlorination［J］. Petrochemical Technology， 2020， 49（1）： 48⁃55.
6	Niu H， Zhao D， Xie G， et al. Deep dechlorination of model oil by reactive adsorption on porous oxides［J］. Fuel， 2021， 304（15）： 121410.
7	Niu H， Feng Y， Ding J， et al. Deep dechlorination of hydrocarbon oil by reactive adsorption on TiO₂⁃based metal oxides［J］. Korean Journal of Chemical Engineering， 2022， 39（7）： 1 936⁃1 945.
8	李瑞丽，王国江，张东媛，等. Cu⁃BTC吸附剂对模拟油中有机氯化物的脱除性能［J］. 石油炼制与化工， 2021， 52（8）： 56⁃63.
	LI R L， WANG G J， ZHANG D Y，et al. Performance of Cu⁃BTC for organic chlorides adsorption form model oil［J］. Petroleum Processing and Petrochemicals， 2021， 52（8）： 56⁃63.
9	李晶晶，李瑞丽，蒋善良，等. 改性SAPO⁃34分子筛对模型油中二氯乙烷的脱除［J］. 化工进展， 2017， 36（10）： 3 730⁃3 736.
	LI J J， LI R L， JIANG S L，et al. Removal of dichloroetha⁃ne in model oil with modified SAPO⁃34 zeolites［J］. Chemical Industry and Engineering Progress， 2017， 36（10）： 3 730⁃3 736.
10	解国应，宫玉洁，周东旭，等. 改性Y型分子筛吸附脱除模拟油品中氯辛烷［J］. 石油学报（石油加工）， 2021， 37（3）： 619⁃625.
	XIE G Y， GONG Y J， ZHOU D X，et al. Adsorption of 1⁃chloroctane in model oil using modified Y zeolite［J］. Acta Petrolei Sinica （Petroleum Processing Section）， 2021， 37（3）： 619⁃625.
11	李瑞丽，张革，张东媛. 硅酸镁铝吸附脱除原油中氯化物的研究［J］. 石油炼制与化工， 2019， 50（4）： 94⁃100.
	LI R L， ZHANG G， ZHANG D Y，et al. Study on removal of chloridedy magnesium aluminum silicate［J］. Petroleum Processing and Petrochemicals， 2019， 50（4）： 94⁃100.
12	牛慧，赵冬汁，张晨，等. 油品中有机氯脱除研究进展［J］. 精细石油化工， 2020， 37（6）： 80⁃84.
	NIU H， ZHAO D Z， ZHANG C，et al. Research progress on removing organochlorine form oil［J］. Speciality Petrochemicals， 2020， 37（6）： 80⁃84.
13	覃妍. 金属有机骨架材料的应用研究进展［J］. 冶金与材料， 2020， 40（2）： 136⁃137.
14	Clark C A， Heck K N， Powell C D， et al. Highly defective UiO⁃66 materials for the adsorptive removal of perfluo⁃rooctanesulfonate［J］. ACS Sustainable Chemistry & Engineering， 2019， 7（7）： 6 619⁃6 628.
15	苏婷. 金属有机骨架UiO⁃66的改性及吸附四环素性能研究［D］. 福州：福建工程学院， 2020.
16	Niu Z， Guan Q， Shi Y， et al. A lithium⁃modified zirco⁃nium⁃based metal organic framework （UiO⁃66） for efficient CO₂ adsorption［J］. New Journal of Chemistry， 2018， 42（24）： 19 764⁃19 770.
17	Yanga Z H， Jiao C， Chena Y P， et al. Mn⁃doped zirco⁃nium metal⁃organic framework as an effective adsorbent for removal of tetracycline and Cr（VI） from aqueous solution［J］. Microporous and Mesoporous Materials， 2018， 277： 277⁃285.
18	周巧云，王淑勤，户家宝，等. 改性UIO⁃66对高浓度Cr（VI）的吸附［J］. 山东化工， 2021， 50（14）： 236⁃240.
	ZHOU Q Y， WANG S Q， HU J B，et al. Adsorption of high concentration Cr（VI） by modified UIO⁃66［J］. Shandong Chemical Industry， 2021， 50（14）： 236⁃240.
19	张雯. UiO⁃66合成、改性及氢气吸附性能研究［D］. 大连：大连理工大学， 2019.
20	Moustafa A， Yas M， Ahmed A， et al. The role of Cobalt to control the synthesis of nanoscale Co/UiO⁃66composite for photocatalysis［J］. Journal of the American Ceramic Society， 2022， 10：18672.
21	Peng Zhang， Xu Yueyang， Guo Konglu， et al. Hierarchical⁃pore UiO⁃66 modified with Ag⁺ for π⁃complexation adsorption desulfurization［J］. Journal of Hazardous Mate⁃rials， 2021， 418： 126247.
22	Lya B， Dwa B， Xla B， et al. One⁃pot synthesis of oxygen⁃vacancy⁃rich Cu⁃doped UiO⁃66 for collaborative adsorption and photocatalytic degradation of ciprofloxacin［J］. Science of The Total Environment， 2021， 815： 151926.
23	俞坤，刘金香，谢水波，等. 聚吡咯/石墨相氮化碳复合材料吸附铀（Ⅵ）的性能与机制［J］. 材料导报， 2020， 34（23）： 23 020⁃23 026.
	YU K， LIU J X， XIE S B，et al. Study on the properties and mechanism of U（Ⅵ） adsorption of PPy/g⁃C₃N₄ ［J］. Materials Reports， 2020， 34（23）： 23 020⁃23 026.
24	Gu Y， Xie D， Ma Y， et al. Size modulation of zirconium⁃based metal organic frameworks for highly efficient phosphate remediation［J］. ACS Applied Materials & Interfa⁃ces， 2017： 10024.
25	李瑞. 改性锆基金属有机骨架对污水中四环素的吸附性能研究［D］. 重庆：重庆大学， 2021.
26	石伟芹. 金属—有机骨架材料ZIFs的制备及其吸附脱硫性能研究［D］. 北京：北京化工大学， 2015.
27	Yang Zhiwang， Xu Xueqing， Liang Xixi. Fabrication of Ce doped UiO⁃66/graphene nanocomposites with enhanced visible light driven photoactivity for reduction of nitroaromatic compounds［J］. Applied Surface Science， 2017： 276⁃285.
28	崔宇晗，赵春艳，周文博，等. 磷钨酸改性ZIF⁃8材料的制备及吸附性能研究［J］. 化学研究与应用， 2022， 34（9）： 2 172⁃2 178.
	CUI Y H， ZHAO C Y， ZHOU W B，et al. Preparation and properties of ZIF⁃8 metal organic frame material modified by phosphotungstic acid. Chemical Research and App⁃lication［J］. 2022， 34（9）： 2 172⁃2 178.
29	田忠宇，杨敬一，王怿兴，等. Fe₃O₄@PGMA⁃Arg磁性吸附剂的制备及对亚铁离子的吸附性能［J］. 化工进展， 2022， 41（2）： 881⁃891.
	TIAN Z Y， YANG J Y， WANG Y X，et al. Preparation of Fe₃O₄@PGMA⁃Arg magnetic adsorbents and its adsorption performance for ferrous ion［J］. Chemical Industry and Engineering Progress， 2022， 41（2）： 881⁃891.
30	李美兰，豆小喻，何娇，等. 羧基化磁性Fe₃O₄复合材料的制备及其对水体中Pb²⁺的吸附研究［J］. 中国塑料， 2021， 35（10）： 37⁃44.
	LI M L， DOU X Y， HE J，et al. Synthesis of carboxyla⁃ted magnetic Fe₃O₄ composites and their adsorption beha⁃vior to Pb²⁺ ［J］. China Plastics， 2021， 35（10）： 37⁃44.
31	向速林，龚聪远，楚明航. Mg⁃Al⁃Cl⁃LDH对磷的吸附性能及其机理［J］. 环境工程学报， 2021， 15（12）： 3 865⁃3 874.
	XIANG S L， GONG C Y， CHU M H. Adsorption performance and mechanism of Mg⁃Al⁃Cl⁃LDH on phosphate［J］. Chinese Journal of Environmental Engineering， 2021， 15（12）： 3 865⁃3 874.
32	刘佳衡，王冬琴，胡盛，等. GO/AT复合材料的制备及其吸附性能分析［J］. 中国塑料， 2020， 34（5）： 45⁃51.
	LIU J H， WANG D Q， HU S，et al. Preparation and adsorption performance of graphene Oxide/Attapulgite composites［J］. China Plastics， 2020， 34（5）： 45⁃51.
33	杨静，沈健，石薇薇. Cu⁃β/SBA⁃15的吸附脱硫性能及吸附动力学［J］. 精细化工， 2017， 34（10）： 1 153⁃1 160.
	YANG J， SHEN J， SHI W W. Adsorption desulfurization and adsorption kinetics of Cu⁃β/SBA⁃15［J］. Fine Chemicals， 2017， 34（10）： 1 153⁃1 160.
34	聂世勇，王学刚，李鹏，等. Mg/Fe层状双金属氧化物材料吸附U（Ⅵ）的性能及吸附机制［J］. 稀有金属， 2019， 43（9）： 920⁃927.
	NIE S Y， WANG X G， LI P，et al. Adsorption of Ura⁃nium（Ⅵ） by Mg /Fe layered double hydroxides［J］. Chinese Journal of Rare Metals， 2019， 43（9）： 920⁃927.
35	单清雯，张娟，王亚娟，等. 聚合离子液体的合成及其吸附脱硫性能［J］. 化工进展， 2022，41（8）： 4 571⁃4 579.
	SHAN Q W， ZHANG J， WANG Y J，et al. Synthesis of polymeric ionic liquid and its performance on adsorption desulfurization［J］. Chemical Industry and Engineering Progress， 2022，41（8）： 4 571⁃4 579.
36	李冉，谷洁，王芳，等. 石脑油中有机氯脱除的研究进展［J］. 化学通报， 2021， 84（12）： 1 351⁃1 355.
	LI R， GU J， WANG F，et al. Research Progress in Removal of Organochlorine from Naphtha［J］. Chemistry， 2021， 84（12）： 1 351⁃1 355.
37	解国应，王佳烽，冯海蛟，等. 吸附法脱除油品中有机氯研究进展［J］. 石油化工， 2020， 49（4）： 411⁃414.
	XIE G Y， WANG J F， FENG H J，et al. Advances on removal of organochlorine in oil using adsorption［J］. Petrochemical Technology， 2020， 49（4）： 411⁃414.
38	Ruan X， Liu H， Wang J， et al. A new insight into the main mechanism of 2，4⁃dichlorophenol dechlorination by Fe/Ni nanoparticles［J］. The Science of the Total Environment， 2019， 697（20）： 1⁃8.
39	Weng Xiulan， Ma Huijing， Owens Gary， et al. Enhanced removal of 2，4⁃dichlorophenol by Fe⁃Pd@ZIF⁃8 via adsorption and dechlorination［J］. Separation and Purification Technology， 2023， 305（122 371）： 1 383⁃5 866.

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