【作者】 唐克；

【导师】 孙兆林；

【作者基本信息】 兰州大学 ， 分析化学， 2006， 博士

【摘要】 吸附脱硫是近些年兴起的一种燃料油脱硫方法，因其可在较低的压力和温度下进行受到了各国高度重视，但如何寻找高效的吸附剂是该方法成功与否的关键。采用杂原子分子筛作为吸附剂进行吸附脱硫有可能得到较好的效果和新的机理。 本论文采用液-固相同晶取代的方法将镓引入到Y型分子筛骨架中，首次利用合成的杂原子分子筛（[Ga]AlY）对含有不同硫化物的模拟燃料进行了吸附脱硫研究。同时采用分子模拟方法计算了各含硫化合物中硫原子上的电荷数，并将硫原子上的电荷数与各含硫化合物的穿透吸附容量相关联，对[Ga]AlY分子筛的吸附脱硫机理进行了深入研究；研究了CeMCM-41的吸附脱硫性能；以介孔碳纳米管为惰性基体，采用限定空间尺寸法成功合成了纳米NaY分子筛。各章内容分别概述如下： 第一章介绍了国内外燃料油脱硫进展，详细介绍了吸附脱硫方法的原理、方法和研究进展，同时还介绍了杂原子分子筛的合成方法及应用。 第二章合成了相对结晶度大于95％的NaY分子筛，NaY分子筛经多次NH₄⁺交换后得到NH₄Y分子筛。以合成的NH₄Y分子筛为原料，采用液-固相同晶取代方法制备了不同镓含量的镓化Y型分子筛。合成样品经XRD表征，[Ga]AlY的晶胞参数由NH₄Y原粉的2.547nm增加到2.656nm，这充分说明镓已经取代分子筛骨架中的铝进入了骨架。IR分析表明[Ga]AlY分子筛中的铝含量降低造成反对称伸缩震动频率向高频移动。ICP结果表明，Al含量由NH₄Y的11.9％下降到[Ga]AlY的8.8％，[Ga]AlY的Ga含量为4.3％。IR和ICP结果进一步说明了Ga取代了骨架中的一部分Al。随着合成体系中氟镓酸铵加入量的增加，进入Y型分子筛骨架的镓量也增加，但镓最多可以取代分子筛骨架中约1／3的铝。[Ga]AlY的BET比表面积为799.9m²／g，与原料NH₄Y相比几乎没有变化，平均孔径和孔容与NH₄Y的相同分别为0.63nm和0.34cm³／g。 第三章详细研究了[Ga]AlY分子筛的吸附脱硫性能。采用[Ga]AlY分子筛处理含烯烃或芳烃的模拟燃料时，烯烃和芳烃对脱除噻吩硫和四氢噻吩中的硫都有较大影响，主要是烯烃和芳烃与[Ga]AlY分子筛中的活性吸附位间形成π络合作用而占用大量的吸附位。处理其它含硫量500μg／g的模拟燃料时，每克更多还原

【Abstract】 Adsorptive desulfurization was a new method to remove sulfur compounds from the transportation fuels. The governments in many countries had paid attention to adsorptive desulfurization in that it would be accomplished at lower temperature and pressure. The success in this method, however, depended on the development of highly selective adsorbents. It was possible to obtain fine results and new mechanism if the heteroatom zeolites could be used to adsorption desulfurization.In this paper, the introduction of heteroatom gallium into the framework of a Y zeolite by the isomorphous substitution method had been reported and the desulfurization of various model fuels over the synthesized Y zeolite （[Ga]AlY） was studied. The charge on S atom of sulfide, calculated by using molecule simulation, was correlated to the sulfur adsorption capacity. The desulfurization over the synthesized CeMCM-41 zeolite was studied. At last, nanosized NaY zeolite had been synthesized inside the mesopore of carbon nanotube. A brief introduction was given as follows:In chapter 1, the adsorption desulfurization development was described in detail, The application and the synthesize method of the heteroatoms zeolites were also introduced.In chapter 2, NaY zeolite whose crystallinity was greater than 95% was synthesized . The NH4Y zeolite could be obtained by several times cation exchange of the NH₄⁺ form. [Ga]AlY with different content of gallium was synthesized from raw material NH4Y by using isomorphous substitution of heteroatoms. The cell parameter of [Ga]AlY, determined by XRD using the internal standard method, was 2.656 nm and that of NH₄Y was 2.547 nm, implying that the Ga atoms had been introduced into the framework of Y zeolite. The internal tetrahedral symmetrical stretching of IR showed a blue shift due to the substitution Ga for Al. ICP analysis showed that the aluminium content decreased from 11.9% for the NH4Y to 8.8 % for the [Ga]AlY. While the gallium content of [Ga]AlY was 4.3%. The results of ICP and IR indicated further that Ga had been substituted into the faujasitic framework.更多还原