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汽油吸附法深度脱硫吸附剂研究

Study on the Adsorbents for Remove Sulfur in FCC Gasoline

【作者】 韩雪莲

【导师】 董群;

【作者基本信息】 大庆石油学院 , 化学工艺, 2003, 硕士

【摘要】 实验以FCC汽油为原料,用燃灯法测定脱硫前后汽油的总硫含量,用酸性硫酸镉溶液萃取法确定硫化氢的含量,用电位滴定法测定硫醇硫的含量,用硝酸汞络合法测定硫醚硫的含量,用差减法测定噻吩及其它硫化物的含量。常温常压下,采用静态吸附法评价了吸附剂的制备条件、吸附时间和剂油比等吸附条件对吸附剂脱硫性能的影响。通过比较不同的吸附剂基质对汽油中硫化物的脱除效果,发现影响吸附剂脱硫率的因素有:吸附剂的类型、极性、硅铝比(分子筛型吸附剂)、结构、以及比表面积等。对于同类吸附剂来说比表面积大,孔隙率高,孔道结构简单,硅铝比高有利于吸附硫化物。不同类型的吸附剂基质脱硫效果差别较大。分子筛类吸附剂脱硫效果最好,其次是活性白土和活性炭纤维,氧化铝和离子树脂脱硫效果较差。考察了HZSM-5、USY、13X和5A四种吸附剂对硫醇的脱除能力,它们的脱硫醇率由大到小为USY>13X>HZSM-5>5A,用吡啶-TPD法测定了这四种吸附剂的表面酸性后,推测对吸附剂脱硫醇起主要作用的是吸附剂的弱酸位。实验中还考察了不同金属离子对HZSM-5、USY、活性白土和γ-Al2O3的改性效果,Fe的改性效果最好,其次是K和其它一些过渡金属,碱土金属的改性效果相对较差。对1%Fe-USY进行了动态吸附实验研究。常温常压下,考察了空速、高径比等对吸附剂脱硫效果的影响以及吸附剂的吸附容量。确定了床层高径比为5,适宜空速为1.0h-1,吸附硫容为1146μg/g。用两种方法对1%Fe-USY吸附剂进行了再生实验,用水加热再生要比直接加热再生效果好。

【Abstract】 The properties of different adsorbents for remove sulfur in FCC gasoline were studied. The total sulfur in the gasoline was measured using burning-lamp method and the amount of hydrogen sulphide was determined with acidic cadmium sulphate. The amount of mercaptan was determined by electric potential titration and the thio-ether was measured by complexometric titration with mercury nitric. Preparation condition, adsorption time, ratio of adsorbent to gasoline etc. were studied at normal temperature and atmospheric pressure in static experiment. The desulfurization results showed that it’s the type, surface polarity, relative surface area, structure and SiO2/Al2O3 (molecule sieves) of adsorbent affect the desulfurization. For the same type adsorbent, the degree of desulfurization increases with the increase of relative surface area, porosity and amount of weak acid. The most effective adsorbent is molecule sieves, the worst one are Al2O3 and cation resin. The desulfurization capability of HZSM-5, USY, 13X and 5A for mercaptan is USY>13X>HZSM-5>5A. The Pyridine-TPD results showed that their desulfurization capability should contribute to weak acidity sites. HZSM-5,USY, active clay and Y -Al2O3 were modified by different metal cations. The most effective modify metal is Fe and the alkali metals gave the worst results. The proper content of Fe on USY is about 1%. l%Fe-USY was used in the dynamic experiment. The suitable rate of highness/diameter is 5, WHSV is about l.0h-1 and the capability of adsorbent is about 1.15mg/g. Adsorbent was impregnated by water before baked is better than baked directly when the adsorbent was regenerated.

【关键词】 FCC汽油吸附吸附剂脱硫USY分子筛
【Key words】 FCC gasolineadsorptionadsorbentdesulfurizationUSY molecule sieves
  • 【分类号】TE624.55
  • 【被引频次】8
  • 【下载频次】940
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