Synthesis of pyridinium based polymerized ionic liquid and its adsorptive desulfurization performance for thiophenic sulfurs from oil

doi:10.11949/j.issn.0438-1157.20160104

Abstract

Abstract:

By using 4-vinyl pyridine (VP) and p-xylylene dichloride (PXDC), a PVP-PXDC, a highly crosslinked polymerized ionic liquid, was synthesized through radical polymerization and quaternary crosslinking reaction. In terms of composition, structure, morphology, thermal stability, specific surface area and pore structure of the ionic liquid polymer, it has been characterized by techniques of gel permeation chromatography, elemental analysis, infrared spectroscopy, scanning electron microscopy, thermo gravimetric analyzer and N₂-adsorption, respectively, followed by the performance evaluation as adsorbent for desulfurization. It showed that the mesoporous ionic liquid polymer features 17.8 nm of average pore size, 56.9 m²·g^-1 of specific area of and above 250℃ of decomposition temperature. The ionic liquid polymer was achieved by synthesis of the linear PVP polymer (160000 of weight-based mean molecular weight) followed by crosslinking with PXDC at molar ratio of VP/PXDC of 2:1 in DMF solvent. Its adsorption capacities for 1000 mg·kg^-1 DBT, BT and T in a representative oil, are 5.65, 5.48 and 4.53 mg S·g^-1 at 303 K and mass ratio of oil/adsorbent of 50:1, respectively, which are much higher than those of conventional pyridinium based ionic liquids. Moreover, the adsorption isotherms follow Freundlich equation.

Key words: 4-vinyl pyridine, poly ionic liquid, adsorbent, desulfurization, thiophenic sulfur

摘要：

以4-乙烯基吡啶（VP）和1,4-对二氯苄（PXDC）为原料，通过自由基聚合和季铵化交联反应，制得了一种高度交联的离子液体聚合物——PVP-PXDC。采用凝胶渗透色谱法、元素分析法、红外光谱分析法、扫描电镜、热重分析及比表面积分析等分析方法对离子聚合物的组成、结构、形貌、热稳定性及比表面积、孔结构参数等进行了表征，并考察了吸附剂的脱硫性能。结果表明，先通过聚合得到重均分子量16万以上的PVP线性聚合物，再在DMF溶剂中按VP与PXDC摩尔比2：1加入交联剂，可得到平均孔径为17.8 nm聚合离子液体介孔材料，其热分解温度在250℃以上，比表面积为56.9 m²·g^-1。在油/剂质量比50：1和30℃条件下，其对1000 mg·kg^-1模型油中二苯并噻吩（DBT）、苯并噻吩（BT）和噻吩（T）的吸附量分别为5.65、5.48和4.53 mg S·g^-1，远高于常规吡啶基离子液体，吸附等温线符合Freundlich方程。

关键词: 4-乙烯基吡啶, 聚合离子液体, 吸附剂, 脱硫, 噻吩硫

CLC Number:

O632.19

LI Chunxi, XU Huihui, ZHU Xuexi, LU Yingzhou, MENG Hong. 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.

李春喜, 许慧慧, 朱学习, 陆颖舟, 孟洪. 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.

References 20

[1]	YUAN J Y, ANTONIETTI M. Poly(ionic liquid)s: polymers expanding classical property profiles [J]. Polymer, 2011, 52 (7): 1469-1482.
[2]	杨雪娇, 方岩雄, 张焜, 等. 基于可聚合离子液体的功能高分子材料研究进展 [J]. 化工进展, 2015, 34 (7): 1919-1927. YANG X J, FANG Y X, ZHANG K, et al. Progress of polymerizable ionic liquids-based functional polymer [J]. Chemical Industry and Engineering Progress, 2015, 34 (7): 1919-1927.
[3]	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及结构调控方法 [J]. 化工进展, 2014, 33 (8): 1941-1950. LI C X, XIONG J L, MENG H, 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.
[4]	MARCILLAR R, BLAZQUEZ J A, RODRIGUEZ J, et al.Tuning the solubility of polymerized ionic liquids by simple anion-exchange reactions [J]. Journal of Polymer Science, Part A: Polymer Chemistry, 2004, 42 (1): 208-212.
[5]	TANG J B, TANG H D, SUN W L, et al. Poly(ionic liquid)s as new materials for CO2 absorption [J]. Journal of Polymer Science, Part A: Polymer Chemistry, 2005, 43 (22): 5477-5489.
[6]	KULKARNI P S, AFONSO C A M. Deep desulfurization of diesel fuel using ionic liquids: current status and future challenges [J]. Green Chemistry, 2010, 12 (7): 1139-1149.
[7]	RAFAEL M P, RAFAEL L. Applications of ionic liquids in the removal of contaminants from refinery feedstocks: an industrial perspective [J]. Energy Environ. Sci., 2014, 7 (8): 2414-2447.
[8]	宋红艳, 何静, 李春喜. 燃料油深度脱硫的技术策略及研究进展 [J]. 石油化工, 2015, 44 (3): 7-14. SONG H Y, HE J, LI C X. Technical strategies and recent advances for deep desulfurization of fuel oils [J]. Petrochemical Technology, 2015, 44 (3): 7-14.
[9]	熊佳丽, 孟洪, 陆颖舟, 等. 对二氯苄-聚乙烯咪唑型聚合离子液体的制备及其对煤焦油中苯酚的吸附性能 [J]. 高校化学学报, 2014, 35 (9): 2031-2036. XIONG J L, MENG H, LU Y Z, et al. Synthesis of 1, 4-bis(chloromethyl) benzene crosslinked poly(vinyl imidazolium) and its adsorptivity for phenol from coal tar [J]. Chemical Journal of Chinese Universities, 2014, 35 (9): 2031-2036.
[10]	GELLERSTEDT G. Gel permeation chromatography [J]. Springer Series in Wood Science, 1992, 8 (1): 487-497.
[11]	JANAKIRAMAN S, FARRELL S L, HSIEH C-Y, et al. Kinetic analysis of the initiated chemical vapor deposition of poly(vinylpyrrolidone) and poly (4-vinylpyridine) [J]. Thin Solid Films, 2015, 595, part B: 244-250.
[12]	JERMAKOWICZ-BARTKOWIAK D, KOLARZ B-N. Poly(4-vinylpyridine) resins towards perrhenate sorption and desorption [J]. Reactive and Functional Polymers, 2011, 71 (2): 95-103.
[13]	郑丽丽, 郭晨, 刘会洲. 离子液体的红外光谱研究 [J]. 光谱学与光谱分析, 2006, 26 (7): 33-34. ZHENG L L, GUO C, LIU H Z. The FTIR Study of the 1-butyl-3-methylimidazoliun based ionic liquids [J]. Spectroscopy and Spectral Analysis, 2006, 26 (7): 33-34.
[14]	JAGTAP S R, RAJE V P, SAMANT S D, et al. Silica supported polyvinyl pyridine as a highly active heterogeneous base catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides [J]. Journal of Molecular Catalysis A: Chemical, 2007, 266 (1/2): 69-74.
[15]	ELMACI A, HACALOGLU J. Thermal degradation of poly(vinylpyridine)s [J]. Polymer Degradation and Stability, 2009, 94 (4): 738-743.
[16]	AZHARI S J, DIAB M A. Thermal degradation and stability of poly(4-vinylpyridine) homopolymer and copolymers of 4-vinylpyridine with methyl acrylate [J]. Polymer Degradation and Stability, 1998, 60 (2/3): 253-256.
[17]	BARRETT E P, JOYNER L G, HALEND P P. The determination of pore volume and area distributions in porous substances (Ⅰ): Computations from nitrogen isotherms [J]. Journal of the American Chemical Society, 1951, 73 (1): 373-380.
[18]	OZKAYA B. Adsorption and desorption of phenol on activated carbon and a comparison of isotherm models [J]. Journal of Hazardous Materials, 2006, 129 (1/2/3): 158-163.
[19]	陈博, 孟洪, MUHAMMAD Y, 等. 改性活性炭对模拟柴油中噻吩类硫化物的吸附性能 [J]. 离子交换与吸附, 2011, 27 (2): 137-144. CHEN B, MENG H, MUHAMMAD Y, et al. Adsorption performance of modified activated carbons for thiophene derivatives in simulative diesel oil system [J]. Ion Exchange and Adsorption, 2011, 27 (2): 137-144.
[20]	JIANG X C, NIE Y, LI C X, et al. Imidazolium-based alkyphosphate ionic liquids-a potential solvent for extractive desulfurization of fuel [J]. Fuel, 2008, 87 (1): 79-84.