Synthesis of polymeric ionic liquid and its performance on adsorption desulfurization

doi:10.16085/j.issn.1000-6613.2021-1963

Abstract

Abstract:

Functionalized ionic liquid monomer was synthesized from N-methyldiallylamine and metal phthalocyanine, and then polymerized on the surface of the carrier(silica gel ball) to prepare a polymeric functionalized ionic liquid as an adsorbent[(NMDA-Pc/Ni²⁺)/SiO₂]. The adsorbent was characterized by infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, and polarized light microscope. The adsorption and desulfurization performance of the adsorbent for dibenzothiophene(DBT) at normal pressure and room temperature was investigated. The optimal adsorption conditions were the amount of adsorbent of 1.5g/10mL model oil, and the adsorption time of 20min, under which the maximum adsorption capacity of DBT was 6.198mg/g. The adsorption behavior of the adsorbent to DBT followed the Freundlich adsorption isotherm model and the pseudo-second-order kinetic model. The adsorbent was washed and regenerated with methanol, and the adsorption performance was not significantly reduced after reused for 5 times. Both olefins and aromatics affected the adsorption desulfurization performance of the adsorbent, with the former being more significant. The adsorbent also had a good adsorption for different sulfur compounds, and the removal order was dibenzothiophene>benzothiophene>thiophene.

Key words: polymerization, ionic liquids, adsorption, desulfurization, dibenzothiophene, silicon dioxide

摘要：

以N-甲基二烯丙基胺与金属酞菁合成的功能化离子液体为单体、硅胶球为载体，在载体表面聚合制备成硅胶球负载的聚合功能化离子液体吸附材料[(NMDA-Pc/Ni²⁺)/SiO₂]。本研究采用红外光谱、X射线衍射、扫描电镜、偏光显微镜对其进行表征。考察了吸附剂在常压室温下对二苯并噻吩（DBT）的吸附脱硫性能。结果表明，(NMDA-Pc/Ni²⁺)/SiO₂的吸附脱硫性能最好。最佳吸附条件为吸附剂用量为1.5g/10mL模型油，吸附时间为20min，DBT的最大吸附量为6.198mg/g。该吸附剂对DBT的吸附行为遵循Freundlich 吸附等温模型和拟二级动力学模型。以甲醇洗涤再生，重复使用5次后，吸附性能没有明显降低。烯烃和芳烃都会影响吸附剂的吸附脱硫效果，但芳烃对DBT选择性吸附的影响小于烯烃。吸附剂对不同的硫化合物也有良好的吸附作用，去除顺序为：二苯并噻吩>苯并噻吩>噻吩。

关键词: 聚合, 离子液体, 吸附, 脱硫, 二苯并噻吩, 二氧化硅

CLC Number:

O647.33

SHAN Qingwen, ZHANG Juan, WANG Yajuan, LIU Wenqiang. Synthesis of polymeric ionic liquid and its performance on adsorption desulfurization[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4571-4579.

单清雯, 张娟, 王亚娟, 刘文强. 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): 4571-4579.

Figures/Tables 21

References 35

1	WU Jianxiang, GAO Yilong, ZHANG Wei, et al. Deep desulfurization by oxidation using an active ionic liquid-supported Zr metal-organic framework as catalyst[J]. Applied Organometallic Chemistry, 2015, 29(2): 96-100.
2	SURYAWANSHI N B, BHANDARI V M, SOROKHAIBAM L G, et al. Investigating adsorptive deep desulfurization of fuels using metal-modified adsorbents and process intensification by acoustic cavitation[J]. Industrial & Engineering Chemistry Research, 2019, 58(18): 7593-7606.
3	张健, 韩磊, 刘树伟, 等. 大孔Ni-Mo/Al₂O₃催化剂上重馏分油加氢脱硫生产低硫船用燃料油[J]. 石油化工, 2021, 50(2): 117-122.
	ZHANG Jian, HAN Lei, LIU Shuwei, et al. Hydrodesulfurization of heavy distillate oil over macroporous Ni-Mo/Al₂O₃ catalyst with the aim of producing low-sulfur marine fuel[J]. Petrochemical Technology, 2021, 50(2): 117-122.
4	FOX E B, LIU Zhongwen, LIU Zhaotie. Ultraclean fuels production and utilization for the twenty-first century: advances toward sustainable transportation fuels[J]. Energy & Fuels, 2013, 27(11): 6335-6338.
5	CHANDRA SRIVASTAVA V. An evaluation of desulfurization technologies for sulfur removal from liquid fuels[J]. RSC Adv., 2012, 2(3): 759-783.
6	刘璇, 崔颖娜, 尹静梅, 等. 金属有机骨架材料在吸附脱硫领域的应用[J]. 化工进展, 2020, 39(8): 3163-3176.
	LIU Xuan, CUI Yingna, YIN Jingmei, et al. Application of meta-organic frameworks materials in adsorptive desulfurization[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3163-3176.
7	张娟, 任腾杰, 胡颜荟, 等. MCM-41分子筛负载金属酞菁在氧化脱硫反应中的催化性能[J]. 化工学报, 2014, 65(8): 3012-3018.
	ZHANG Juan, REN Tengjie, HU Yanhui, et al. Catalytic performance of metal phthalocyanine loaded on MCM-41 molecular sieve in oxidation desulfurization[J]. CIESC Journal, 2014, 65(8): 3012-3018.
8	易成高, 于寒颖, 赵欢, 等. 石油和天然气生物脱硫技术分析和展望[J]. 石油化工, 2010, 39(6): 681-687.
	YI Chenggao, YU Hanying, ZHAO Huan, et al. Technique analysis and prospect of biologic desulphurization process for crude oil and natural gas[J]. Petrochemical Technology, 2010, 39(6): 681-687.
9	张娟, 李俊盼, 任腾杰, 等. [C _n mim]Br/FeCl₃型离子液体萃取脱除二苯并噻吩[J]. 化工学报, 2013, 64(10): 3647-3651.
	ZHANG Juan, LI Junpan, REN Tengjie, et al. Extraction desulfurization of dibenzothiophene with [C_3~8mim]Br/FeCl₃ ionic liquids[J]. CIESC Journal, 2013, 64(10): 3647-3651.
10	刘卉, 高金森, 赵亮. 吸附脱除噻吩类硫化物机理的研究进展[J]. 石油化工, 2010, 39(9): 1059-1065.
	LIU Hui, GAO Jinsen, ZHAO Liang. Advances in adsorptive desulfurization mechanism for thiophene-type sulfide[J]. Petrochemical Technology, 2010, 39(9): 1059-1065.
11	WANG Sihua, ZU Yun, QIN Yucai, et al. Fabrication of effective desulfurization species active sites in the CeY zeolites and the adsorption desulfurization mechanisms[J]. Journal of Fuel Chemistry and Technology, 2020, 48( 1): 52-62.
12	BAGHERI M, MASOOMI M Y, MORSALI A. High organic sulfur removal performance of a cobalt based metal-organic framework[J]. Journal of Hazardous Materials, 2017, 331: 142-149.
13	BLANCO-BRIEVA G, CAMPOS-MARTIN J M, AL-ZAHRANI S M, et al. Effectiveness of metal-organic frameworks for removal of refractory organo-sulfur compound present in liquid fuels[J]. Fuel, 2011, 90(1): 190-197.
14	肖永厚, 朱科润, 董晓莹, 等. 燃油选择性吸附脱硫的多孔材料研究进展[J]. 化工进展, 2020, 39(6): 2241-2250.
	XIAO Yonghou, ZHU Kerun, DONG Xiaoying, et al. Research progress on porous materials for desulfurization of fuel by selective adsorption[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2241-2250.
15	杨诗, 蔡阳, 李长平, 等. 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, et al. 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.
16	ZHANG Junheng, CHEN Shiyuan, HE Qianjun, et al. Toughening benzoxazines with hyperbranched polymeric ionic liquids: effect of cations and anions[J]. Reactive and Functional Polymers, 2018, 133: 37-44.
17	李春喜, 熊佳丽, 孟洪, 等. 从ILs到PILs: 聚合离子液体介孔材料的制备性质及结构调控方法[J]. 化工进展, 2014, 33(8): 1941-1950.
	LI Chunxi, XIONG Jiali, MENG Hong, et al. From ILs to PILs: synthesis and structure tuning of poly ionic liquids mesoporous materials[J]. Chemical Industry and Engineering Progress, 2014, 33(8): 1941-1950.
18	冯建朋, 张香平, 尚大伟, 等. 离子液体中电化学还原CO₂研究评述与展望[J]. 化工学报, 2018, 69(1): 69-75.
	FENG Jianpeng, ZHANG Xiangping, SHANG Dawei, et al. Review and prospect of CO₂ electro-reduction in ionic liquids[J]. CIESC Journal, 2018, 69(1): 69-75.
19	CHEN Yuanzhe, ZHANG Fengwei, FANG Yiyun, et al. Phosphotungstic acid containing ionic liquid immobilized on magnetic mesoporous silica rod catalyst for the oxidation of dibenzothiophene with H₂O₂ [J]. Catalysis Communications, 2013, 38: 54-58.
20	孙爽, 李未康, 张娟, 等. 聚合离子液体的吸附分离应用研究进展[J]. 现代化工, 2017, 37(6): 38-42.
	SUN Shuang, LI Weikang, ZHANG Juan, et al. Research progress on application of polymeric ionic liquids in adsorption separation[J]. Modern Chemical Industry, 2017, 37(6): 38-42.
21	QIAN Wenjing, TEXTER J, YAN Feng. Frontiers in poly(ionic liquid)s: syntheses and applications[J]. Chemical Society Reviews, 2017, 46(4): 1124-1159.
22	李春喜, 许慧慧, 朱学习, 等. 吡啶基聚合离子液体的制备及其对油中噻吩硫的吸附性能[J]. 化工学报, 2016, 67(7): 2880-2886.
	LI Chunxi, XU Huihui, ZHU Xuexi, et al. Synthesis of pyridinium based polymerized ionic liquid and its adsorptive desulfurization performance for thiophenic sulfurs from oil[J]. CIESC Journal, 2016, 67(7): 2880-2886.
23	ZHANG Juan, SUN Shuang, BIAN Yuhang, et al. Adsorptive desulfurization of metal phthalocyanine functionalized poly-ionic liquids grafted to silica gel[J]. Fuel, 2018, 220: 513-520.
24	BI Wentao, ZHU Tao, PARK D W, et al. Sorption of carbon dioxide by ionic liquid-based sorbents[J]. Asia-Pacific Journal of Chemical Engineering, 2012, 7(1): 86-92.
25	HAN Peng, ZHANG Hongming, QIU Xuepeng, et al. Palladium within ionic liquid functionalized mesoporous silica SBA-15 and its catalytic application in room-temperature Suzuki coupling reaction[J]. Journal of Molecular Catalysis A: Chemical, 2008, 295(1/2): 57-67.
26	SAHOO S, KUMAR P, LEFEBVRE F, et al. Oxidative kinetic resolution of alcohols using chiral Mn-salen complex immobilized onto ionic liquid modified silica[J]. Applied Catalysis A: General, 2009, 354(1/2): 17-25.
27	ZHAO Dishun, ZHANG Juan, DUAN Erhong, et al. Adsorption equilibrium and kinetics of dibenzothiophene from n-octane on bamboo charcoal[J]. Applied Surface Science, 2008, 254(10): 3242-3247.
28	SRIVASTAV A, SRIVASTAVA V C. Adsorptive desulfurization by activated alumina[J]. Journal of Hazardous Materials, 2009, 170(2/3): 1133-1140.
29	MITCHELL L A, LEVAN M D. Development of adsorption equilibrium relations for mixtures from pure component isotherms and Henry’s law behavior with components in excess[J]. Industrial & Engineering Chemistry Research, 2014, 53(40): 15531-15537.
30	KUNDU S, GUPTA A K. Arsenic adsorption onto iron oxide-coated cement (IOCC): regression analysis of equilibrium data with several isotherm models and their optimization[J]. Chemical Engineering Journal, 2006, 122(1/2): 93-106.
31	SARDA K K, BHANDARI A, PANT K K, et al. Deep desulfurization of diesel fuel by selective adsorption over Ni/Al₂O₃and Ni/ZSM-5 extrudates[J]. Fuel, 2012, 93: 86-91.
32	MA Xiaoliang, SUN Lu, SONG Chunshan. A new approach to deep desulfurization of gasoline, diesel fuel and jet fuel by selective adsorption for ultra-clean fuels and for fuel cell applications[J]. Catalysis Today, 2002, 77(1/2): 107-116.
33	XU Xinhai, ZHANG Shuyang, LI Peiwen, et al. Equilibrium and kinetics of Jet-A fuel desulfurization by selective adsorption at room temperatures[J]. Fuel, 2013, 111: 172-179.
34	HERNÁNDEZ-MALDONADO A J, YANG R T. Desulfurization of commercial liquid fuels by selective adsorption via π-complexation with Cu( Ⅰ )-Y zeolite[J]. Industrial & Engineering Chemistry Research, 2003, 42(13): 3103-3110.
35	CHENG Bei, LE Yao, CAI Weiquan, et al. Synthesis of hierarchical Ni(OH)₂ and NiO nanosheets and their adsorption kinetics and isotherms to Congo red in water[J]. Journal of Hazardous Materials, 2011, 185(2/3): 889-897.

等温吸附模型	参数	数值
Langmuir	q_m/mg·g^-1	6.198
	K_L	20.156
	R²	0.89416
Freundlich	K_F	0.5048
	1/n	0.581
	R²	0.99632

等温吸附模型	参数	数值
Langmuir	q_m/mg·g^-1	6.198
	K_L	20.156
	R²	0.89416
Freundlich	K_F	0.5048
	1/n	0.581
	R²	0.99632

吸附剂	硫化物种类	脱硫量 /mg·g^-1	参考文献
Ni/ZSM-5	DBT	0.496	［31］
过渡金属化合物负载的硅胶体系	DBT	0.5184	［32］
Ni-Ce/Al₂O₃-SiO₂	DBT	3.97	［33］
Cu(Ⅰ)-Y 分子筛	DBT	4.925	［34］
(NMDA-Pc/Ni²⁺)/SiO₂	DBT	6.196	本实验

吸附剂	硫化物种类	脱硫量 /mg·g^-1	参考文献
Ni/ZSM-5	DBT	0.496	［31］
过渡金属化合物负载的硅胶体系	DBT	0.5184	［32］
Ni-Ce/Al₂O₃-SiO₂	DBT	3.97	［33］
Cu(Ⅰ)-Y 分子筛	DBT	4.925	［34］
(NMDA-Pc/Ni²⁺)/SiO₂	DBT	6.196	本实验

模型	参数	数值
拟一级动力学	k₁/min^-1	0.06523
	q_e，cal/mg·g^-1	1.4619
	R²	0.78241
拟二级动力学	k₂/min^-1	0.1063
	q_e，cal/mg·g^-1	4.6081
	R²	0.99416