Background of the Invention

This invention is directed to the removal of sulfur compounds from Heavy fuel such as Fuel Oil etc. Also more particularly, their removal by a combination of four steps: ultrasound, catalysts, oxidation and extraction.

One of the main concerns of today's world is the environment, the reduction and management of environmental pollutants. Environmental pollution management will be the recovery, conversion and decomposing of existing pollutants. But for a significant change, it is necessary to identify the sources of pollution and act to prevent the spread of pollution. One of the sources of air pollution is the compounds in the gases resulting from the combustion of fossil fuels. One of these special compounds was sulfur, which in the past decades, these gases had an increasing trend. With the identification of the problems caused by the emission of these gases, appropriate international standards and requirements for the quality of fuel consumption and the performance of vehicle engines reduced these gases. In 2020, the International Maritime Organization set a requirement in relation to the oil Tankers, which reduced the allowed amount of sulfur content from 3.5% to 0.5% wt.

Major fuel oil produced in the world has a sulfur content of more than 0.5% wt and industrial desulfurization methods such as hydrotreating methods are not able to remove sulfur in fuel oil effectively and economically due to the molecular nature of these compounds. Compounds such as benzothiophene, dibenzothiophene and other cyclic sulfur-containing compounds are not changed under hydrotreating methods and remain in the fuel. Therefore, relatively extensive studies are being conducted in this regard, and this invention provides a new method to reduce the sulfur content of heavy fuels, especially fuel oil, in an effective and economical way.

Sulfur removal from the fuel oil has been a challenging operation even after petroleum refining, and the issue remains critical to petrochemical industries. Thiols, thiophenes, benzothiophenes, dibenzothiophenes, and 4,6-dimethylbenzothiophene are examples of sulfur-containing compounds present in liquid fuels . Owing to the damaging impact of the sulfur compounds, most countries set stringent regulations on the needed amount of sulfur in fuel toward achieving a sustainable environment. The European Union and other developed countries like Japan and the USA set the highest permissible sulfur content limit for gasoline at 10 ppm and diesel at 15 ppm . The need to develop an efficient desulfurization technology that will remove sulfur compounds from fuel based on the recent strict environmental regulations is therefore necessary. Technologies such as hydrodesulfurization, biodesulfurization, extractive distillation, selective adsorption, and oxidative desulfurization have been proposed for fuel oil desulfurization. A summary of the effect of sulfur emission due to the S -compounds in the surrounding environment, the consequence of regulatory bodies to push researchers in the study for sustainable alternatives. Green technology of ODS employed a suitable catalyst that is considered to increase the activity of oxidants for rapid sulfur removal from oil under mild reaction conditions of temperature and pressure.

Indeed, numerous catalysts such as MOFs based and their composites with, titanate nanotubes, materials with hexagonal 2D structure, supported metal oxides, and phase transfer materials, have been previously studied as a catalyst for desulfurization of fuel oil. Among the recent used of the catalysts for ODS application, the newly emerging class of advanced materials, are one of the most commonly used catalysts for deep oil desulfurization. There is rapid progress in desulfurization studies involving fuel oil worldwide to tackle industrial and environmental concerns.

Advances in the development of new techniques and materials have offered exciting research opportunities to revolutionize the desulfurization processes toward increasing the standards of producing green oil fuel. Although research on desulfurization has been reported in the recent past, a focused review on oxidative desulfurization of fuel oil using advanced materials is significantly lacking. Noteworthy, there are many reports to boost the quality of fuel oil by employing advanced materials for deep desulfurization, and have been reviewed by researchers. In addition, the catalytic ODS performance over various types of catalysts is compared and discussed from a scientific point of view.

Summary of The Invention

In order to overcome the above-mentioned problems, one aspect of this disclosure is directed to a method of mixing-assisted oxidative desulfurization of fossil fuels in which the fossil fuel is combined with an aqueous oxidizer Solution including hydrogen peroxide having at least one carbon chain of 8 or more carbon atoms as a phase transfer catalyst to achieve improved conversion of sulfides to sulfoxides with higher yield and without the unwanted formation of side products. The mixing-assisted oxidative desulfurization process of this disclosure is also advantageous over the conventional Sono-reactor or ultrasonic desulfurization process with fixed bed catalyst, for example, with respect to have much fewer problems relating to scale up to mass production because of the lack of the accompanying corresponding function generator and RF amplifier that are found in Sono-reactors, and not presenting long term detriment to possible chain cracking of long chain hydrocarbons. The evaporative tower is coupled to one decanter and to one mixing tank So as to produce Sulfones, the decanter yields an organic phase that is Substantially Sulfone-free. Brief Description of The Drawing

The drawing is included to provide a further understanding of the invention also it is incorporated in and constitute a part of this specification. The drawing illustrates embodiments of the invention together with the description, explain the principles of the invention.

FIG. 1 is a schematic diagram of a portable continuous desulfurization device in accordance with a first embodiment of the present disclosure.

Description of Innovation

The aqueous solution is mixed with the fuel oil and the oxidizer aqueous solution including hydrogen peroxide or other organic peroxide and carboxylic acid such as formic acid or acetic acid. The ratio of the fuel oil and oxidizer aqueous solution may vary from about 3:1 to about 1:3, and preferably about 3:1.25. The concentration of hydrogen peroxide in the oxidizer aqueous solution is substantially in the range of 20% to 30%. And although they may affect the efficiency of the process or the ease of handling the fluids, the ratio is critical to this invention.

In most cases, however, improved results will be achieved when using metal oxide catalyst into the Sono-reactor. When the hydroperoxide is H2O2, improved results are generally achieved in most systems with an H2O2 con centration within the range from about 20% to about 30% by Volume (as H2O2) of the combined aqueous and organic phases, and preferably from about 3%. For hydroperoxides other than H2O2, the preferred relative volumes will be those of equivalent molar amounts.

The mixture passes through the reactor bed and it is subjected to ultrasound. The residence time in the invention varies from 2 minutes to 20 minutes and depends on the ultrasonic power (250 to 2000 watts), ultrasonic intensity (5 to 50 watts per square centimeter), ultrasonic frequency (16000 to 32000 Hz), the amount of catalyst in the reactor, also depends on the type of catalyst (molybdenum oxide (MoO2), vanadium oxide (V2O5), Iron(III) oxide (Fe2O3), Titanium oxide (TiCh), Magnesium oxide (MgO), Alumina (AI2O3)).

After the Sono-reactor stage, the output material is mixed with a polar solvent such as distilled water, ethanol, acetonitrile, acetone, etc. Moreover, separated into aqueous and organic phases in a decanter. There is very little sulfur in the organic phase of fuel oil. The solvent and oxidizer are sent to a stripping tower for recovery, and sulfonic and sulfoxide compounds are separated from the oxidizer solvent and returned to the storage tank.

The foregoing is offered primarily for illustrative purposes. The present disclosure is not limited to the above-described embodiments, various variations and modifications might be possible without departing from the scope of the present invention.