金属酞菁催化氧化脱除油品中的硫化物

发布时间：2018-01-23 14:21

本文关键词： 十六氯铁酞菁二苯并噻吩吡啶双氧水高价铁活性种　出处：《浙江理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：随着环境污染愈加严重,世界各国政府环保意识加强,纷纷制定更加严格的汽油、柴油含硫标准,燃料油的超深度脱硫成为世界性亟待解决的问题。目前成熟应用于工业化的脱硫方法是加氢脱硫,但是该方法反应过程需要高温高压,并且无法脱除二苯并噻吩及其衍生物等含硫化合物,因此,非加氢脱硫方法成为研究热点。卟啉是酶活性成分之一,众所周知,酶在温和条件下能高效选择性催化目标物,但是其化学稳定性以及热稳定性不高,金属酞菁结构类似卟啉,具有出色的化学稳定性,耐酸耐碱,耐光辐射等,而且合成过程简单,价格便宜,因此,本文利用十六氯铁酞菁(FePcCl_(16))设计仿生催化脱硫体系。首先,制备FePcCl_(16),通过紫外可见光、傅里叶红外等分析仪器对其结构进行表征,确定合成的产物为FePcCl_(16)。其次,考察了催化剂用量、水油比、氧硫比等因素的影响,确定最佳工艺条件。结果表明,在30°C,催化剂用量为15mg,氧硫比n(O/S)=40,水油比n(H2O/oil)=2,催化剂和吡啶的物质的量比n(catalyst/pyridine)=1:100的条件下反应1 h,它们对原始含硫量为200 ppm模拟油脱硫率能达到100%。通过阿伦尼乌斯公式计算得到本催化脱硫反应的活化能为25.5 KJ/mol,表明该反应进行仅仅需要少量的能量。循环反应测试发现,循环反应23次后,脱硫率仍能达到99%以上,表明本催化体系稳定,循环性能优异。然后,本文研究了本催化体系的催化氧化脱硫机理,研究发现,自由基不参与反应,而高价铁是本催化反应的反应活性种,配体吡啶在反应过程中扮演重要的角色,吡啶有利于FePcCl_(16)活化H2O2形成的中间体倾向于异裂,形成更多的高价铁活性种。最后,本文用FePcCl_(16)催化剂对吖啶等含氮化合物的脱除进行了初步探索,研究结果表明FePcCl_(16)催化剂不仅能脱除油品中的含硫化合物,而且也能脱除含氮化合物。
[Abstract]:With the increasingly serious environmental pollution, governments around the world have strengthened their awareness of environmental protection, and have formulated more stringent standards for sulfur in gasoline and diesel. The ultra-deep desulfurization of fuel oil has become an urgent problem in the world. At present, the mature desulfurization method is hydrodesulfurization, but the reaction process needs high temperature and high pressure. And the sulfur compounds such as dibenzothiophene and its derivatives can not be removed. Therefore, non-hydrodesulfurization method has become a research hotspot. Porphyrin is one of the active components of enzyme, which is well known. The enzyme can catalyze the target compound efficiently and selectively under mild conditions, but its chemical stability and thermal stability are not high, the structure of metal phthalocyanine is similar to porphyrin, it has excellent chemical stability, acid and alkali resistance, light radiation resistance and so on. Moreover, the synthesis process is simple and the price is cheap. Therefore, the bionic catalytic desulfurization system is designed by using 16 FePcClN (FePcCl1 / 16). First, FePcClS16) is prepared. The structure of the product was characterized by UV-Vis and FTIR, and the synthesized product was determined as FePcClS16. Secondly, the amount of catalyst and the ratio of water to oil were investigated. The results show that the catalyst dosage is 15mg, the ratio of oxygen to sulfur is 40, and the ratio of water to oil is n H 2O / oil. The mass ratio of catalyst to pyridine is 1: 100 and the ratio of catalyst to pyridine is 1: 100. The desulfurization efficiency of the simulated oil with the original sulfur content of 200 ppm can reach 100 and the activation energy of this catalytic desulfurization reaction is 25.5 KJ/mol calculated by the Arrhenius formula. The results showed that the reaction needed only a small amount of energy. After 23 times of cyclic reaction, the desulfurization rate was still over 99%, which indicated that the catalytic system was stable and had excellent cycling performance. In this paper, the mechanism of catalytic oxidation and desulfurization was studied. It was found that free radicals did not participate in the reaction, and high valence iron was the reactive species of the catalytic reaction, and the ligand pyridine played an important role in the reaction process. Pyridine is favorable to FePcClC16) the intermediates formed by activating H2O2 tend to be heterolysis and form more active species of high valence iron. Finally. In this paper, the removal of nitrogen-containing compounds such as acridine was studied with FePcClS16) catalyst. The results show that the FePcCl-1 _ (16) catalyst can not only remove the sulfur compounds in the oil, but also the nitrogen-containing compounds.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TE624.55

【相似文献】