TECHNICAL FIELD

[0001] The present disclosure generally relates to oxidative desulfurization of liquid fuels, and particularly, to ultra-deep oxidative desulfurization of heavy liquid hydrocarbon fuels by ozone gas utilizing metal sulfide quantum dots intercalated over graphene oxide layers.

BACKGROUND ART

[0002] Hydrocarbon fuels contain sulfur compounds which form sulfur oxide during a combustion process and eventually lead to sever issues in environment and health of human. Also, higher concentrations of sulfur compounds results in acidic rains. Furthermore, when the concentration of sulfur in oil derivatives exceeds an allowable value, it leads to corrosion of metallic vessels, reactors, tubes and joints, and poisons the high-cost down-stream catalysts in addition to polluting the atmosphere. Considering the above-mentioned facts, desulfurizing the oil cuts is an essential process in hydrocarbon fuels processing.

[0003] Desulfurization of sulfur containing solutions is performed through Hydrodesulfurization (HDS) and nonhydrotreating desulfurization processes. The nonhydrotreating desulfurization processes include extractive, oxidative desulfurization (ODS), adsorption, biological desulfurization (BDS), etc. which are known to be complementary to HDS process. The catalytic oxidative desulfurization may be an appropriate alternative to HDS process, since this method is carried out in normal reaction conditions such as atmospheric pressure and low temperatures in which there is no need for hydrogen. However, catalytic oxidative desulfurization processes require one or more oxidizers such as organic peroxides, hydroperoxides, peroxide salts, nitrogen oxide, oxygen (0 ₂ ), hydrogen peroxide and tetra butyl hydrogen peroxide, etc., which decrease safety of the sweetening process due to their low stability and complicated conditions for their maintenance in reaction environment. Additionally, these oxidizers have a high cost making it not cost effective to conduct the catalytic oxidative desulfurization process.

[0004] For example, Raja L. AL Otaibi et al. in Appl Petrochem Res. 2015, 5, 355-362, reported desulfurization of Saudi Arabian crudes by an oxidation-extraction method utilizing H ₂ 0 ₂ and acetic acid as oxidant agents. However, sulfur reduction was less than about 40% initial sulfur content of the crudes. Additionally, Shujiro Otsuki et al. in Energy & Fuels 2000, 14, 1232-1239, reported oxidative desulfurization of light gas oil and vacuum gas oil (VGO) by an oxidation-extraction method using H ₂ 0 ₂ and formic acid as oxidant agents. The process was considerably time-consuming with a sulfur removal of less than about 90%.

[0005] The catalysts used in oxidative desulfurization process include heterogeneous and homogenous catalysts. In desulfurization processes which adopt homogenous catalysts, catalysts such as formic acid and acetic acid, etc. are utilized. However, the efficiency of the desulfurization in these processes is low and an adequate standard amount of safety is not provided. In the desulfurization processes using heterogeneous catalysts, a solid catalyst is utilized along with the oxidizer agent in which the active catalyst is supported over catalyst supports such as alumina, silica, etc. Alternatively, the solid catalyst is used solely. However, supporting the catalyst over catalyst supports involves low surface area, low pore volume, no- uninform distribution of the active catalyst, and possibly the agglomeration of the metallic particles; consequently, it is not an easy task to impregnate the catalyst support by high amount of metallic particles which is necessary for desulfurization of a fuel feedstock containing dibenzothiophene and alkyl dibenzothiophenes.

[0006] Hence, there is a need for an oxidative desulfurization process and catalyst which may overcome the high cost and low efficiency of common oxidative desulfurization procedures. Also, there is a need for an oxidative desulfurization process and catalyst to alleviate the reaction conditions (atmospheric pressure and low temperature) for oxidative desulfurization and also reduction of the consumption of catalyst while increasing sulfur reduction efficiency. Additionally, there is a need for utilizing a catalyst for oxidative desulfurization of fuels, which may not involve the agglomeration of catalyst and may facilitate the formation of active sites over the catalyst. Moreover, there is a need for a method for oxidative desulfurization that may utilize suitable and optimized process conditions.

SUMMARY OF THE DISCLOSURE

[0007] This summary is intended to provide an overview of the subject matter of this patent, and is not intended to identify essential elements or key elements of the subject matter, nor is it intended to be used to determine the scope of the claimed implementations. The proper scope of this patent may be ascertained from the claims set forth below in view of the detailed description below and the drawings. [0008] In one general aspect, the present disclosure is directed to an exemplary method for oxidative desulfurization of liquid hydrocarbon fuels. The method may include contacting a liquid fuel with a quantum dot hybrid catalyst in a reactor vessel, heating the reactor vessel to a temperature between 25°C and 200°C, and reducing sulfur content of the liquid fuel with a sulfur reduction amount of more than 95% wt. The quantum dot hybrid catalyst may include metal sulfide quantum dots intercalated over graphene oxide layers. In an exemplary implementation, reducing the sulfur content of the liquid fuel with the sulfur reduction amount of more than 95% wt. may include producing sulfone and sulfoxide compounds by oxidizing the liquid fuel with ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between 25°C and 200°C, and separating the sulfone and sulfoxide compounds from the liquid fuel by extracting the sulfone and sulfoxide with an extraction solvent.

[0009] In an exemplary implementation, contacting the liquid fuel with the quantum dot hybrid catalyst in the reactor vessel may include adding the quantum dot hybrid catalyst to the reactor vessel containing the liquid fuel with a weight ratio of the quantum dot hybrid catalyst to the liquid fuel in a range between 1% wt. and 5% wt. In an exemplary implementation, contacting the liquid fuel with the quantum dot hybrid catalyst in the reactor vessel further may further include mixing the quantum dot hybrid catalyst and the liquid fuel in the reactor vessel with a mixing rate in a range between 200 rpm and 2000 rpm.

[0010] In an exemplary implementation, heating the reactor vessel to the temperature between 25°C and 200°C may include maintaining the reactor vessel at a temperature between 25°C and l00°C.

[0011] In an exemplary implementation, producing the sulfone and sulfoxide compounds by oxidizing the liquid fuel with the ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between 25 °C and 200°C may include flowing the ozone gas into the reactor vessel while mixing the liquid fuel and the quantum dot hybrid catalyst in the reactor vessel at the temperature between 25 °C and 200°C. In an exemplary implementation, producing the sulfone and sulfoxide compounds by oxidizing the liquid fuel with the ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between 25 °C and 200°C may include flowing the ozone gas into the reactor vessel with a flow rate between 100 ml/min and 700 ml/min for a period of time between 1 hour and 12 hours.

[0012] In an exemplary implementation, separating the sulfone and sulfoxide compounds from the liquid fuel by extracting the sulfone and sulfoxide with the extraction solvent may include extracting the sulfone and sulfoxide compounds from the liquid fuel using at least one of methanol, water, acetonitrile, sulfolane, dimethylformamide (DMF), and combinations thereof.

[0013] In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a boiling temperature in a range between 38°C and 750°C. In an exemplary embodiment, the liquid fuel may include at least one of naphtha, kerosene, diesel, gas oil, vacuum gas oil (VGO), mazot, atmospheric residue of petroleum, and combinations thereof. In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a sulfur content in a range between 50 ppm and 60000 ppm (6 %wt.). In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a sulfur content in a range between 10000 ppm (1 %wt.) and 60000 ppm (6 %wt.).

[0014] In an exemplary embodiment, the metal sulfide quantum dots may include at least one of molybdenum disulfide quantum dots (MoS ₂ QDs), chromium sulfide quantum dots (Cr ₂ S ₃ QDs), tungsten disulfide quantum dots (WS ₂ QDs), nickel sulfide quantum dots (Ni ₃ S ₂ QDs), and combinations thereof. In an exemplary embodiment, the quantum dot hybrid catalyst may include the metal sulfide quantum dots with a size between 0.5 nm and 5 nm. In an exemplary embodiment, the quantum dot hybrid catalyst may include a weight ratio of the metal sulfide quantum dots to the graphene oxide in a range between 0.02% wt. and 0.1% wt.

[0015] In an exemplary implementation, the exemplary method for oxidative desulfurization of liquid hydrocarbon fuels may further include synthesizing the quantum dot hybrid catalyst. In an exemplary implementation, synthesizing the quantum dot hybrid catalyst may include synthesizing a suspension of the metal sulfide quantum dots, and intercalating the metal sulfide quantum dots between layers of graphene oxide.

[0016] In an exemplary implementation, synthesizing the metal sulfide quantum dots may include forming a suspension by dispersing metal sulfide particles in a mixture of an alcohol and a chelating agent at a temperature between 20°C and 40°C, exfoliating the metal sulfide particles by sonicating the suspension with ultrasonic waves for a period of time between 10 minutes and 1 hour at a sonication power between 50 W/cm ² and 300 W/cm ² , and forming the suspension of the metal sulfide quantum dots by separating a suspension of the exfoliated metal sulfide particles by centrifuging the sonicated suspension.

[0017] In an exemplary embodiment, the alcohol may include at least one of methanol, ethanol, propanol, and combinations thereof. In an exemplary embodiment, the chelating agent may include at least one of polyvinylpyrrolidone (PVP), sodium dodecyl sulfate (SDS), potassium laurate (K-LAURATE), and combinations thereof.

[0018] In an exemplary implementation, intercalating the metal sulfide quantum dots between layers of graphene oxide may include forming a metal sulfide/graphene oxide mixture by adding a solution of graphene oxide to the suspension of the metal sulfide quantum dots, stirring the metal sulfide/graphene oxide mixture for a time period between 15 minutes and 2 hours with a mixing rate between 200 rpm and 2000 rpm, and drying the stirred metal sulfide/graphene oxide mixture at a temperature between 50°C and 200°C for a period of time between 4 hours and 24 hours.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The drawing figures depict one or more implementations in accord with the present teachings, by way of example only, not by way of limitation. In the figures, like reference numerals refer to the same or similar elements.

[0020] FIG. 1A illustrates an exemplary method for oxidative desulfurization of liquid hydrocarbon fuels, consistent with one or more exemplary embodiments of the present disclosure.

[0021] FIG. IB illustrates an exemplary implementation of an exemplary process for reducing the sulfur content of the liquid fuel with the sulfur reduction amount of more than about 95% wt., consistent with one or more exemplary embodiments of the present disclosure.

[0022] FIG. 1C illustrates another implementation of an exemplary method for oxidative desulfurization of liquid hydrocarbon fuels, consistent with one or more exemplary embodiments of the present disclosure.

[0023] FIG. ID illustrates an exemplary method for synthesizing the quantum dot hybrid catalyst, consistent with one or more exemplary embodiments of the present disclosure.

[0024] FIG. 2 illustrates a schematic flow diagram of an exemplary implementation of an exemplary setup for oxidative desulfurization of liquid hydrocarbon fuels, consistent with one or more exemplary embodiments of the present disclosure.

[0025] FIG. 3 illustrates a comparative chart of the fluorescent spectra intensity for exemplary MOS ₂ quantum dots and an exemplary synthesized M0S2 QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure. [0026] FIG. 4A illustrates UV/Vis spectra of exemplary MoS ₂ quantum dots, consistent with one or more exemplary embodiments of the present disclosure.

[0027] FIG. 4B illustrates UV/Vis spectra of exemplary synthesized MoS2 QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure.

[0028] FIG. 5A illustrates Raman spectra of exemplary M0S ₂ quantum dots, consistent with one or more exemplary embodiments of the present disclosure.

[0029] FIG.5B illustrates Raman spectra of an exemplary synthesized M0S ₂ QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure.

[0030] FIG. 6 illustrates a transmission electron microscopy (TEM) image of an exemplary synthesized M0S ₂ QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure.

[0031] FIG. 7 A illustrates an atomic force microscopy (AFM) image representing the morphology of exemplary M0S ₂ quantum dots, consistent with one or more exemplary embodiments of the present disclosure.

[0032] FIG. 7B illustrates an AFM image representing the morphology of exemplary graphene oxide (GO), consistent with one or more exemplary embodiments of the present disclosure.

[0033] FIG. 7C illustrates an AFM image representing the morphology of an exemplary synthesized M0S ₂ QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure.

[0034] FIG. 8 illustrates nanoparticle size distribution of exemplary synthesized M0S ₂ quantum dots, consistent with one or more exemplary embodiments of the present disclosure.

DESCRIPTION OF EMBODIMENTS

[0035] In the following detailed description, numerous specific details are set forth by way of examples in order to provide a thorough understanding of the relevant teachings. However, it should be apparent that the present teachings may be practiced without such details. In other instances, well known methods, procedures, components, and/or circuitry have been described at a relatively high-level, without detail, in order to avoid unnecessarily obscuring aspects of the present teachings.

[0036] Herein, an exemplary method for oxidative desulfurization of liquid hydrocarbon fuels using an exemplary quantum dot hybrid catalyst is disclosed. Exemplary method may include oxidizing heavy hydrocarbon fuels by ozone gas at mild conditions (atmospheric pressure and low temperature) in the presence of exemplary quantum dot hybrid catalyst, which may include metal sulfide quantum dots that may be intercalated over graphene oxide layers. The exemplary method may be utilized for ultra-deep desulfurization of liquid hydrocarbon fuels by reducing sulfur contents of such fuels to less than about 10 ppm at mild conditions.

[0037] The presence of exemplary metal sulfide quantum dots over graphene oxide layers may provide a higher specific surface area, increased pore volume, and higher pore diameters in the structure of exemplary quantum dot hybrid catalyst as an exemplary oxidative desulfurization catalyst. Furthermore, exemplary quantum dot hybrid catalyst may be prepared through a simple synthesis procedure with no need to a calcination process. Regarding an exemplary catalyst formulations of the present disclosure, using exemplary metal sulfide quantum dots in size of about 0.5-2 nm over graphene oxide layers may prevent catalyst agglomeration and facilitate the formation of active sites over the exemplary catalyst. Also, high efficiency may be obtained for the prepared oxidative desulfurization catalysts at alleviated reaction conditions.

[0038] FIG. 1A shows an exemplary method 100 for oxidative desulfurization of liquid hydrocarbon fuels, consistent with one or more exemplary embodiments of the present disclosure. Exemplary method 100 may include contacting a liquid fuel with a quantum dot hybrid catalyst in a reactor vessel (step 102), heating the reactor vessel to a temperature between 25°C and 200°C (step 104), and reducing sulfur content of the liquid fuel with a sulfur reduction amount of more than 95% wt. (step 106). Where, the quantum dot hybrid catalyst may include metal sulfide quantum dots which may be intercalated over graphene oxide layers.

[0039] In an exemplary implementation, an exemplary setup may be utilized to perform exemplary method 100 for oxidative desulfurization of liquid hydrocarbon fuels. FIG. 2 shows a schematic flow diagram of an exemplary implementation of an exemplary setup 200 for oxidative desulfurization of liquid hydrocarbon fuels, consistent with one or more exemplary embodiments of the present disclosure. In an exemplary embodiment, exemplary setup 200 may include an oxidative reactor 202, an ozone generator 204, a separator 206, a solvent recovery unit 208, and a polishing unit 210. In an exemplary embodiment, exemplary setup 200 may further include mass flow controller (MFC) 212 that may be configured to adjust ozone flow rate in a rage between about 100 cc/min and about 1000 cc/min by measuring and controlling the ozone flow rate. [0040] Referring to FIG. 1A, step 102 may include contacting a liquid fuel with a quantum dot hybrid catalyst in a reactor vessel. In an exemplary implementation with reference to FIG. 2, contacting the liquid fuel with the quantum dot hybrid catalyst in the reactor vessel may include adding the quantum dot hybrid catalyst via line 214 to exemplary reactor vessel 202 that may contain the liquid fuel. The quantum dot hybrid catalyst may be added to exemplary reactor vessel 202 containing the liquid fuel with a weight ratio of the quantum dot hybrid catalyst to the liquid fuel in a range between about 1% wt. and about 5% wt. In an exemplary implementation, contacting the liquid fuel with the quantum dot hybrid catalyst in exemplary reactor vessel 202 may further include mixing the quantum dot hybrid catalyst and the liquid fuel in exemplary reactor vessel 202 with a mixing rate in a range between about 200 rpm and about 2000 rpm.

[0041] In an exemplary embodiment, exemplary reactor vessel 202 may include a batch reactor vessel or a continuous reactor vessel. In an exemplary embodiment, exemplary reactor vessel 202 may include a glass reactor vessel or a steel reactor vessel. In an exemplary embodiment, exemplary reactor vessel 202 may be equipped with a stirrer or an agitator.

[0042] In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a boiling temperature in a range between about 38°C and about 750°C. In an exemplary embodiment, the liquid fuel may include at least one of naphtha, kerosene, diesel, gas oil, vacuum gas oil (VGO), mazot, atmospheric residue of petroleum, and combinations thereof. In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a sulfur content in a range between about 50 ppm and about 60000 ppm (6 %wt.). In an exemplary embodiment, the liquid fuel may include a hydrocarbon fuel cut with a sulfur content in a range between about 10000 ppm (1 %wt.) and about 60000 ppm (6 %wt.). In an exemplary embodiment, the liquid fuel may include at least one of naphtha with a sulfur content of about 1000 ppm to about 3000 ppm, kerosene with a sulfur content of about 1500 ppm to about 3000 ppm, diesel with a sulfur content of about 10000 ppm to about 15000 ppm, gas oil with a sulfur content of about 10000 ppm to about 15000 ppm, vacuum gas oil (VGO) with a sulfur content of about 16000 ppm to about 35000 ppm, mazot with a sulfur content of about 28000 ppm to about 40000 ppm, atmospheric residue of petroleum with a sulfur content of about 37000 ppm to about 60000 ppm, and combinations thereof.

[0043] In an exemplary embodiment, the metal sulfide quantum dots may include at least one of molybdenum disulfide quantum dots (MoS ₂ QDs), chromium sulfide quantum dots (Cr ₂ S ₃ QDs), tungsten disulfide quantum dots (WS ₂ QDs), nickel sulfide quantum dots (N13S2 QDs), and combinations thereof. In an exemplary embodiment, the metal sulfide quantum dots may include metal sulfide quantum dots of the sixth group (group VIB) of the periodic table, for example, at least one of M0S2 QDs, CnS i QDs, WS2 QDs, and combinations thereof.

[0044] In an exemplary embodiment, the quantum dot hybrid catalyst may include a layered structure that may include the metal sulfide quantum dots with a size between about 0.5 nm and about 5 nm supported over graphene oxide (GO) layers. In an exemplary embodiment, the metal sulfide quantum dots may include quantum dots with a size between about 0.5 nm and about 2 nm.

[0045] In an exemplary embodiment, the quantum dot hybrid catalyst may include a weight ratio of the metal sulfide quantum dots to the graphene oxide (GO) in a range between about 0.02% wt. and about 0.1% wt. The metal sulfide quantum dots may be intercalated between GO layers in such a way that the metal sulfide quantum dots may be uniformly dispersed and attached on structural defects of the GO layers.

[0046] In an exemplary embodiment, the quantum dot hybrid catalyst may include about 0.05 gr to about 0.1 gr of the metal sulfide quantum dots and the graphene oxide with a concentration range of about 0.5-5 mg/mL. Furthermore, in an exemplary embodiment, the quantum dot hybrid catalyst may contain the graphene oxide in %vol. range of about 10-40%.

[0047] Additionally, referring again to FIG. 1A and FIG. 2, step 104 may include heating exemplary reactor vessel 202 to a temperature between about 25 °C and about 200°C. In an exemplary implementation, heating exemplary reactor vessel 202 to the temperature between about 25 °C and about 200°C may include heating exemplary reactor vessel 202 to a temperature between about 25°C and about l00°C, and maintaining exemplary reactor vessel 202 at the temperature between about 25°C and about l00°C. So, the oxidative desulfurization of the liquid hydrocarbon fuels may be carried out at a temperature of less than about 200°C, and specifically, less than about l00°C.

[0048] In an exemplary implementation, pressure of exemplary reactor vessel 202 may be maintained at atmospheric pressure (ambient pressure) during applying steps 102, 104, and 106. So, the oxidative desulfurization of the liquid hydrocarbon fuels may be carried out at atmospheric pressure. Furthermore, the oxidative desulfurization of the liquid hydrocarbon fuels may be carried out at mild conditions, including atmospheric pressure and low temperatures of less than about l00°C. [0049] Furthermore, referring more to FIG. 1A, step 106 may include reducing sulfur content of the liquid fuel with a sulfur reduction amount of more than about 95% wt. FIG. IB shows an exemplary implementation of an exemplary process for reducing the sulfur content of the liquid fuel with the sulfur reduction amount of more than about 95% wt. (step 106), consistent with one or more exemplary embodiments of the present disclosure. In an exemplary implementation, reducing the sulfur content of the liquid fuel with the sulfur reduction amount of more than about 95% wt. (step 106) may include producing sulfone and sulfoxide compounds by oxidizing the liquid fuel with ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between about 25°C and about 200°C (step 110) and separating the sulfone and sulfoxide compounds from the liquid fuel by extracting the sulfone and sulfoxide with an extraction solvent (step 112).

[0050] In an exemplary implementation, producing the sulfone and sulfoxide compounds by oxidizing the liquid fuel with the ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between about 25°C and about 200°C (step 110) may include flowing the ozone gas into exemplary reactor vessel 202 while mixing the liquid fuel and the quantum dot hybrid catalyst in exemplary reactor vessel 202 at a temperature between about 25 °C and about 200°C; thereby, forming the sulfone and sulfoxide compounds responsive to oxidation of the liquid fuel by the ozone gas in the presence of the quantum dot hybrid catalyst. In an exemplary implementation, referring to FIG. 2, the ozone gas may be generated by exemplary ozone generator 204 and the generated ozone gas may be introduced into exemplary reactor vessel 202 via line 216. In an exemplary implementation, producing the sulfone and sulfoxide compounds by oxidizing the liquid fuel with the ozone gas in the presence of the quantum dot hybrid catalyst at the temperature between about 25 °C and about 200°C may include flowing the ozone gas into exemplary reactor vessel 202 with a flow rate between about 100 ml/min and about 700 ml/min for a period of time between about 1 hour and about 12 hours.

[0051] Moreover, separating the sulfone and sulfoxide compounds from the liquid fuel by extracting the sulfone and sulfoxide with an extraction solvent (step 112) may include extracting the sulfone and sulfoxide compounds from the liquid fuel by a liquid extraction solvent that may include at least one of methanol, water, acetonitrile, sulfolane, dimethylformamide (DMF), and combinations thereof.

[0052] In an exemplary implementation with further reference to FIG. 2, separating the sulfone and sulfoxide compounds from the liquid fuel by extracting the sulfone and sulfoxide compounds with an extraction solvent (step 112) may include discharging the oxidized liquid fuel containing the sulfone and sulfoxide compounds from exemplary reactor vessel 202 and entering the oxidized liquid fuel into exemplary separator 206 via line 218, and mixing the oxidized liquid fuel with the liquid extraction solvent in exemplary separator 206. So, the sulfone and sulfoxide compounds may be extracted by the liquid extraction solvent in exemplary separator 206.

[0053] In an exemplary implementation, extracting the sulfone and sulfoxide compounds with the extraction solvent (step 112) may be carried out once or repeated iteratively. For iterative extraction, the extraction solvent containing the separated sulfone and sulfoxide compounds from the liquid fuel may be entered into exemplary solvent recovery unit 208 via line 220. The extraction solvent may be recovered in exemplary solvent recovery unit 208 by separating or stripping the sulfone and sulfoxide compounds from the extraction solvent. The recovered extraction solvent may be introduced into exemplary polishing unit 210 via line 222 and the separated liquid fuel from the sulfone and sulfoxide compounds may be introduced into exemplary polishing unit 210 via line 224, where the recovered extraction solvent and the separated liquid fuel may be mixed more to obtain a deep desulfurized liquid fuel that may exit from exemplary polishing unit 210 via line 226.

[0054] In an exemplary embodiment, the obtained deep desulfurized liquid fuel may include the liquid fuel with a reduced sulfur content by an amount of sulfur reduction of more than about 85%. In another exemplary embodiment, the obtained deep desulfurized liquid fuel may include liquid fuel with a reduced sulfur content by an amount of sulfur reduction of more than about 95%. In further exemplary embodiments, the obtained deep desulfurized liquid fuel may include liquid fuel with a reduced sulfur content by an amount of sulfur reduction of about 100%.

[0055] In an exemplary implementation, exemplary method 100 may further include synthesizing the quantum dot hybrid catalyst. FIG. 1C shows an implementation of exemplary method 120 for oxidative desulfurization of liquid hydrocarbon fuels which includes method 100, consistent with one or more exemplary embodiments of the present disclosure. Accordingly, exemplary method 120 may further include synthesizing the quantum dot hybrid catalyst (step 101) that may be carried out before steps 102, 104, and 106.

[0056] FIG. ID shows an exemplary method for synthesizing the quantum dot hybrid catalyst (step 101), consistent with one or more exemplary embodiments of the present disclosure. Specifically, FIG. ID provides the details for step 101 of FIG. 1C. Accordingly, synthesizing the quantum dot hybrid catalyst may include synthesizing a suspension of the metal sulfide quantum dots (step 130), and intercalating the metal sulfide quantum dots between layers of graphene oxide (step 132).

[0057] In detail, according to an exemplary implementation, synthesizing the suspension of the metal sulfide quantum dots (step 130) may include synthesizing the metal sulfide quantum dots through an up-down procedure. Macromolecules of a metal sulfide may be converted to quantum dots by reducing size of the metal sulfide through exfoliation of the metal sulfide. Exfoliation of the metal sulfide may include separating nanosheets of the metal sulfide using a polar solvent, for example, an alcohol.

[0058] In an exemplary implementation, synthesizing the suspension of the metal sulfide quantum dots (step 130) may include forming a suspension by dispersing metal sulfide particles in a mixture of an alcohol and a chelating agent at a temperature between about 20°C and about 40°C, exfoliating the metal sulfide particles by sonicating the suspension with ultrasonic waves for a period of time between about 10 minutes and about 1 hour at a sonication power between about 50 W/cm ² and about 300 W/cm ² , and forming the suspension of the metal sulfide quantum dots by separating a suspension of the exfoliated metal sulfide particles by centrifuging the sonicated suspension.

[0059] In an exemplary embodiment, the alcohol may include at least one of methanol, ethanol, propanol, and combinations thereof. In an exemplary embodiment, the chelating agent may include at least one of polyvinylpyrrolidone (PVP), sodium dodecyl sulfate (SDS), potassium laurate (K-LAURATE), and combinations thereof.

[0060] Additionally, intercalating the metal sulfide quantum dots between layers of graphene oxide (step 132) may include forming a metal sulfide/graphene oxide mixture by adding a solution of graphene oxide to the suspension of the metal sulfide quantum dots, stirring the metal sulfide/graphene oxide mixture for a time period between about 15 minutes and about 2 hours with a mixing rate between about 200 rpm and about 2000 rpm, and drying the stirred metal sulfide/graphene oxide mixture at a temperature between about 50°C and about 200°C for a period of time between about 4 hours and about 24 hours.

[0061] In an exemplary implementation, drying the stirred metal sulfide/graphene oxide mixture at the temperature between about 50°C and about 200°C for the period of time between about 4 hours and about 24 hours may include drying the stirred metal sulfide/graphene oxide mixture at a temperature between about 50°C and about l20°C for a period of time between about 4 hours and about 15 hours. In an exemplary implementation, drying the stirred metal sulfide/graphene oxide mixture at the temperature between about 50°C and about 200°C may include drying the stirred metal sulfide/graphene oxide mixture at a temperature of about l20°C. In an exemplary embodiment, drying the stirred metal sulfide/graphene oxide mixture may be carried out in a rotary drier.

[0062] EXAMPLE 1: Synthesis of quantum dot hybrid catalyst

[0063] In this example, an exemplary quantum dot hybrid catalyst was synthesized according to exemplary process of step 102 described hereinabove. Exemplary synthesized quantum dot hybrid catalyst may include molybdenum sulfide quantum dots intercalated over graphene oxide layers with a chemical formula of MoS ₂ QDs/GO.

[0064] In exemplary synthesis process, about 0.05 gr of molybdenum sulfide (M0S2) was dissolved in about 10 mL of ethanol solvent containing polyvinylpyrrolidone (PVP) and placed under ultrasonic for about 1 hour to obtain a suspension. Then, the obtaining suspension was kept in ambient condition so that the M0S2 particles that were not completely dispersed were separated and precipitated. Afterwards, the suspension was centrifuged at about 9000 rpm for about 20 minutes. After that, the suspension was separated as a clear solution in which the quantum dot molybdenum sulfides (exfoliated molybdenum sulfide particles) were dispersed. The resulting solution may have high stability in ambient conditions. Furthermore, about 1 mL of an aqueous solution of graphene oxide (GO) with about 3 mg GO/mL was added to the solution containing the exfoliated molybdenum sulfides and was mixed for about 30 minutes. The obtained mixture was dried at about 60°C for about 6 hours.

[0065] For comparing characteristics of the synthesized M0S2 QDs/GO catalyst with M0S2 quantum dots, a number of characterization analyses were carried out. FIG. 3 shows a comparative chart of the fluorescent spectra intensity for exemplary M0S2 quantum dots (curve 302) and exemplary synthesized M0S2 QDs/GO catalyst (curve 304), consistent with one or more exemplary embodiments of the present disclosure. The fluorescent spectra 302 of exemplary M0S2 quantum dots has two peaks at 490 nm and 528 nm, whereas the fluorescent spectra 304 of exemplary synthesized M0S2 QDs/GO catalyst shows less intensity in the fluorescent spectra.

[0066] FIG. 4A shows UV/Vis spectra of exemplary M0S2 quantum dots, consistent with one or more exemplary embodiments of the present disclosure. Moreover, FIG. 4B shows UV/Vis spectra of exemplary synthesized MoS ₂ QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure. It may be observed from FIGS. 4A and 4B that two absorbance peaks are obtained at the same wavelengths for both M0S2 quantum dots and exemplary synthesized M0S2 QDs/GO catalyst. Peaks 402 and 406 occurred at wavelength 612 nm for both M0S2 quantum dots and exemplary synthesized M0S2 QDs/GO catalyst, and peaks 404 and 408 occurred at wavelength 673 nm for both M0S2 quantum dots and exemplary synthesized M0S2 QDs/GO catalyst. Peaks 402 and 404 may represent exfoliation of M0S2 structure. Additionally, a lower intensity of peaks 406 and 408 in comparison with corresponding peaks 402 and 404 may be an indicator of hybridizing M0S2 into GO structure.

[0067] FIG. 5A shows Raman spectra of exemplary M0S2 quantum dots, consistent with one or more exemplary embodiments of the present disclosure. FIG. 5B shows Raman spectra of exemplary synthesized M0S2 QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure. The peaks of the Raman spectra in FIGS. 5A and 5B shows the formation of exemplary M0S2 quantum dots and exemplary synthesized M0S2 QDs/GO catalyst, respectively. The peaks at 382 nm and 407 nm are associated to M0S2 nanostructures (QDs), and the peaks at 1340 nm, 1600 nm, and 2600 nm are associated to GO. The peak at 1340 nm (ID) is associated to Dbond which represents the structural defects of GO structure. The peak at 1600 nm (IG) is associated to Gbond which represents the graphite structure of GO. Higher values of ID/IG represents more structural defects and functional groups in GO structure. The peak at 2600 nm is associated to 2D or G ^* , which is a G-complementary structure. Higher values of 12 D/IG represents less layers or sheets in GO structure which shows 2-3 layers of GO herein.

[0068] FIG. 6 shows a transmission electron microscopy (TEM) image of exemplary synthesized M0S2 QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure. It may be seen that M0S2 quantum dots 602 with a size of less than about 5 nm are intercalated between GO layers 604, so that M0S2 quantum dots 602 are dispersed on the GO surface at the structural defects of GO layers 604.

[0069] For more clarification of how M0S2 quantum dots are intercalated between GO layers and structural analysis of exemplary synthesized M0S2 QDs/GO catalyst, comparative atomic force microscopy (AFM) analysis was carried out for exemplary M0S2 quantum dots, exemplary GO, and also, for exemplary synthesized M0S2 QDs/GO catalyst. FIG. 7A shows an AFM image representing the morphology of exemplary M0S2 quantum dots, consistent with one or more exemplary embodiments of the present disclosure. FIG. 7B shows an AFM image representing the morphology of exemplary GO, consistent with one or more exemplary embodiments of the present disclosure. Moreover, FIG. 7C shows an AFM image representing the morphology of exemplary synthesized MoS ₂ QDs/GO catalyst, consistent with one or more exemplary embodiments of the present disclosure. It may be seen that exemplary M0S2 quantum dots 702 are uniformly dispersed on exemplary GO layers 704.

[0070] To obtain an accurate size distribution of exemplary synthesized M0S2 quantum dots that were intercalated between GO layers, their size distribution was obtained from three- dimension AFM images. FIG. 8 shows nanoparticle size distribution of exemplary synthesized M0S2 quantum dots, consistent with one or more exemplary embodiments of the present disclosure. It may be seen that exemplary M0S2 quantum dots have a size of less than about 2.5 nm with an average size of about 1.25 nm.

[0071] EXAMPLE 2: oxidative desulfurization of VGO in the presence of molybdenum sulfide (M0S2) (macro) at 25°C

[0072] An exemplary oxidative desulfurization reaction was performed in a batch reactor equipped with a stirrer. About 20 gr of the VGO feedstock containing about 16800 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3% wt. of M0S2 (macro) was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 25 °C for about 8 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 9936 ppm; i.e. about 41% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 2 herein below.

[0073] EXAMPLE 3: Oxidative desulfurization of VGO in the presence of molybdenum sulfide (M0S2) (macro) at 75°C

[0074] An exemplary oxidative desulfurization reaction was performed in a batch reactor equipped with a stirrer. About 20 gr of the VGO feedstock containing about 16800 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3% wt. of M0S2 (macro) was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 75°C for about 8 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 1732 ppm; i.e. about 89% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 2 herein below.

[0075] EXAMPLE 4: Oxidative desulfurization of VGO in the presence of molybdenum sulfide (M0S2) quantum dots

[0076] An exemplary oxidative desulfurization reaction was performed in a batch reactor equipped with a stirrer. About 20 gr of the VGO feedstock containing about 16800 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3 wt.% of exemplary M0S2 quantum dots that were synthesized according to EXAMPLE 1 was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 75°C for about 8 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 553 ppm; i.e. about 97% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 2 herein below.

[0077] EXAMPLE 5: Oxidative desulfurization of VGO in the presence of M0S2 ODs/GO

[0078] An exemplary oxidative desulfurization reaction similar to exemplary method 100 was performed in a batch reactor equipped with a stirrer. About 20 gr of the VGO feedstock containing about 16800 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3 wt.% of exemplary synthesized M0S2 QDs/GO catalyst that were synthesized according to EXAMPLE 1 was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 75°C for about 6 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 410 ppm; i.e. about 98% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 2 herein below.

[0079] A comparison between reaction conditions of exemplary oxidative desulfurization, catalyst type, catalyst consumption, and sulfur amount of the feedstock before and after desulfurization process may clarify the efficiency of the process, which are summarized in Table 2 herein below. Table. 2 shows the comparison between the performance criteria of different catalysts for oxidative desulfurization of VGO that were described through EXAMPLES 2-5.

[0080] Table. 1 Specifications of the Vacuum gas oil (VGO) feedstock

Distillation Range (°C)

Recovered mass% BP (°C)

Initial Boiling Point (IBP) at 760 mmHg 195.8

5 265.6

10 290.8

20 330.4

30 349.4

40 363.8

50 376.4

60 387.6

70 398.4

80 408.4

90 419.8

95 428.0

_ Final Boiling Point (FBP) _ 705.8

_ Total sulfur (ppm) _ 16800

_ Density at (15 °C) gr/cm ³ _ 0.930

Color (ASTM D 1500) 5.0

[0081] Table. 2 Comparison between the performance of different catalysts used for oxidative desulfurization of VGO through EXAMPLES 2-5

Reaction Conditions

_ Sulfur Sulfur

Ozone

Example ^Tem · Pressure Other Solvent/ Feed Product

Fuel flow rate

No. (°C ) (bar) oxidant bubbling N2 (PP ^m ) (ppm)

(ml/min)

Vacuum DMF

EXM. 2 25 1 400 16800 9936 gas oil (One times)

Vacuum DMF

EXM. 3 75 1 400 16800 1732 gas oil (One times)

Vacuum DMF

EXM. 4 75 1 400 16800 553 gas oil (One times)

Vacuum DMF

EXM. 5 75 1 400 16800 410 gas oil (One times)

[0082] EXAMPLE 6: Oxidative desulfurization of heavy diesel in the presence of M0S2 ODs/GO hybrid catalyst [0083] An exemplary oxidative desulfurization reaction similar to exemplary method 100 was performed in a batch reactor equipped with a stirrer. About 20 gr of the heavy diesel containing about 12000 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3 wt.% of exemplary synthesized MoS ₂ QDs/GO catalyst that were synthesized according to EXAMPLE 1 was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 75°C for about 6 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed once during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 100 ppm; i.e. about 99.2% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 3.

[0084] Table. 3 The oxidative desulfurization conditions and results for heavy diesel using M0S2 QDs/GO hybrid catalyst

Reaction Conditions Sulfur Sulfur

Tem. Pressure . Ozone flow rate Other Solvent/ Feed Product

(°C ) (bar) ^Ue (ml/min) oxidant bubbling N2 (ppm) (ppm)

DMF

75 1 Heavy diesel 400 12000 100

(One times)

[0085] EXAMPLE 7: oxidative desulfurization of Kerosene in the presence of M0S2

[0086] An exemplary oxidative desulfurization reaction similar to exemplary method 100 was performed in a batch reactor equipped with a stirrer. About 20 gr of Kerosene containing about 2000 ppm sulfur (other specifications of the feedstock are presented in Table 1 herein below) was placed in the reactor and about 3 wt.% of exemplary synthesized M0S2 QDs/GO catalyst that were synthesized according to EXAMPLE 1 was added to reactor. Ozone gas was introduced into the reactor with a flow rate of about 400 ml/min at about 75°C for about 6 hours. Then, the output of the reactor containing oxidized sulfur compounds was washed once during an extraction process by dimethyl formaldehyde (DMF) and the sulfur content of the product was evaluated which reached the value of about 30 ppm; i.e. about 98.5% desulfurization was achieved. A summary of the reaction conditions and obtained result is shown in Table 4. [0087] Table. 4 The oxidative desulfurization conditions and results for Kerosene using M0S2 QDs/GO hybrid catalyst

Reaction Conditions

Sulfur Sulfur

Tem. Pressure Ozone flow rate Other Solvent/ Feed Product

Fuel

(°C ) (bar) (ml/min) oxidant bubbling N ₂ (ppm) (ppm)

DMF

75 1 Kerosene 400 2000 30

(One times)

Industrial Applicability

[0088] The exemplary method and catalyst disclosed herein may be utilized for fast, cost- effective and highly efficient sulfur removal of liquid hydrocarbon fuels, oil cuts and crudes, such as VGO. The exemplary method benefits from using ozone gas as oxidizing agent, which may be continuously and in-situ produced during sulfur removal process. Additionally, ozone may be used for sulfur removal in large scales through a simply-controllable process. On the other hand, use of the exemplary catalyst (quantum dot hybrid catalyst) in ODS processes may result in completely removal of sulfur content of liquid hydrocarbon fuels, oil cuts and crudes in moderate conditions, such as environment temperature and pressure.

[0089] While the foregoing has described what are considered to be the best mode and/or other examples, it is understood that various modifications may be made therein and that the subject matter disclosed herein may be implemented in various forms and examples, and that the teachings may be applied in numerous applications, only some of which have been described herein. It is intended by the following claims to claim any and all applications, modifications and variations that fall within the true scope of the present teachings.

[0090] Unless otherwise stated, all measurements, values, ratings, positions, magnitudes, sizes, and other specifications that are set forth in this specification, including in the claims that follow, are approximate, not exact. They are intended to have a reasonable range that is consistent with the functions to which they relate and with what is customary in the art to which they pertain.

[0091] The scope of protection is limited solely by the claims that now follow. That scope is intended and should be interpreted to be as broad as is consistent with the ordinary meaning of the language that is used in the claims when interpreted in light of this specification and the prosecution history that follows and to encompass all structural and functional equivalents. Notwithstanding, none of the claims are intended to embrace subject matter that fails to satisfy the requirement of Sections 101, 102, or 103 of the Patent Act, nor should they be interpreted in such a way. Any unintended embracement of such subject matter is hereby disclaimed.

[0092] Except as stated immediately above, nothing that has been stated or illustrated is intended or should be interpreted to cause a dedication of any component, step, feature, object, benefit, advantage, or equivalent to the public, regardless of whether it is or is not recited in the claims.

[0093] It will be understood that the terms and expressions used herein have the ordinary meaning as is accorded to such terms and expressions with respect to their corresponding respective areas of inquiry and study except where specific meanings have otherwise been set forth herein. Relational terms such as first and second and the like may be used solely to distinguish one entity or action from another without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms“comprises,” “comprising,” or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by“a” or“an” does not, without further constraints, preclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0094] The Abstract of the Disclosure is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in various implementations. This is for purposes of streamlining the disclosure, and is not to be interpreted as reflecting an intention that the claimed implementations require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed implementation. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separately claimed subject matter.

[0095] While various implementations have been described, the description is intended to be exemplary, rather than limiting and it will be apparent to those of ordinary skill in the art that many more implementations and implementations are possible that are within the scope of the implementations. Although many possible combinations of features are shown in the accompanying figures and discussed in this detailed description, many other combinations of the disclosed features are possible. Any feature of any implementation may be used in combination with or substituted for any other feature or element in any other implementation unless specifically restricted. Therefore, it will be understood that any of the features shown and/or discussed in the present disclosure may be implemented together in any suitable combination. Accordingly, the implementations are not to be restricted except in light of the attached claims and their equivalents. Also, various modifications and changes may be made within the scope of the attached claims.