【作者】 李翔宇；

【导师】 赵地顺；

【作者基本信息】 河北科技大学 ， 化学工艺， 2007， 硕士

【摘要】 近年来随着原油资源的减少，大量的重质、劣质原油被开采使用，直接造成了催化裂化柴油中含硫化合物的增加。这些含硫化合物燃烧时生成的硫的氧化物会造成严重的环境污染。随着柴油发动机用量的增加，开展催化裂化柴油脱硫技术的研究已成为当务之急，催化裂化柴油的低硫清洁化问题亟需解决。为了生产出超低硫水平的燃料，早期的加氢脱硫工艺要求在严格的条件下进行，包括高温、高氢压、高活性的催化剂以及更长的反应时间。由于这些限制，非加氢脱硫的研究工作具有重要的理论和实践意义，其中选择性氧化脱硫由于具有投资小、工艺简单、工艺条件温和、脱硫效果明显等特点，受到了炼油行业的极大关注，我们采用氧化-萃取脱硫工艺对催化裂化柴油进行了选择性氧化脱硫的研究，并着重研究了空气作为氧化剂的氧化脱硫工艺。本实验在常压条件下，分别设计并研究了三种脱硫方案：催化裂化柴油双氧水氧化脱硫工艺；催化裂化柴油空气氧化脱硫工艺；相转移催化氧化脱硫工艺。通过考察氧化时间、氧化温度、催化剂、相转移催化剂的制备筛选、相转移催化剂的加入量等工艺条件对脱硫率的影响，结合氧化脱硫后的谱图进行分析。结果表明：1、无相转移催化剂存在时，氧化-萃取脱硫工艺中柴油的脱硫率和收率是一对矛盾；2、相转移催化剂存在时，一方面避免了有效氧化剂和催化剂的溶剂化效应，一方面以相转移的形式把催化剂和有效氧化剂及时转移到油相，促进了氧化反应的进行，使催化裂化柴油的脱硫率大幅度提高。本实验最优的脱硫工艺条件为：空气为氧化剂，磷钼酸相转移催化剂，在50℃下，反应2h，气速120h·L^-1，柴油的脱硫率达88.2％，此时柴油的收率达90％以上。更多还原

【Abstract】 With the decrease of crude oil resources, a lot of low quality crude oil which contains more sulfur compounds is exploitated which caused the increase of sulfur compounds in Fluid Catalytic Cracking diesel directly. Those sulfur compounds will make more sulfoxides, which are the main fact of environment pollution. With the increase of diesel engines, it is very time to do research on desulphudzation technology of Fluid Catalytic Cracking diesel. The demand of low-sulfur clean Fluid Catalytic Cracking is urgent.At early time, for the production of ultra low-sulfur fuel, hydrogen desulphurization should be taken such as high temperature, high hydrogen pressure, highly active catalyst and longer reaction time. Since the limitation above, working on non-hydrogen desulphurization took a great significance both on theoretical and practical. Among various methods, researcher focus on the selective oxide desulphurization because of low-level investment, simple process, mild process condition, obvious desulphurization effort. So we started selective oxide desulphufization research on Fluid Catalytic Cracking diesel and made a discussion on the air effort as oxidant.On normal atmosphere, we took the research on: hydrogen peroxide oxide desulphurization on Fluid Catalytic Cracking diesel, air oxide desulphufization on Fluid Catalytic Cracking’ diesel and phase transfer catalysis oxide desulphurization. We investigated the influence on desulphurization rate caused by oxidization time, temperature, sort of catalyst accelerator, quantum of phase transfer catalysis, usage of phase transfer catalysis, and so on. And we analyzed the spectrum after oxide desulphurization. Then we made the conclusion as below:At oxide-extraction desulphurization,1. Without phase transfer catalysis, it’s a contradiction between desulphurization rate and yisld while mass’ use of extractant inceased the cost.2. With phase transfer catalysis, it can avoid the solvating effort between effictive oxide agent and catalyst. Otherwise, phase transfer catalysis can transfer the effictive oxide agent and catalyst to oil phase which promote oxide reaction and incease the desulphurization rate of Fluid Catalytic Cracking diesel.The final desulphurization process we chose is on condition of: air as oxide; phosphomolybdic acid phase transfer catalyst; at 50℃; 2 hours; air flow speed 120 L/h. Finally we got the reault were the desulphurization rate wae 88.2% and yield wae above 90%.更多还原