Abstract

Fuel desulfurization methods based on hydrogenation and oxidation processes were compared in order to find an optimum method for desulfurization of marine gasoil (MGO) obtained by a process involving heavy distillates. Marine gasoil subjected to these two desulfurization processes had different physicochemical and performance characteristics due to the formation of different hydrocarbon compositions in these chemical processes. Hydrotreatment of marine gasoil led to a decrease in its lubricating ability, flash point, and fuel susceptibility with respect to a depressor–dispersant additive compared to these characteristics for fuel after oxidation with a hydrogen peroxide–acetic acid system. This is explained by the formation of low-boiling fractions and the removal of polysulfides and high-boiling alkanes from the sample under hydrotreatment conditions. Unlike hydrotreatment, oxidative desulfurization does not lead to isomerization and cracking of aliphatic and polyaromatic hydrocarbons, and organosulfur compounds are removed in oxidized forms (sulfoxides, sulfones, and sulfonate esters), as confirmed by chromato-mass spectroscopy and IR spectrometry. The change in the molecular mass characteristics of fuel components in these desulfurization processes was studied by gel permeation chromatography. Under the conditions of hydrotreatment, destructive hydrogenation of aromatics and cracking of heavy aliphatics occur, while during oxidation, the degradation processes of hydrocarbons occur to a lesser extent. After oxidative desulfurization, the characteristics of marine gasoil are more suitable for operational requirements than those for fuel after hydrotreatment. Due to milder process conditions and simple and accessible apparatuses and raw materials for oxidation compared to hydrotreatment, oxidative desulfurization is preferable as a method for improving the fuel performance.

中文翻译：

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提高海洋柴油性能的加氢和氧化方法比较

摘要

对基于加氢和氧化过程的燃料脱硫方法进行了比较，以找到一种用于重质馏分工艺获得的船用柴油（MGO）脱硫的最佳方法。由于在这些化学过程中形成了不同的碳氢化合物成分，经过这两种脱硫过程的海洋柴油具有不同的物理化学和性能特征。与用过氧化氢-乙酸系统氧化后的燃料相比，船用轻油的加氢处理导致其润滑能力、闪点和燃料对抑制剂-分散剂添加剂的敏感性降低。这可以通过在加氢处理条件下形成低沸点馏分以及从样品中去除多硫化物和高沸点烷烃来解释。与加氢处理不同，氧化脱硫不会导致脂肪烃和多环芳烃的异构化和裂解，并且有机硫化合物以氧化形式（亚砜、砜和磺酸酯）被去除，色谱质谱和红外光谱证实。通过凝胶渗透色谱法研究了这些脱硫过程中燃料组分的分子质量特性的变化。在加氢处理条件下，芳烃的破坏性加氢和重质脂肪烃的裂化，而在氧化过程中，烃类的降解过程发生的程度较小。经氧化脱硫后，船用柴油的特性比加氢处理后的燃料更适合操作要求。与加氢处理相比，由于工艺条件温和，氧化装置和原料简单易得，因此氧化脱硫作为改善燃料性能的方法是优选的。