【作者】 孙剑峰；

【导师】 刘建忠； 王智化；

【作者基本信息】 浙江大学 ， 能源环境工程， 2010， 硕士

【摘要】 采用普通浸渍法、超声浸渍法和溶胶凝胶法三种方式制备高温煤气脱硫剂,通过ICP、SEM、XRD、氮吸附等手段对脱硫剂进行表征,并在一立式固定床上进行活性评价。得出结论如下：(1)采用超声浸渍法和普通浸渍法制备铁、锰、铜、锌、铈、钙六种物系脱硫剂,ICP-AES结果表明超声浸渍不仅缩短了浸渍时间,还促进了活性成分的负载。BET分析结果和粒径分布曲线表明,超声浸渍丰富了脱硫剂的孔隙结构,增加了比表面积和孔容,并具有细化颗粒的效果。SEM结果显示,超声浸渍制备得到的脱硫剂颗粒较小而且分布均匀,烧结程度较轻。XRD分析表明超声浸渍对脱硫剂的晶粒分布状态有影响。在固定床上对所有脱硫剂进行活性评价,结果表明超声波浸渍法制备得到的脱硫剂的穿透硫容有显著提高。6种物系的脱硫穿透硫容比较结果为：Mn>Fe>Cu>Ce>Ca>Zn,但超声波处理后Fe的穿透硫容提高最为明显。(2)采用超声浸渍法分别制备Mn/SiO2、Mn/TiO2、Mn/γ-Al2O3三种高温煤气脱硫剂,研究载体对于脱硫剂活性的影响。三种载体的比较研究表明,Mn/γ-Al2O3比表面积大,脱硫活性大,能满足IGCC中硫化氢的净化要求,是一种较好的高温煤气脱硫剂。而Mn/SiO2不能较长时间维持硫化氢在低浓度,Mn/TiO2高温稳定性差。(3)采用溶胶凝胶法和超声浸渍法分别制备相同负载的锰系脱硫剂,并对其进行表征和活性评价,得出结论：溶胶凝胶法制备得到的脱硫剂孔隙更为丰富,具有良好的微观结构,XRD测试结果显示其活性成分在载体上的分布更为均匀,能够更好的进行脱硫反应。溶胶凝胶法制备得到的脱硫剂活性比相同负载下的超声浸渍法制得的脱硫剂来得高。温度越大,脱硫剂活性增大,但是涨幅并不大。总体上讲,溶胶法具有较为优良的性能,各种参数比超声浸渍来得好；但是,由于其制备工艺较为复杂,费用高,目前难以在工业化推广应用。更多还原

【Abstract】 Hot-gas desulfurization sorbents were prepared by three methods respectively, including ultrasound-assisted impregnation method, classical impregnation method and sol-gel method. The physical and chemical properties of sorbents were analyzed by means of ICP-AES, SEM, and XRD. The desulfurization activities of high temperature desulfurization sorbents were studied in a fixed-bed reactor. The results are as follows.(1) Six hot-gas desulfurization metal sorbents including Fe, Mn, Cu, Ce, Ca and Zn were prepared by an ultrasound-assisted impregnation method and by a classical impregnation method. ICP results showed that the use of ultrasond increased the content of active ingredient in the sorbents, improved the pore structure, and thinned the particles. SEM results revealed that the sorbents was small in granule, uniform grading and less sintering with ultrasonic treatment. XRD results showed that the use of ultrasond had an affect on the dispersion of crystal grain. The activity test results indicated that the desulfurization activity of the sorbents prepared by ultrasound impregnation was much higher than those without ultrasonic treatment, especially for the Fe sorbent. The desulfurization activity order of the six metal sorbents is Fe>Mn>Cu>Ce>Ca>Zn.(2) Three hot-gas desulfurization metal sorbents including Mn/SiO2, Mn/TiO2, and Mn/γ-Al2O3, were prepared by ultrasound-assisted impregnation method for the purpose of studying the effect of the carrier. The carrier study showed that, Mn/γ-Al2O3 got higher BET surface area and better performance, was fit for IGCC hot-gas desulfurization. But Mn/SiO2 cannot keep the H2S concentration at a low level in a long time, and Mn/TiO2 was bad in high temperature stability.(3) Mn desulfurization sorbents were prepared by an ultrasound-assisted impregnation method and a sol-gel method with the same load. The sol-gel method got higher BET surface area, better performance and activity. XRD results showed that Mn active ingredient was in uniform distribution, which is good for the desulfurization reaction. The activities of the sorbents increased with the increasing of the temperature. In short, sol-gel method gets better performance, but in high price and with difficult preparation. It is still difficult to get a widely industry application now.更多还原