羧基取代酞菁键合MCM-41的合成及其去除乙硫醇的催化活性研究

【作者】 薛科创；

【导师】 张维萍；

【作者基本信息】 西北大学 ， 材料化学， 2011， 硕士

【摘要】 由于环境问题的加剧,除去大气中SOx迫在眉睫。这些SOx主要来自于油品中含硫化合物(硫醇、硫醚、噻吩、苯并噻吩以及二甲基苯并噻吩等)的燃烧。因此,除去油品中的含硫化合物成为首要任务。本文选用航空煤油做溶剂,以邻苯二甲酸和邻苯二甲酸酐的衍生物为前驱体,采用溶剂法合成了四羧基酞菁TCPcM (M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ)),2-羧基不对称酞菁CPcM(M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ))以及双核六羧基酞菁BNHCPcM(M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ))三大系列共24种化合物,通过元素分析、紫外可见光谱和红外光谱对其进行了表征。此外,还合成了一种全新的四(4-羧基)苯胺基酞菁钴,以相同的方法对其进行了表征。在水热条件下合成了全硅介孔分子筛MCM-41,测得其比表面积可以达到953.81 m2/g,孔径2.41 nm,孔容0.7242 ml/g。然后将合成的酞菁键合在介孔分子筛MCM-41上,红外光谱、X-ray粉末衍射以及X-ray光电子能谱都对键合结果进行了证实。以乙硫醇的石油醚溶液为模拟对象,通过非均相滴定法测定了乙硫醇的去除率,从实验结果可以看出：(1)MCM-41-NH-BNHCPcM的催化活性是最高的,MCM-41-NH-CPcM的催化活性是最低的。MCM-41-NH-TCPcM的催化活性介于MCM-41-NH-BNHCPcM和MCM-41-NH-CPcM之间。(2)MCM-41-NH-BNHCPcCo的催化性能是最好的,其去除率可以达到92.74%。更多还原

【Abstract】 Because the environmental problem becomes more severe, removing the SOx in the air is a necessitous assignment. These sulfur compounds (SOx) are generated from the combustion of sulphur-containing compounds in crude oil, such as mercaptans, sulphides, thiophenes, benzothiophenes and their alkyl-substituted phthalic anhydride. Removing these sulphur compounds becomes a chief mission.Firstly, in this paper, aviation kerosene using as a solvent and the phthalic anhydride of o-phthalic acid and phthalic anhydride as precursors, tetracarboxyl-phthalocyanines (TCPcM) (M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ)),2-carboxylphthalocyanines (CPcM) (M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ)) and binuclear hexacarboxylphthalocyanines (BNHCPcM) (M=2H, Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ), Fe(Ⅱ), Mn(Ⅱ), Cr(Ⅲ)) were synthesed, and their structures were determined by element analysis, UV-Vis and FT-IR. A new phthalocyanine was synthesed and its structure was characterized by element analysis, UV-Vis and FT-IR.Secondly, mesoporous molecular sieve (MCM-41) of pure silicon was synthesed by hydrothermal method, and its BET surface area, the pore size and pore volume is 953.81 m2/g,2.41 nm and 0.7242 ml/g, respectively. Then, the phthalocyanines were anchored onto MCM-41 and were confirmed by FT-IR, XRD and X-ray photoelectron spectroscopy.Finally, using the petroleum ether solution dissolving ethanethiol as a simulative object, the catalytic activity of removing ethanethiol was tested, showing that:(1) The catalytic activity of MCM-41-NH-BNHCPcM is higheset, and MCM-41-NH-CPcM is lowest. The catalytic activity of MCM-41-NH-TCPcM is between MCM-41-NH-BNHCPcM and MCM-41-NH-CPcM.(2) The catalytic activity of MCM-41-NH-BNHCPcCo for removing ethanethiol is the best, reaching 92.74%.更多还原