Influence of N- and O-containing heteroatoms on the continuous desulfurization of heavy oils and liquid fuels using catalytic oxidation of organic compounds with aqueous polyoxometalate solutions

基于我们成功的初步研究，萃取氧化脱硫的液体燃料与原位产品分离（ECODS），后续项目的总体目标是将以前开发的技术扩展到更多的杂原子从燃料中分离，并从根本上了解它们对脱硫的影响。关于新开发的方法的技术实施，两个反应步骤的空间分离（通过氧气的底物氧化，用氧气负载催化剂水溶液）也应该在连续的过程中进行。在以前非常成功的项目中，一种高效的氧化-萃取脱硫系统，（HPA-5水溶液）被发现作为迄今为止非均相催化加氢脱硫的工业方法的替代。我们的系统的优点是所有脱硫产物（硫酸、磺酸、羧酸）都是从有机相原位提取到水相的。这一点在模型油和真实的油中都能得到证实。继续研究的关键是我们新开发的用于液体燃料原位脱硫的反应系统（HPA-5水溶液）具有有效脱硫芳香族和脂肪族体系的潜力。然而，已发现分解产物在水相中的积累抑制催化剂体系。这可以通过添加草酸来避免。基于这些有希望的结果，进一步的调查（如计划中的延续建议）是必要的燃料中的含N和O的成分对脱硫的影响。因此，例如，含N燃料组分如吲哚或喹啉可以对我们的催化剂体系具有类似的活化作用，这可以显著有助于我们概念的技术实施。因此，在该提案的延续中，应从根本上研究各种含N和O组分对液体燃料的氧化-萃取脱硫的影响。为此，应研究和了解基于适当的模型物质的影响，例如脱氮作用对燃料脱硫的影响。这种方法有可能进一步提高我们新开发的脱硫技术，理想情况下，联合收割机与从液体燃料中去除更多杂原子相结合。

Based on our successful preliminary investigations on the extractive-oxidative desulfurization of liquid fuels with in-situ product separation (ECODS), the overall goal of the follow-up project is to extend the previously developed technology to the separation of further heteroatoms from fuels and to fundamentally understand their effect on desulfurization. With regard to a technical implementation of the newly developed method, a spatial separation of the two reaction steps (substrate oxidation by oxygen, loading of the aqueous catalyst solution with oxygen) should also be carried out in a continuous process.In the previous, very successful project, an efficient system for oxidative-extractive desulfurization (aqueous HPA-5 solution) was found as an alternative to the hitherto industrial process of heterogeneously catalyzed hydrodesulfurization. The advantage of our system is that all desulfurization products (sulfuric acid, sulfonic acids, carboxylic acids) are extracted in-situ from the organic to the aqueous phase. This could be shown for model oils as well as for real oils.Essential for the continuation proposal is that our newly developed reaction system (aqueous HPA-5 solution) for the in-situ desulfurization of liquid fuels has the potential to efficiently desulfurize both aromatic and aliphatic systems. However, accumulation of decomposition products in the aqueous phase has been found to inhibit the catalyst system. This could be circumvented by the addition of oxalic acid. Based on these promising results, further investigations (as planned in the continuation proposal) are necessary with regard to the influence of N- and O-containing components in fuels on desulfurization. Thus, for example, N-containing fuel components such as indoles or quinolines could have a similar activating effect on our catalyst system, which could significantly contribute to the technical implementation of our concept. Therefore, in the continuation of the proposal, the influence of various N- and O-containing components on the oxidative-extractive desulfurization of liquid fuels should be fundamentally investigated. For this purpose, the influence on the basis of suitable model substances, e.g. the denitrification effect on the desulfurization of fuels should be investigated and understood. This approach has the potential to further enhance our newly developed desulfurization technology and, ideally, to combine it with the removal of further heteroatoms from liquid fuels.