氧化脱硫论文：基于多酸催化新材料的燃油深度脱硫研究.doc

氧化脱硫论文：基于多酸催化新材料的燃油深度脱硫研究【中文摘要】随着全球范围内燃料油的使用量不断增大,车用燃料中含硫化合物,已成为大气污染的主要原因。世界范围内已经建立了日趋严格的环保法规,限定车用燃料的硫含量,发展低硫“清洁燃料”已成为必然趋势。氧化脱硫技术,在常温常压操作下,不需要氢源,同时能达到深度脱硫的要求,是一种很有发展潜力的脱硫技术,成为各国研究人员的研究重点。氧化脱硫技术是,在催化剂的作用下,利用氧化剂将有机硫化物转化成极性较强硫化物,再与萃取或吸附等脱硫方法联用,进一步脱除含硫化合物。氧化脱硫催化剂的选择,决定了脱硫效率的高低,因此,选择优良的催化剂对脱硫效果有至关重要的作用。将环境友好型杂多化合物(heteropoly compounds,简写为HPCs)应用于燃料油的催化氧化脱硫,显示了良好的研究开发前景。本文制备不同结构的杂多化合物和复合型杂多化合物,做为氧化脱硫实验催化剂,并以过氧化氢作为氧化剂,考察以上催化剂对油品中含硫化合物的脱除效果,选择出氧化脱硫效果最优的催化剂。通过设计对比实验,优化实验体系。最后,考察了最优催化剂对于真实燃料油品的应用效果。主要内容包括：第一部分,在正辛烷/乙腈双相体系中,以过氧化氢作为催化剂,Keggin结构、Dawson结构以及缺位结构杂多化合物作为催化剂时,考察三个实验体系的氧化脱硫性能,并且分别在每个催化体系中选取最优催化剂。进一步,考察在不同的实验条件下,最优催化剂的脱硫效果,并确定催化剂的最优反应条件。同时验证催化剂,以不同种类的含硫化合物作为处理对象时的脱硫效率第二部分,选取杂多化合物-载体复合型“硅胶负载型杂多酸铯盐”和“笼中船型杂多酸”两种容易回收的催化体系,考察氧化脱硫性能。同样的,在每个催化体系中选取最优催化剂。进一步,考察在不同的实验条件下,最优催化剂的脱硫效果,并确定催化剂的最优反应条件。第三部分,考察以缺位结构杂多化合物Na5、硅胶负载型杂多化合物20% Cs2.5H0.5PW12O40硅胶以及笼中船型杂多化合物作10%PMo-Y为催化剂时,对于真实燃料油品的氧化脱硫性能。每个体系催化剂的实验条件为各自的最佳反应条件。【英文摘要】The presence of sulfur compounds in transportation fuels has been recognized as a major source of SOx which contributes to air pollution, acid rain and damage of exhaust after-treatment devices. With the issues of increasingly stringent legislations on sulfur level in transportation fuels, the development of clean fuels with lower sulfur content has become a globle trend in environmental field. Oxidative desulfurization(ODS), which requires mild conditions as ambient temperature and atmospheric pressure, is one of the most promising desulfurization processes and was focusd by worldwide researchers. In ODS process, organosulfur compounds was oxidized to corresponding polarity sulfoxide and sulfone products. Then the products can be removed by extraction or absorption processes. Particularly, the performance of catalysts determines the desulfurization efficiency. Heteropoly compounds (HPCs), known as green catalysts, are regarded as potential catalysts for deepen desulfurization.In this paper, various structured HPCs and composite type HPCs were prepared and were evaluated with hydrogen peroxide as the oxidant in catalytic oxidative experiment. The catalysts with highest catalytic activiy for ODS were determined selected. Meanwhile, main factors affecting the process were investigated to determine the optimum reaction condition by contrast experiments. Finally, The practical application of the catalyst was exemplified in veritable diesel oil under favorable conditions. The paper is composed of the following three sections.In the first section, the Keggin type, Dawson type and lacunary type HPCs were evaluated as promising catalytic agents for the oxidation of dibenzothiophene with hydrogen peroxide in a normal octane/acetonitrile biphasic system and the representative catalyst with highest activity was chosen in three experiment systems respectively. Furthermore, the key factors affecting the reaction were investigated. The conditions favourable to the reaction were also determined. Meanwhile, the performance of the catalyst for the oxdition of refractory organosulfur compounds was testified in the favourable conditions. In the second section, the supported type Cs2.5H0.5PW12O40/SiO2 and the “ship-in-the-bottle” type HPCs were studied as promising catalytic agents for the oxidation of dibenzothiophene with hydrogen peroxide, and the representative catalyst with highest activity was chosen in the two experiment systems respectively. Furthermore, the key factors affecting the reaction were investigated and the optimum conditions were also determined.In the third section, the practical application of the catalysts, including lacunary type HPCs, supported type Cs2.5H0.5PW12O40/SiO2 and the “ship-in-the-bottle” type HPCs, were exemplified in veritable diesel oil under favorable conditions.【关键词】氧化脱硫 杂多化合物 噻吩 二苯并噻吩 过氧化氢【英文关键词】Oxidative desulfurization Heteropoly compounds Thiophene Dibenzothiophene Hydrogen peroxide【目录】基于多酸催化新材料的燃油深度脱硫研究摘要8-9Abstract9-10第一章 绪论11-331.1 燃油深度脱硫的必然趋势11-121.2 氧化脱硫研究进展12-221.2.1 过氧化氢氧化脱硫法12-191.2.2 有机氧化剂氧化脱硫法19-201.2.3 光催化氧化脱硫法20-221.2.4 等离子体液相氧化脱硫法221.3 杂多化合物简介22-301.3.1 杂多化合物的结构及其特点23-251.3.2 杂多化合物的合成方法251.3.3 杂多化合物的催化特性25-291.3.4 杂多化合物的催化反应29-301.3.5 小结301.4 小结30-311.5 本课题研究内容31-33第二章 多酸化合物的制备和表征33-402.1 多酸化合物的制备33-352.1.1 主要试剂和药品33-342.1.2 主要实验仪器342.1.3 样品的制备34-352.2 多酸催化新体系的表征与分析35-402.2.1 分析仪器352.2.2 样品的表征与分析35-40第三章 不同结构杂多化合物对含硫化合物脱硫性能研究40-553.1 实验仪器与方法40-423.1.1 主要实验仪器与试剂40-413.1.2 实验方法与评价体系41-423.2 Keggin结构杂多化合物对含硫化合物的脱除42-433.3 Dawson结构杂多化合物对含硫化合物的脱除43-483.3.1 催化剂的选择43-443.3.2 影响催化氧化脱硫率的反应条件44-473.3.3 其他含硫化合物47-483.4 缺位结构杂多化合物对含硫化合物的脱除48-543.4.1 催化剂的选择49-503.4.2 影响催化氧化脱硫的反应条件50-533.4.3 其他含硫化合物53-543.5 本章小结54-55第四章 复合型杂多化合物对含硫化合物脱硫性能研究55-664.1 硅胶负载型杂多酸铯盐对含硫化合物的脱除55-594.1.1 催化剂的选择55-564.1.2 影响催化氧化脱硫的反应条件56-594.2 笼中船型杂多酸对DBT的脱除59-654.2.1 催化剂的选择59-