磷钨酸-尿素/四氧化三铁磁性氧化脱硫催化剂反应性能

doi:10.11944/j.issn.1000-0518.2015.03.140234

摘要/Abstract

摘要：

制备了铁磁性Fe₃O₄基质,并引入磷钨酸尿素复合物制备了有机硫化物氧化催化剂(HPW-Urea/Fe₃O₄),并通过IR、XRD、Raman和TG等技术手段测定了磁性催化剂的物理化学和热学性质。研究结果表明,在Fe₃O₄上引入HPW-Urea后,磷钨酸尿素复合物以Keggin结构存在于载体Fe₃O₄上,且和载体之间是化学键作用。在以有机硫化物乙硫醇的正己烷溶液的H₂O₂氧化反应中,磷钨酸尿素复合物的引入提高了磁性Fe₃O₄对乙硫醇的氧化活性,并探讨了尿素在活性改善中的作用。

关键词: 磷钨酸, 四氧化三铁, 乙硫醇, 尿素, 过氧化氢

Abstract:

Oxidation catalysts of organic sulfide were synthesized by the ferromagnetic Fe₃O₄ matrix and phosphotungstic acid urea complexes(PAUC). The properties of products were characterized by IR, XRD, Raman and TG. With introduction of oxidation catalysts of organic sulfide, it is found that PAUC exists on Fe₃O₄ support in a Keggin structure and there is a chemical bond effect between them. If the H₂O₂ oxidation of ethanethiol proceeds in n-hexane, the oxidation activity of ethanethiol over ferromagnetic Fe₃O₄ matrix is increased in the presence of the PAUC. The effect of urea on activity has been discussed.

Key words: phosphotungstic acid, magnetic iron oxide, ethanethiol, urea, hydrogen peroxide

中图分类号:

宋鹏月, 朱江, 于博浩, 王旭阳, 杨娇, 李禹蒙, 李传鹏, 杨晓宇, 陈立东, 姜春杰. 磷钨酸-尿素/四氧化三铁磁性氧化脱硫催化剂反应性能[J]. 应用化学, 2015, 32(3): 317-321.

SONG Pengyue, ZHU Jiang, YU Bohao, WANG Xuyang, YANG Jiao, LI Yumeng, LI Chuanpeng, YANG Xiaoyu, CHEN Lidong, JIANG Chunjie. Performance of Phosphotungstic Acid-Urea/Ferroferric Oxide Magnetic Oxidative Desulfurization Catalyst[J]. Chinese Journal of Applied Chemistry, 2015, 32(3): 317-321.

参考文献

[1]	JI Li,LIU Jinqiang,QIAN Chao,et al.Advances in the Application of Urea-Hydrogen Peroxide to Oxidation Reactions[J]. Chinse J Org Chem,2012,32(2):254-265(in Chinese). 计立,刘金强,钱超,等. 过氧化脲在氧化反应中的应用研究进展[J]. 有机化学,2012,32(2):254-265.
[2]	YU Fengli,WANG Rui. Study on Oxidative Desulfurization Catalyzed by Organic-Inorganic Heteropolyacids as Phase Transfer Catalyst[J]. Acta Chim Sin,2014,72(1):105-113(in Chinese). 于凤丽,王睿. 有机-无机型杂多酸相转移催化氧化脱硫性能研究[J]. 化学学报,2014,72(1):105-113.
[3]	Sasaki Y,Ushimaru K,Iteya K,et al.Tetrabutylammonium Phosphomolybdate on Fluorapatite:An Efficient Solid Catalyst for Solvent-Free Selective Oxidation of Sulfides[J]. Tetrahedron Lett,2004,45(52):9513-9515.
[4]	Li C,Jiang Z X,Gao J B,et al.Ultra-Deep Desulfurization of Diesel:Oxidation with a Recoverable Catalyst Assembled in Emulsion[J]. Chem-Eur J,2004,10(9):2277-2280.
[5]	ZHANG Li,ZHANG Jian,ZHANG Zulei, Preparation of Magnetic Nanomaterials and Its Adsorption Properties Towards Cr2O72-[J]. Chinese J Appl Chem, 2013, 30(8): 927-931(in Chinese).
[6]	LI Shi,LI Minghui,ZHAI Shangru,et al.Designed Synthesis and Catalytic Applications of Magnetic Solid Acids[J]. Prog Chem,2013,25(2/3):231-247(in Chinese). 李适,李明慧,翟尚儒,等. 磁性固体酸的设计制备及其催化应用[J]. 化学进展,2013,25(2/3):231-247.
[7]	XIONG Xiaolong,LIU Zili,XU Cui,et al.Preparation and Structure Characterization of Superparamagnetic Supported Catalyst H3PW12O40/Fe3O4@SiO2 and Its Application in Olefinic Alkylation Desulfurization[J]. J Chem Ind Eng,2014,65(3):921-928(in Chinese). 熊小龙,刘自力,许翠,等. 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,2104,65(3):921-928.
[8]	Chen L D,Wang X S,Guo H C,et al.Hydroconversion of n-Octane over Nanoscale HZSM-5 Zeolites Promoted by 12-Molybdophosphoric Acid and Ni[J]. Catal Commun,2007,8(3):416-423.
[9]	Chen L D,Wang X S,Guo X W,et al.In Situ Nanocrystalline HZSM-5 Zeolites Encaged Heteropoly Acid H3PMo12O40 and Ni Catalyst for Hydroconversion of n-Octane[J]. Chem Eng Sci,2007,62(16):4469-4478.
[10]	JIANG Chunjie,SUN Shengnan,WANG Xuyang,et al.Synthesis of Dimethyl Ether from Methanol over Heteropoly Acid/Nanocrystalline HZSM-5 Complex Solid Acidic Catalyst[J]. Acta Chim Sin,2013,71(05):810-814(in Chinese). 姜春杰,孙胜男,王旭阳,等. 甲醇脱水制二甲醚的杂多酸/纳米HZSM-5复合固体酸催化剂[J]. 化学学报,2013,71(05):810-814.
[11]	CHEN Lidong,YU Bohao,Li Chuanpeng,et al.Phosphovanadomolybdic Acid/Nanocrystalline HZSM-5 Zeolite Highly Active Hydrofining Catalyst[J]. J Liaoning Normal Univ(Nat Sci Edn),2014,37(3):385-388(in Chinese). 陈立东,于博浩,李传鹏,等. 磷钼钒多酸基固体酸催化剂高效加氢精制FCC汽油[J]. 辽宁师范大学学报,2014,37(3):385-388.
[12]	WANG Xuyang,SONG Pengyue,WANG Xiangsheng,et al.In-situ Characterization and Reactivity of Heteropoly Acid-based Catalysts for Deep Hydrodesulfurization of Fluid Catalytic Cracking Gasoline[J]. Chinese J Appl Chem,2014,31(8):990-992(in Chinese). 王旭阳,宋鹏月,王祥生,等.多酸基深度加氢脱硫催化剂的原位表征和反应性能[J].应用化学,2014,31(8):990-992.
[13]	Zhang H,Xie A,Wang C,et al.Novel r-GO/α-Fe2O3 Composite Hydrogel:Synthesis, Characterization and High Performance of Electromagnetic Wave Absorption[J]. J Mater Chem A,2013,1(30):8547-8552.
[14]	WANG Guanglong,ZHANG Fangjun,ZHANG Baolin. Study on Solid Urea Sulfate[J]. J Zhengzhou Univ(Eng Sci),2006,27(4):32-35(in Chinese). 王光龙,张芳军,张宝林. 固体硫酸脲研究[J]. 郑州大学学报(工学版),2006,27(4):32-35.
[15]	LIU Yuting,CHEN Yanan,XING Yanjun. Synthesis of Quaternary Phosphonium-Polyoxomatalate Room-Temperature Ionic Liquids and Its Photocatalytic Degradation of Rhodamine-B[J]. Chinese J Appl Chem,2014,31(4):431-436(in Chinese). 刘玉婷,陈彦安,邢彦军. 季膦-磷钨酸室温离子液体的合成及光催化降解罗丹明B[J]. 应用化学,2014,31(4):431-436.
[16]	Atia H,Armbruster U,Martin A,et al.Dehydration of Glycerol in Gas Phase Using Heteropolyacid Catalysts as Active Compounds[J]. J Catal,2008,258(1):75-82.
[17]	Li Y S,Church J S,Woodhead A L. Infrared and Raman Spectroscopic Studies on Iron Oxide Magnetic Nano- Particles and their Surface Modifications[J]. J Magn Magn Mater,2012,324(8):1543-1550.
[18]	Maksimov G M. Advances in the Synthesis of Polyoxometalates and in the Study of Heteropolyacids[J]. Russ Chem Rev,1995,64(5):445-461.