超顺磁催化剂H3PW12O40/Fe3O4@SiO2的制备、结构表征及在汽油烷基化脱硫中的应用

doi:10.3969/j.issn.0438-1157.2014.03.022

化工学报 ›› 2014, Vol. 65 ›› Issue (3): 921-928.DOI: 10.3969/j.issn.0438-1157.2014.03.022

• 催化、动力学与反应器 • 上一篇下一篇

超顺磁催化剂H₃PW₁₂O₄₀/Fe₃O₄@SiO₂的制备、结构表征及在汽油烷基化脱硫中的应用

熊小龙¹, 刘自力¹, 许翠霞², 秦祖赠²

1 广州大学化学化工学院, 珠江三角水质安全与保护教育部重点实验室, 广东广州 510006;
2 广西大学化学化工学院, 广西南宁 530004

收稿日期:2013-09-06 修回日期:2013-12-18 出版日期:2014-03-05 发布日期:2014-03-05
通讯作者: 刘自力
作者简介:熊小龙（1989—），男，硕士研究生。
基金资助:
国家自然科学基金项目（21076047， 21276054）。

Preparation and structure characterization of superparamagnetic supported catalyst H₃PW₁₂O₄₀/Fe₃O₄@SiO₂and its application in olefinic alkylation desulfurization

XIONG Xiaolong¹, LIU Zili¹, XU Cuixia², QIN Zuzeng²

1 Key Laboratory of Ministry of Education for Water Quality Security and Protection in Pearl River Delta, School of Chemistry & Chemical Engineering, Guangzhou University, Guangzhou 510006, Guangdong, China;
2 School of Chemistry & Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China

Received:2013-09-06 Revised:2013-12-18 Online:2014-03-05 Published:2014-03-05
Supported by:
supported by the National Natural Science Foundation of China (21076047, 21276054).

摘要/Abstract

摘要： 采用改进Stöber法制备超顺磁Fe₃O₄@SiO₂复合粒子作为催化剂载体，再通过浸渍法将H₃PW₁₂O₄₀（HPW）负载在Fe₃O₄@SiO₂载体上，制备了一系列超顺磁负载型催化剂HPW/Fe₃O₄@SiO₂。并使用X射线衍射（XRD）、傅里叶红外（FT-IR）、氨的程序升温脱附（NH₃-TPD）、扫描电镜（SEM）、N₂吸附-脱附和振动样品强磁计（VSM）对催化剂进行表征。结果表明，HPW固定并均匀分散在Fe₃O₄@SiO₂载体上，40% HPW/Fe₃O₄@SiO₂催化剂具有较高的饱和磁强度（30.1 emu·g^-1）和较大的比表面积（303.6 m²·g^-1），并可用外加磁场进行分离。采用40% HPW/Fe₃O₄@SiO₂催化噻吩与1-辛烯组成的模拟汽油的烷基化脱硫反应，在160℃下反应2 h，噻吩转化率达到85.5%，有较好的催化脱硫性能，且可以多次循环利用。

关键词: 超顺磁性, 烷基化, 磷钨酸, 催化剂, 复合材料, 二氧化硅

Abstract: Fe₃O₄@SiO₂ nanocomposite was prepared via modified Stöber method and used as catalyst support. Superparamagnetic supported catalystsprepared by loading H₃PW₁₂O₄₀ (HPW) onto Fe₃O₄@SiO₂ support through a wet impregnation method, were used for alkylation reaction, and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), NH₃-temperature programmed desorption (TPD), scanning electron microscope (SEM), N₂-adsorption and vibrating sample magnetometer (VSM). Their physicochemical characterization revealed that HPW had been immobilized and dispersed on Fe₃O₄@SiO₂. Moreover, 40%(mass) HPW loading catalyst, been of high magnetization 30.1 emu·g^-1, mesoporous structure and the surface area 303.6 m²·g^-1, could be considered to be a proper catalyst for olefinic alkylation of thiophenic sulfur (OATS) and they can be easy separated by external magnetic field. In addition, their catalytic activity was also investigated in alkylation reaction of a model mixture of thiophene and 1-octene, and the conversion of thiophene was up to 85.5% after 2 h at 160℃.

Key words: superparamagetism, alkylation, phosphotungstic acid, catalyst, composites, silica

中图分类号:

TE624

熊小龙, 刘自力, 许翠霞, 秦祖赠. 超顺磁催化剂H₃PW₁₂O₄₀/Fe₃O₄@SiO₂的制备、结构表征及在汽油烷基化脱硫中的应用[J]. 化工学报, 2014, 65(3): 921-928.

XIONG Xiaolong, LIU Zili, XU Cuixia, QIN Zuzeng. Preparation and structure characterization of superparamagnetic supported catalyst H₃PW₁₂O₄₀/Fe₃O₄@SiO₂and its application in olefinic alkylation desulfurization[J]. CIESC Journal, 2014, 65(3): 921-928.

参考文献 27

[1]	Bellière V, Lorentz C, Geantet C, et al. Kinetics and mechanism of liquid-phase alkylation of 3-methylthiophene with 2-methyl-2-butene over a solid phosphoric acid[J]. Appl. Catal. B: Environ., 2006, 64(2): 254-261
[2]	Sun Junnan(孙俊楠),Han Fengshan(韩凤山). Status-quo of research & development of FCC gasoline deep desulfurization technologies[J].Petroleum Refinery Engineering(炼油技术与工程), 2012, 42(7):18-21
[3]	Kong Huiqing(孔会清), Zhang Kongyuan(张孔远), Zhang Jingcheng(张景成), et al. Preparation selective hydrodesulfurization catalyst Co-Mo/MgAl2O4-Al2O3 for FCC gasoline[J]. Acta Petrolei Sinica:Petroleum Processing Section (石油学报:石油加工),2010, 26(4):499-505
[4]	Wang L H, Wen S Z, Hua M L, et al. Heteropolyanion-based ionic liquid for deep desulfurization of fuels in ionic liquids[J]. Ind. Eng. Chem. Res., 2010, 49(19):8998-9003
[5]	Takatsuka T, Inoue S, Wada Y. Deep hydrodesulfurization process for diesel oil[J]. Catal. Today, 1997, 39(1/2): 69-75
[6]	Ke Ming (柯明), Zhou Aiguo(周爱国), Zhao Zhensheng(赵振盛), et al. Alkylation of thiophenic sulfur technology in the production of clean fuel[J]. Chemical Industry and Engineering Progress (化工进展), 2006, 25(4):357-361
[7]	Jaimes L, Badillo M, de Lasa H. FCC gasoline desulfurization using a ZSM-5 catalyst Interactive effects of sulfur containing species and gasoline components[J].Fuel, 2011, 90 (1/2): 2016-2025
[8]	Martínez-Magadán J M, Oviedo-Roa R, García P, et al. DFT study of the interaction between ethanethiol and Fe-containing ionic liquids for desulfuration of natural gasoline[J]. Fuel Process. Technol., 2012, 97(1):24-29.
[9]	Guo Qiaoxia(郭巧霞), Tang Xiaodong(唐晓东), Zhao Hongyi(赵红义), et al. Advances in alkylation catalysts for FCC gasoline desulfurization[J]. Speciality Petrochemicals (精细石油化工), 2009, 26(4):68-72
[10]	Hu L, Zhang Z, Xie S, et al. Effect of grain size of zeolite Y on its catalytic performance in olefin alkylation thiophenic sulfur process[J]. Catal. Commun., 2009, 10(8): 900-904
[11]	Zhang Z K, Niu X L, Liu S L, et al. The performance of HMCM-22 zeolite catalyst on the olefin alkylation thiophenic sulfur in gasoline[J]. Catal. Commun., 2008, 9(1): 60-64
[12]	Zhang Z K, Liu S L, Zhu X X, et al. Modification of Hβ zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline[J]. Fuel Process. Technol., 2008, 89(4): 103-109
[13]	Shi R G, Li Y H, Wang R, et al. Alkylation of thiophenic compounds with olefins and its kinetics over MCM-41 supported phosphoric acid in FCC gasoline[J]. Catal. Lett., 2010, 139(14): 114-122
[14]	Guo B S, Wang R, Li Y H. The performance of solid phosphoric acid catalysts and macroporous sulfonic resins on gasoline alkylation desulfurization[J]. Fuel Process. Technol., 2010, 91(9): 1731-1735
[15]	Arias M, Laurenti D, Bellière V, Geantet C, et al. Preparation of supported H3PW12O40·6H2O for thiophenic compounds alkylation in FCC gasoline[J]. Appl. Catal. A: Gen., 2008, 348(34): 142-147
[16]	Arias M, Laurenti D, Bellière V, et al. Gasoline desulfurization by catalytic alkylation over silica-supported heteropolyacids: from model reaction to real feed conversion[J]. Catal. Today, 2008, 130(3): 190-194
[17]	Guo B S, Wang R, Li Y H. Gasoline alkylation desulfurization over amberlyst 35 resin: influence of methanol and apparent reaction kinetics[J]. Fuel, 2011, 90(9): 713-718
[18]	Wang Desheng(王德胜),Yan Liang(闫亮),Wang Xiaolai(王晓来). Research progress of heteropolyacid catalyst[J]. J. Mol. Catal. (分子催化), 2012, 26(4): 366-375
[19]	Li Weiyuan(李威渊), Liu Yuanyuan(刘媛媛), Zheng Huayan(郑华艳), et al. Molecular structure and application of heteropolyacid (salt) catalysts for organic synthesis[J]. Chemical Industry and Engineering Progress (化工进展), 2010, 29(2): 243-250
[20]	Wang Enbo(王恩波), Hu Changwen(胡长文), Xu Lin(许林). Introduction to Polyoxometalate Chemistry(多酸化学导论)[M]. Beijing: Chemical Industry Press,1998
[21]	Ji J H, Zeng P h, Ji S, et al. Catalytic activity of core-shell structured Cu/Fe3O4@SiO2 microsphere catalysts[J]. Catal. Today, 2010, 158(26): 305-309
[22]	Yadav G D, Bokade V V. Novelties of heteropoly acid supported on clay: etherification of phenethyl alcohol with alkanols[J]. Appl. Catal. A: Gen., 1996, 147(12): 299-323
[23]	Wen Langyou(温朗友), Shen Shikong(沈师孔), Min Enze(闵恩泽). Physicochemical and catalytic properties of 12-phosphotungstic acid supported on different silica[J]. Chinese Journal of Catalysis(催化学报),2000,21(6):524-528
[24]	Arias M, Laurenti D, Belliere V, et al. Preparation of supported H3PW12O40·6H2O for thiophenic compounds alkylation in FCC gasoline[J]. Applied Catalysis A: General, 2008, 348(1):142-147
[25]	Zhang Fumin(张富民), Yuan Chaoshu(袁超树), Ren Xiaoqian(任晓乾), et al. Characterization of supported heteropoly acid (salt) and its catalytic behavior in synthesis of fructone[J]. Journal of Chemical Industry and Engineering(China) (化工学报), 2006, 57 (4): 762-767
[26]	Kroll E, Winnik F M. In situ preparation of nanocrystalline g-Fe2O3 in iron (Ⅱ) cross-linked alginate gels[J]. Chem. Mater., 1996, 8(2): 1594-1596
[27]	Blasco T, Corma A, Martínez A, et al. Supported heteropolyacid (HPW) catalysts for the continuous alkylation of isobutane with 2-butene: the benefit of using MCM-41 with larger pore diameters[J]. J. Catal., 1998, 177(10): 306-313

超顺磁催化剂H₃PW₁₂O₄₀/Fe₃O₄@SiO₂的制备、结构表征及在汽油烷基化脱硫中的应用

Preparation and structure characterization of superparamagnetic supported catalyst H₃PW₁₂O₄₀/Fe₃O₄@SiO₂and its application in olefinic alkylation desulfurization

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[2]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[3]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[4]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[5]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[6]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[7]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[8]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[9]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[10]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[11]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[12]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[13]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[14]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[15]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.