“枣糕状”结构杂多酸离子液体负载磁性复合材料的制备及超声脱硫的催化性能

doi:10.11896/cldb.20050031

材料导报

2021, Vol. 35

Issue (12): 12181-12189 https://doi.org/10.11896/cldb.20050031

高分子与聚合物基复合材料

“枣糕状”结构杂多酸离子液体负载磁性复合材料的制备及超声脱硫的催化性能

陈定宁^1,2, 沈昊宇¹, 成瑾瑾¹, 胡美琴¹

1 浙大宁波理工学院,宁波 315100
2 浙江大学化学工程与生物工程学院,杭州 310058

Preparation of Jujube-cake-like Structured Heteropoly Acid Ionic Liquids Supported Magnetic Composite and Its Catalytic Property for Ultrasound-assisted Desulfurization

CHEN Dingning^1,2, SHEN Haoyu¹, CHENG Jinjin¹, HU Meiqin¹

1 NingboTech University,Ningbo 315100, China
2 College of Chemistry and Biological Engineering, Zhejiang University, Hangzhou 310058, China

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摘要石油中的含硫化合物不仅影响油品质量,其燃烧生成的硫氧化物(SO_x)还会对生态环境和人类健康构成极大威胁。此外,燃油中的硫化物燃烧使得燃油尾气处理设备中催化剂中毒,从而排放一些其他有害的汽车尾气,如氮氧化物(NO_x)、碳氢化合物和一氧化碳(CO)等。为了降低燃油中的硫含量,世界各国政府都颁布了严格的标准,如美国环保署在2006年将柴油中的硫含量降低到15 mg/kg;2007年欧盟和日本将柴油中的硫含量上限设定为10 mg/kg 。自2017年起,我国政府发布了国V标准,将柴油中的硫含量限制在10 mg/kg以下。随着各项政策的出台,如何通过高效深度脱硫技术降低石油中的硫含量已成为石油化工领域的研究热点。同时,超深脱硫在解决工业废物再利用中也发挥着重要作用。
目前常用的深度脱硫的方法主要有加氢脱硫(HDS)和非加氢脱硫(NHDS)。由于传统的HDS方法存在去除噻吩类物质困难、成本高、条件苛刻、耗时耗能等缺点,NHDS以其低能耗、环保等优点逐渐受到人们的青睐。NHDS技术包括氧化脱硫、吸附脱硫、萃取脱硫和生物脱硫等。其中,氧化脱硫可以通过氧化剂将有机硫化物转化为砜或亚砜,提高有机硫化物在极性溶剂中的溶解度,通过萃取和蒸馏等方法将有机硫化物从石油中分离出来,达到深度脱硫的目的。与机械搅拌、生物或光催化氧化脱硫等传统脱硫方法相比,超声辅助氧化脱硫法是反应时间最短、效率最高的方法之一。
近年来,离子液体因良好的热稳定性和化学稳定性而受到越来越多的关注,并被广泛应用于催化氧化脱硫。在杂多酸中引入离子液体可以形成具有氧化活性中心的杂多酸离子液体,有望表现出优异的催化活性。Xun等采用溶胶-凝胶法制备了杂多酸离子液体催化剂(SiW₁₂O₄₀-IL),该催化剂在脱硫方面具有优异的催化活性,当温度为60 ℃,n(O)/n(S)为4时,其脱硫率达到99.9%。然而,作为均相催化剂,杂多酸离子液体也存在回收率低、可重复利用性差等缺点,因此选择合适的固载化方法,实现杂多酸离子液体催化剂的异相化十分关键。常用的载体有SiO₂、Al₂O₃、Fe₃O₄等,其中磁性复合材料可以实现催化剂和油样在磁场作用下的快速分离,已成为目前最为流行的载体之一。将磁性复合材料通过改性结合到催化剂上,有望得到具有较高的脱硫催化活性和优异分离效果的催化剂。为此,本研究设计并成功合成了一种具有“枣糕状”结构的、杂多酸离子液体[BMIM]₃PW₁₂O₄₀负载的三乙烯四胺(TETA)功能化的Fe₃O₄复合材料([BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA)。以正辛烷为模拟油样,二苯并噻吩为硫源,过氧化氢为氧化剂,[BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA为催化剂,通过超声协助考察了催化剂的催化氧化脱硫。采用响应面法(RSM)研究了超声时间、H₂O₂用量、反应温度对催化剂脱硫的影响;并考察了催化剂的稳定性和再生性能。对[BMIM]₃PW₁₂O₄₀/Fe₃O₄@ TETA的脱硫机理进行了初步探讨,结果表明,采用0.025 g [BMIM]₃PW₁₂O₄₀/Fe₃O₄@ TETA对50 mL浓度为500 mg/g的二苯并噻吩的模拟油样进行脱硫实验时,最佳脱硫条件为:反应温度325 K,超声时间15 min,n(O)∶n(S)=8∶1,脱硫率可达96.5%。该催化剂重复使用五次后,脱硫率仍保持在93.7%,表明[BMIM]₃PW₁₂O₄₀/Fe₃O₄@ TETA具有良好的催化脱硫性能,可以重复使用。初步的脱硫机理研究表明,[BMIM]₃PW₁₂O₄₀/Fe₃O₄@ TETA的催化活性中心可能为其含有的杂多酸阴离子;Fe₃O₄@TETA起到载体的作用,而离子液体起到协同增强作用。

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关键词: 杂多酸离子液体磁性复合材料 “枣糕状”结构氧化脱硫响应面法(RSM)

Abstract: Heteropoly acid ionic liquid [BMIM]₃PW₁₂O₄₀ was firstly synthesized, followed by being loaded on the triethylenetetramine-functionalized Fe₃O₄ (Fe₃O₄@TETA) via ultrasonic impregnation. A jujube-cake-like structure magnetic composite, i. e., [BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA was obtained. It was characterized by FTIR, XRD, VSM, XPS, TEM and SEM and used as catalyst for the oxidation of n-octane simulated oil samples with dibenzothiophene as sulfur source, via hydrogen peroxide as oxidant. The effects of ultrasonic time, H₂O₂ usage amount, and reaction temperature were investigated via the response surface methodology (RSM). The results showed that the optimized catalytic degradation rate reached 96.5% when 0.025 g [BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA was used for the desulfurization of 50 mL simulated oil sample with the concentration of dibenzothiophene at 500 mg/g. The optimum desulfurization rate was obtained when the ultrasound time was at 15 min with n(O)∶n(S) at 8∶1 and reactive temperature at 325 K. After being reused for 5 times, the catalytic degradation rate can still remained 93.7%, which indicated that the [BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA was of good catalytic desulfurization performance and can be reused. The primary desulfurization mechanism study showed that the catalytic active center might be the heteropoly acid anion of the [BMIM]₃PW₁₂O₄₀/Fe₃O₄@TETA, with the Fe₃O₄@TETA as a supporter and the ionic liquid as a cooperative enhancer, respectively.

Key words: heteropoly acid ionic liquids magnetic composite material jujube-cake-like structure oxidative desulfurization response surface methodology (RSM)

出版日期: 2021-06-25 发布日期: 2021-07-01

ZTFLH:

TB332

基金资助: 北京教委重点项目(KZ201810005008)

通讯作者: hyshen@nit.zju.edu.cn

作者简介: 陈定宁,2019年6月毕业于湖南科技大学。目前为浙江大学与浙大宁波理工学院联合培养的硕士研究生,主要从事废水净化和离子色谱柱填料制备的研究。
沈昊宇,1999年6月毕业于南开大学。目前为浙大宁波理工学院教授,主要从事纳米功能材料及其在环境化学中的应用研究。

引用本文:

陈定宁, 沈昊宇, 成瑾瑾, 胡美琴. “枣糕状”结构杂多酸离子液体负载磁性复合材料的制备及超声脱硫的催化性能[J]. 材料导报, 2021, 35(12): 12181-12189.
CHEN Dingning, SHEN Haoyu, CHENG Jinjin, HU Meiqin. Preparation of Jujube-cake-like Structured Heteropoly Acid Ionic Liquids Supported Magnetic Composite and Its Catalytic Property for Ultrasound-assisted Desulfurization. Materials Reports, 2021, 35(12): 12181-12189.

链接本文:

http://www.mater-rep.com/CN/10.11896/cldb.20050031 或 http://www.mater-rep.com/CN/Y2021/V35/I12/12181

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