WO2015057108A1

WO2015057108A1 - Method for cleaning liquid motor fuels of sulfur-containing compounds

Info

Publication number: WO2015057108A1
Application number: PCT/RU2014/000768
Authority: WO
Inventors: Мария Владимировна НЕФЕДЬЕВА
Original assignee: Мария Владимировна НЕФЕДЬЕВА
Priority date: 2013-10-18
Filing date: 2014-10-14
Publication date: 2015-04-23
Also published as: RU2541315C1

Abstract

The given method relates to a method for cleaning liquid motor fuels of sulfur-containing compounds, including of difficult-to-crack sulfur-containing compounds. The invention relates to a method for cleaning motor fuels (gasoline and diesel fractions, naphtha and gasoils produced from gas condensate and petroleum fractions), including extracting sulfur-containing compounds from a fuel into an ionic liquid, partially oxidizing the extracted sulfur-containing compounds under the influence of a catalyst in an alcohol alkaline solution or in an acidic aqueous solution, separating-out the hydrocarbon fraction, and regenerating the ionic liquid with the possibility of subsequently reusing same multiple times. The following are used as the ionic liquid: 1-hexyl pyridinium-bis(trifluoromethylsulfonyl)imide, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-methyl-3-butylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium triflate, 1-methyl-3-octylimidazolium hexafluorophosphate, 1-butylimidazolium hydrogen sulfate, and 1-methyl-3-butylimidazolium chloride. The catalyst is comprised of dissolved salts or oxides of transition metals selected from a group including molybdenum, vanadium, tungsten, manganese, and chromium. The partial oxidation is carried out in an alcohol alkaline solution or in an aqueous acid solution with the help of ozone, hydrogen peroxide, a superacid or a peroxide of organic acids. The technical result is an increase in the level of cleaning of motor fuels, wherein the extractant (IL) is capable of operating without a decrease in activity, relative to the sulfur-containing compounds, for up to 20-30 cycles, and for an additional 10-15 cycles following regeneration.

Description

METHOD FOR CLEANING LIQUID ENGINE FUELS FROM SULFUR CONTAINING COMPOUNDS

The present invention relates to the purification of motor fuels from sulfur-containing compounds. More specifically, it relates to the process of desulphurization of motor fuels, including gasoline and diesel fractions, naphtha and gas oils, including those obtained from gas condensate and oil fractions and containing organo-sulfur compounds, by extraction of organo-sulfur compounds in a regenerated ionic liquid (IL) modified with salts and transition metal oxides, including molybdenum, vanadium, tungsten, manganese, chromium.

The primary task facing the domestic oil refining industry today is to achieve the European level of quality of motor fuels in accordance with the Euro-4 and Euro-5 standards.

For the large-scale production of high-quality gasolines and diesel fuels (DT) in accordance with European standards, it is necessary to introduce secondary processes for the deep processing of crude oil - hydrotreating, catalytic reforming, alkylation, isomerization, and others. The properties of the catalysts and the specificity of these processes cause a severe restriction on the residual content of sulfur, chlorine, nitrogen in straight-run oil fractions, which are the raw materials of these processes.

It is obvious that the quality of straight-run oil distillates directly depends on the chemical composition of the processed oil. Moreover, practice shows that in addition to the total sulfur content in oil, information on the content of mercaptan sulfur is very important. In some cases, with an increased content of chlorine or nitrogen compounds in oil, a detailed determination of the type and nature of heteroatomic compounds is necessary.

Involvement of gas condensate with a high mercaptan content in processing can cause a disruption in the technological process of the hydrotreating unit of the reforming unit. And the presence of volatile organochlorine compounds introduced in the process of oil production causes increased corrosion of equipment. The excessive content of nitrogenous components in straight-run gasoline and diesel fractions leads to a decrease in the activity of the catalysts during hydrotreating of these fractions.

From the foregoing, the relevance of research to determine the qualitative composition and concentrations of S-, O-, Ν-containing compounds in oils follows as the basis for creating an improved quality system. According to GOST R 51858, oil by quantitative sulfur content is divided into 3 classes:

Class 1 - low sulfur, containing not more than 0.6% sulfur;

Class 2 - sulfur, with a content of from 0.61 to 1.8% sulfur;

Class 3 - sour, containing more than 1.8% sulfur [GOST 9965-76

“Oil for refineries. Technical conditions ”].

To a lesser extent than sulfur, nitrogen-containing heterocyclic compounds also belong to undesirable oil components. These S, N-containing compounds complicate the implementation of many technological processes and impair the quality of oil products, contribute to the stabilization of oil-water emulsions, give products increased corrosion activity, low thermal and thermo-oxidative stability [Shabalina TN, Badyshtova KM, Elasheva O. M . et al. Prediction of the potential of light fractions and their sulfur content // Chemistry and Technology of Fuels and Oils. - 1999. - Jsfs 3.— p.6-7; Gerasimova N.N., Kovalenko E.Yu., Sergun V.P. et al. Distribution and composition of heteroorganic compounds in oils from the Upper Jurassic deposits of Western Siberia // Neftekhimiya. - 2005. - T.45. -. 2 4. - C. 251].

Thus, annually (million tons) are emitted from the products of fuel combustion into the atmosphere: about 80 oxides of sulfur, 30–50 oxides of nitrogen, 300 — of carbon monoxide, and 10–15 billion tons of carbon dioxide. The environmentally harmful effects of these products, in particular, sulfur dioxide and nitric oxide, on humans and the environment, lead to very serious consequences, including respiratory irritation, the formation of acid rain, the destruction of catalytic converters of automobile exhaust gases, etc. [Abrosimov A. A Ecology of the processing of hydrocarbon systems: Textbook / Ed. Doctor of Chemistry, prof. Dolomatova M.Yu., Doctor of Technical Sciences, prof. Telyasheva E.G. - M .: Chemistry, 2002. - 608 s: ill.]. The threat of environmental disaster has led to a sharp tightening of requirements for the quality of motor fuels. The leaders in this movement are Sweden and Germany, followed by the United States. The integration of Russia into the world economic processes and the European Community has led to the development of new environmental standards that are more stringent from the standpoint of gasoline - GOST 51105-97 and GOST R 51866-2002, legalizing the abandonment of tetraethyl lead, reducing the content of sulfur and aromatic hydrocarbons (especially benzene). In terms of sulfur content, the new standards in the current versions are fully consistent with their European counterparts: 150 mg / kg (Euro-3), 50 mg / kg (Euro-4) and 10 mg / kg (Euro-5) [Mitusova T.N. Polina E.V. Diesel fuel meeting European requirements // World of Petroleum Products. - 2002. - N ° 3.— p. 28-29; Druzhinin O. A., Sannikov A. L., Khavkin V. A. et al. Production of deeply purified diesel fuel by hydrogenation of straight-run distillates at moderate hydrogen pressure // World of Petroleum Products. - 2004.— Ν ° 2.— p. 12-13], against 0.05-0.1% according to GOST 2084-77.

The main requirements for the quality of diesel fuels in Europe are defined by the standard ΕΝ590: 2004, in Russia GOST R 52368-2005 (ΕΝ 590: 2004), which is its authentic translation. In accordance with these standards, the sulfur content in diesel fuel should not exceed (mg / kg):

View 1 - 350;

View 2 - 50;

View 3 - 10.

Undesirable is also a high content of aromatic hydrocarbons, especially condensed ones (not more than 11.0%), as well as nitrogen-containing compounds [Ponadiy OM, Nemamkina LG Comparative characteristics of standard domestic and foreign methods for testing the quality of motor gasolines // World of Petroleum Products - 2007. - Ν ° 8. - p.26-32; Nikitina E.A., Emelyanova V.E., Alekseeva S.I., Alexandrova E.V. Production of motor gasoline for Euro-3 and Euro-4 cars at Russian refineries // World of Petroleum Products. - 2006. - Ν ° 1. - p. 28-30].

All of the above allows us to state that one of the most important tasks of the domestic oil refining industry is to organize the production of high-quality motor fuels of environmental standards of Euro- 4 and Euro-5, which necessitates a review of the structure of production processes of oil refining [Donchenko VV, Kunin Yu.I., Kazmin DM The problem of providing international carriers with European-level diesel fuel in Russia // World of Petroleum Products.— 2006. - JY ^O 1. - C.3-5].

In the near future, of course, the widespread introduction of promising catalytic processes will begin: alkylation, isomerization, hydrocracking, etc. The development of new technological processes significantly increases the importance of monitoring the quality of raw materials (straight-run and mixed), intermediate and target products. Moreover, the determination of small and microconcentrations of sulfur compounds should be recognized as priority, since the latter can cause poisoning of the platinum reforming catalyst [Belinsky B.I., Berdnikov V.M., Vyuchny Yu.I. et al. Hydrotreating of mercaptans-containing gas condensate feedstock // Chemistry and technology of fuels and oils. - 2002. - N ° 3. - p.8-10.], influence the flow of technological processes, determine the compliance of target and intermediate products with regulatory requirements [Turova A.V., Mikishev V.A., Kuzora I.E. et al. Hydrogenosyl chloro-, nitrogen- and organosulfur compounds in gasoline fractions / ТН Oil and petrochemicals. - 2005. - N ° 6. - p. 18-21], which makes the classical hydrotreating method not always economically feasible in comparison with other alternative, for example, extraction and electrochemical methods of purification from sulfur- and nitrogen-containing compounds.

Sulfur can be contained in oils and petroleum fractions both in a free form and in the form of various compounds, of which hydrogen sulfide, mercaptans, sulfides, disulfides, thiophenes and thiophanes can be noted [Siraev I.N., Ulendeyeva A.D. , Parfyonova M.A. and other Organo-sulfur compounds of oils of various types // Oil refining and petrochemicals. - 2002. - Ν ° 9. - p. 33-39].

For economic and environmental reasons, there is an increasing need for liquid hydrocarbon mixtures containing very low sulfur concentrations. For example, in automobile fuel, the sulfur content should not exceed 30 rh. At present, hydrotreating is most often used for industrial cleaning of liquid petroleum hydrocarbons. This method, as you know, provides almost complete removal of mercaptans, sulfides and disulfides from liquid hydrocarbons (see "Technology of oil and gas processing", part 3, "Chemistry", Moscow, 1966). The disadvantage of this method is the high residual thiophene content and the high cost of the process.

Now, basically, work is underway aimed at improving the properties of catalysts: increasing activity, ignition temperature, increasing porosity and mechanical strength, by varying the chemical composition of the catalysts and the method for their preparation. In the work [Klicpera T., Zdraz CM. // Catal. Lett., 1999, Vol. 58, N2I, p. 47-51], Mo0 ₃ / MgO samples with a large specific surface area were studied, obtained by the new paste-like impregnation method and having high activity in the sulfated state during the hydrodesulfurization of benzothiophene.

Authors of the work [Yu Z.K., Verkade J.G. Energy & Fuels, 1999, Vol. 13, 1, p. 23-

28] suggest the use of metallic Na in tetradecane, which leads to the desulfurization of dibenzothiophene to biphenyl under fairly mild conditions (T = 150 ° C for 24 hours). Benzothiophene and acyclic organosulfur compounds were effectively desulfurized using Li or Na in a hydrocarbon solvent by heating to 254 ° C and 150 ° C, respectively.

One of the alternative hydrotreating methods proposed by Loginov and Nesterov [Loginov AV, Nesterov IV, Group “Field”, source - www.pole.tl.ru/innotech/]. is the use of enzymatic processes, however, this is complicated by the high cost of the required enzymes and the need to comply with strict conditions, in particular, temperature conditions.

Other known methods for purifying liquid hydrocarbon feedstocks include oxidizing organosulfur compounds by contacting the feedstock with an aqueous solution of sulfuric acid containing metal ions selected from the group consisting of manganese, vanadium, chromium, cobalt, cerium, or a mixture thereof, and pretreated with electrolysis under oxidation conditions, increasing the oxidation state of these ions. The resulting contact mixture is separated to obtain a purified liquid hydrocarbon feed and spent working solution containing reduced metal ions, followed by regeneration by electrolysis under oxidation of metal ions in an oxidation state exceeding their minimum oxidation state and returning to the process (see RF patent j ° 2101320, IPC C10G27 / 00, 01/10/1998). The disadvantages of this method are the impossibility of its use for the purification of gaseous hydrocarbons and high concentrations of sulfuric acid. These disadvantages were eliminated by oxidizing sulfur compounds by contacting a hydrocarbon feed with a working reagent containing transition metal ions in an oxidation state exceeding their minimum oxidation state, separating the resulting mixture to obtain purified hydrocarbon feed and a spent working reagent, which additionally contains ions of at least one and / or the metal itself, selected from the group of non-transition metals, including copper, lead, tin, gold, deposited on the surface of the sorbent. The presence of metal ions or the metals themselves increases the oxidizing ability of the working reagent and provides additional complexation with sulfur compounds found in the purified hydrocarbon feed. Metal salts deposited on the surface of the sorbent make it possible to simplify the process of purification of hydrocarbon feeds, since the separation of the mixture obtained by contacting can be carried out by simple filtration (see RF patent X ° 2166530, IPC C10G27 / 00, 05/10/2001). The disadvantages of this method include the use of metals (copper, lead, tin, gold) as oxidizing agents, and in general, the selected metals and their ions are environmentally hazardous (copper, lead, tin) or expensive (gold).

Improving the quality of hydrocarbons due to a more complete removal of organo-sulfur substances is achieved by treating the hydrocarbons being purified with an aqueous solution of a monovalent cation chloride in a turbulent mode under the influence of an electric field with a gradient of intensity of at least 0.01 V / cm ² . As an aqueous solution of the chloride of the monovalent cation, aqueous solutions of the compounds NaCl, KC1, LiCl, NH ₄ C1 or their mixtures are used in the ratio of the target product: an aqueous solution of the chloride of the monovalent cation 1-H-1 + 50. In this way, paraffin, olefin and aromatic hydrocarbons in liquid condition (see RF patent X ° 2026335, IPC C10G27 / 02, 01/09/1995). The disadvantage of this method of oxidation of organosulfur compounds in the conditions of generation of active chlorine is the possibility of the formation of various supertoxic organochlorine aromatic compounds, including dioxins, especially on carbon electrodes.

The task of reducing the content of organosulfur compounds in the final refined products can be solved by increasing the degree of extraction of sulfur compounds from hydrocarbon materials by their electrochemical oxidation using ionic liquids (see patent US 6274026 B1, IPC C10G31 / 00, 08/14/2001). The method is based on electrochemical oxidation of sulfur-containing compounds in an ionic liquid, followed by removal of the oxidation products by centrifugation and / or distillation of the hydrocarbon fraction. The method is applicable to mercaptans and non-mercaptan sulfur-containing compounds present in oil, present in oil in the form of thiophenes and benzothiophenes and capable of forming dimers or oligomers during electrochemical oxidation that precipitate on the anode or form an insoluble precipitate in the ionic liquid. As ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-butylpyridinium nitrate, 1-butyl-3-methylimidazolium tetrafluoroborate and mixtures thereof are used. The oxidation is carried out in an electrochemical reactor with a potential of 1.0-2.5 mA / cm ² on platinum, nickel, graphite electrodes in the temperature range 0-100 ° C. The disadvantage of this method is the restriction on its use only in the case of sulfur-containing compounds capable of oxidative electropolymerization, and such compounds as, for example, dibenzothiophene are not removed in principle.

The authors of US2004045874 (IPC B01J21 / 08; C10G29 / 20, 1.03.2004) propose a method for removing sulfur and nitrogen-containing compounds from hydrocarbons using IL of the general formula K ⁺ A ^~ . A ^"is selected from halides, nitrate, sulfate, phosphate, acetate, tetrafluoroborate, hexafluorophosphate, trifluoroacetate, triflate, sulfonylamide and others. K ^{+ is} selected from phosphonium, ammonium, sulfonium, mono-, di- and tetrasubstituted on an alkyl radical containing C from 1 to 30 atoms, for example, butylpyridinium, ethylpyridinium, pyridinium, ethylmethylimidazolium, butylmethylimidazolium, methylmethylimidazolium, etc. Method based on the removal of sulfur- and nitrogen-containing compounds from the hydrocarbon phase in the IL, followed by separation of the two-phase system by decantation and regeneration of the IL. The optimization of the process is carried out by selecting time, temperature, adding an alkylating agent of the general formula RX. R is selected from alkyl, alkene, arene, and radicals. X is identical to the anion of IL. This method is applicable for the removal of mercaptans, benzothiophenes, dibenzothiophenes. Optimization improves the recovery of butanediol from 7.7% to 99%.

The disadvantages of this method are the use of an inert atmosphere (argon) and duration (up to 10 hours). Based on the examples, only butanediol is described, and it is not possible to draw unambiguous conclusions about the effectiveness of the claimed method for removing the remaining sulfur-containing compounds.

Closest to the present invention in combination of essential features is US patent US7001504 (IPC C10G29 / 00, 02.21.2006), where the authors propose to extract organosulfur compounds from hydrocarbons by ionic liquids. The method is based on the removal of sulfur-containing organic compounds by extraction from a liquid or gaseous hydrocarbon phase into an ionic liquid, followed by separation of the resulting two-phase system by decantation or centrifugation and regeneration of the ionic liquid. As ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butylpyridinium nitrate, 1-butyl-3-methylimidazolium tetrafluoroborate and mixtures thereof are used. The extraction process is optimized by selecting contact time (5-60 min), temperature (30-50 ° C), pressure (1-50 atm), partial oxidation of sulfur-containing compounds to sulfoxides or sulfones before or during the extraction process. Oxidation is carried out by biological or chemical methods using salts or metal oxides selected from the group of platinum, palladium, vanadium, nickel as oxidation catalysts. The method for removing sulfur-containing compounds from an ionic liquid is selected from known methods: heating the ionic liquid · for evaporation of sulfur-containing compounds, extraction of sulfur-containing compounds from ionic liquid with other solvents, passing inert gases through the ionic liquid, evaporation of sulfur-containing compounds under vacuum, oxidation sulfur-containing compounds to sulfur dioxide by extraction with supercritical C0 ₂ or a combination of these methods. The content of sulfur-containing compounds in the hydrocarbon phase after contact with the ionic liquid is reduced by 10-15%. To reduce the content of sulfur-containing compounds in the hydrocarbon phase by 50-80%, a multiple extraction step is required. The disadvantage of this method is the need for multiple extraction to reduce the content of sulfur-containing compounds in the hydrocarbon phase by 50-80% with continuous regeneration of the ionic liquid after one extraction stage to restore the absorption capacity.

The objective of the present invention is to provide an effective method for purifying motor fuels, including the extraction of sulfur-containing compounds from fuel into an ionic liquid, their partial oxidation under the influence of a catalyst, and thus achieving a more complete removal of sulfur-containing organic substances.

The technical result is an increase in the degree of purification of motor fuels, and the extractant (IL) is able to work without reducing activity with respect to organosulfur compounds up to 20-30 cycles, and an additional 10-15 cycles after regeneration.

The technical result is achieved by creating a method for purifying motor fuels based on oil and gas condensate fractions from sulfur-containing compounds, including extraction of sulfur-containing compounds from fuel into an ionic liquid, partial oxidation of extracted sulfur-containing compounds by the action of a catalyst in an alcohol-alkaline solution or in an acidic aqueous solution, and separation of hydrocarbon fractions from ionic liquid.

According to preferred embodiments, the specified technical result is also achieved by the fact that:

- after separation of the hydrocarbon fraction, ionic liquid is regenerated with the possibility of subsequent reuse;

- regeneration is carried out in a soda-water solution by adding stoichiometric amounts of an oxidation-catalytic mixture; - use an ionic liquid that has a melting point below 50 ° C, and the solubility of hydrocarbons in said ionic liquid is less than 1%;

- use an ionic liquid consisting of: a cation selected from the group of alkylimidazolium, alkylpyridinium, polyalkylammonium, alkylpiperidinium, and an anion selected from the group of tetrafluoroborate, hexafluorophosphate, trifluoromethyl sulfonate (triflate), bis (trifluoromethyl sulfonyl, sulfate, nitrate, nitrate, nitrate;

said ionic liquid is selected from the group consisting of 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide, 3-octyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium tetrafluoroborate, 3-octyl-1-methylimidazolium triflate -methylimidazolium hexafluorophosphate and 1-butylpyridinium hydrosulfate;

- use an ionic liquid, which is taken in a volume ratio of 1: 10-1: 5 to the fuel being cleaned;

- use an alcohol-alkaline solution, which is a mixture of an aqueous solution of alkali and alcohol in a volume ratio of 1: 1; 1: 2; 1: 5: 1: 10 and 1: 20;

- said alkali is selected from the group comprising sodium hydroxide and potassium hydroxide;

- use an alcohol-alkaline solution containing at least one monobasic organic alcohol with a carbon atom number from 1 to 10;

- use an acidic aqueous solution, which is an aqueous acid solution with a pH in the range from 4.5 to 6.5;

- use an acidic aqueous solution containing at least one monobasic organic acid with a carbon atom number from 1 to 7;

- partial oxidation is carried out by a partial oxidizing agent selected from the group comprising ozone, hydrogen peroxide, superacid, peroxides of organic acids and superacids;

- said super acid selected from the group consisting of antimony pentafluoride and fluorosulfonic acid;

- said organic acid peroxide is selected from the group consisting of trifluoroacetic acid, fluorosulfonic acid, perbenzoic acid, peracetic acid; - the mentioned partial oxidizing agent is taken in a volume ratio of 1: 10-1: 5 to the fuel being cleaned;

- use a catalyst in solution containing at least one metal and / or metal oxide of the highest degree of oxidation with a concentration of from 1, 0 to 4.0 mmol / l;

- the metal is selected from the group of transition metals, including molybdenum, vanadium, tungsten, manganese, chromium;

- it is carried out with mechanical stirring on a magnetic stirrer in a closed vessel at a temperature not exceeding the boiling point of the fuel;

- the cleaning process is carried out from 0.2 to 1.5 hours;

- use a soda-water solution for regeneration, which is an aqueous solution of sodium carbonate with a concentration of from 0.94 to 1.88 mol / l;

- said oil and gas condensate fractions are selected from the group consisting of gasoline fractions, diesel fractions, naphtha, atmospheric, vacuum and cracked gas oils, stable gas condensate;

- said sulfur-containing compounds are compounds selected from the group consisting of elemental sulfur, hydrogen sulfide, thiols (mercaptans), thiophenols, sulfides (thioethers), disulfides, cyclic sulfides (thiocylanes), alkyl aryl sulfides, mercaptides, sulfur-containing compounds with condensed rings (bi- and polycyclic), including thiophenes, thiophanes, benzothiophenes, dibenzothiophenes, sulfones and sulfonic acids.

The problem is solved by creating a method for purifying hydrocarbon materials from sulfur compounds by oxidizing them by contacting the hydrocarbons with a working reagent - an ionic liquid and an alkaline-alcohol (or acidic aqueous) solution containing transition metal ions to the maximum degree of oxidation (or without their addition), separation of the mixture obtained by contacting motor fuel with a working reagent to obtain purified hydrocarbon feedstock and spent working reagent, the difference of which is the fact that the working reagent in addition to the alkaline alcohol or acidic solution additionally contains ions of at least one metal and / or a metal oxide selected from the group of transition metals, including molybdenum, vanadium, tungsten, manganese, chromium.

It is advisable as a working reagent to use salts and oxides of transition metals selected from the group: molybdenum, vanadium, tungsten, manganese, chromium.

The presence in the working reagent of metal ions or metal oxides selected from the group of transition metals, including molybdenum, vanadium, tungsten, manganese, chromium, increases the oxidizing ability of the working reagent and provides additional complexation with sulfur compounds in purified hydrocarbon feedstocks.

Metal salts and oxides can simplify the process of cleaning hydrocarbon feeds, since the separation of the mixture obtained by contacting can be solved by simple decanting, reduce the consumption of oxidizing agent and medium, and also increase the number of extractions without regeneration of a working reagent (IL).

The proposed method does not require preliminary hydrotreatment of hydrocarbon feeds, since the working reagent is operable in the presence of heteroatomic, unsaturated and gum-forming compounds, which is associated with the low acidity of the working reagent.

The working reagent is used in conjunction with an alcohol-alkaline or acidic solution of an oxidizing agent and is prepared by dissolving salts or oxides of transition metals of the highest oxidation state, selected from the group: platinum, palladium, molybdenum, vanadium, tungsten.

In the preparation of the working reagent, salts or oxides of transition metals in higher oxidation states are used, since they have optimal catalytic properties in the chemical oxidation of organosulfur compounds.

The oxidation process with simultaneous contacting of the working reagent is carried out at a temperature not exceeding the evaporation temperature of the fraction being purified and at atmospheric pressure. The actual temperature range is determined based on the composition and physico-chemical characteristics of the motor fuel, available technological equipment and requirements for refined hydrocarbons.

The contacting of the hydrocarbon feedstock and the working reagent can be carried out with stirring, barbation or passing one component through another (for example, gaseous or liquid hydrocarbon feeds are passed through a layer of working reagent).

If the working reagent and the initial hydrocarbon feed were in liquid form, then the separation of the mixture obtained by contacting with the release of purified hydrocarbon feed may be carried out by settling, distillation or other method.

The spent working reagent can be regenerated with a soda-water solution by known methods or sent for disposal.

The molar ratio of metals and oxidizing agent, taken in a small stoichiometric excess, in the prepared working reagent to elemental sulfur contained in the hydrocarbon feed should be in the range from 1.5 to 99. The volume of the prepared working reagent is 1-20% (mass.) from the volume of the original motor fuel.

Contacting of motor fuel and working reagent in calculated quantities is carried out in a special sealed container, which can be equipped with a device for mixing and a device for maintaining a given temperature.

At the end of the process, the purified motor fuel and the spent working reagent are separated. The residual content of total elemental sulfur in purified motor fuel is determined in accordance with GOST R 51.947.

The spent working extractant is regenerated with a soda solution from

10 to 20 times without a significant decrease in the adsorption capacity / activity of sulfur-containing compounds of the working reagent.

The extractant (IL) is able to work without reducing activity with respect to organosulfur compounds up to 20-30 cycles and after regeneration - an additional 10-15 cycles. As a result of this, a purified gasoline fraction (BP) with the following characteristics was obtained at the output: - a product purified from sulfur, which retained the octane number (04) of the feedstock, which was confirmed by the research method according to GOST R 52947 (04 of the initial BF - 72.01; OCh after the desulfurization process - 79.50; the error of the method is 0.5) ;

- regenerated IL (for example, IL 1, IL 2, IL 3, IL 4, IL 5 and IL 6) is able to work without regeneration up to 20-30 times when the oxidizing agents described in the examples with a concentration of 0.5 mmol are introduced before each subsequent extraction / l in similar acidic (pH 4.5-6.5) and alcohol-alkaline media (pH 8.5-1.5), which also confirmed the data according to GOST R 51947, and up to 10-15 times after regeneration ( washing) with a soda-water solution with a concentration of 0.94-1.88 mol / l;

- a mixture of organosulfur compounds and excipients with minimal volumes for disposal.

With the simultaneous use of highly oxidized metal oxides from the group of molybdenum, vanadium, tungsten, manganese, chromium as catalysts, washing to regenerate the extractant (IL) with an aqueous-soda solution with a concentration of 0.94-1.88 mol / L is required after each extraction with a decrease in the activity of the extractant for 5-15 cycles, which simultaneously leads to an increase in the volume of effluents for disposal.

The best results for the first disposal method are shown in table 1.

Table 1. The residual sulfur content in the gasoline fraction after the listed regeneration cycles. ftb n / a Number Time Content Class

extraction of mixing, total sulfur obtained

h mg / l fuel (BP)

BF PS “single” 194 3

(Ex. 1) (to

carrying out

extraction)

1 2 0.25 2.5 5

2 5 0.25 4.3 5

3 10 0.25 6.4 5

4 15 0.25 9.0 5

5 20 0.25 13.2 4 6 25 0.25 16.9 4

In embodiments of the invention, the purification of gasoline fractions is considered. However, it is obvious to a person skilled in the art that this method can also be used for diesel fractions, ligroin (naphtha), atmospheric, vacuum and cracking gas oils, stable gas condensate and other oil fractions and crude oil with an organo-sulfur content of less than 3 000 ppm.

Preferably, the method is carried out by creating a method for purifying motor fuels based on oil and gas condensate fractions from the main classes of sulfur-containing compounds, characterized in that almost all classes of sulfur-containing compounds are removed from real motor fuels, and not only heterocyclic compounds, which occurs more fully ( sulfur reduction occurs not by 5 times for model heterocyclic compounds, but by 15-20 of the total sulfur) for a shorter reaction time - 15-30 minutes instead of 1-6 hours, in addition to Under the medium, the possibility of using more gentle conditions, an alcohol-alkaline solution, is shown. Regeneration takes place in an aqueous-soda solution with a soda concentration from 0.94 to 1.88 mol / L or without replacing the ionic liquid, but only when stoichiometric amounts of the oxidation-catalytic mixture are added without reducing the adsorption capacity of the ionic liquid by 10-20 times, unlike 5-9 times, as in the prototype.

The proposed method for reducing the content of the main classes of sulfur-containing compounds in hydrocarbon feedstocks is based on the higher solubility of sulfur-containing compounds in ionic liquids compared to hydrocarbons. The extraction process involves mixing the hydrocarbon phase with an ionic liquid with a catalyst (metal oxide or its salt) and partial oxidation in an alcohol-alkaline solution or acidic medium, followed by separation of the hydrocarbon phase and regeneration with an ionic liquid for repeated reuse. The proposed method can be implemented in relatively mild conditions (heating to 50-60 ° C), atmospheric pressure using available reagents and standard operations, which leads to a significant reduction in capital costs. The proposed method is applicable for the removal of most classes of sulfur-containing organic compounds (mercaptans, organic sulfides and disulfides), including difficultly cracked (thiophenes, thiophanes, benzo and dibenzothiophenes and their derivatives, sulfones and sulfonic acids), from any hydrocarbon raw material without restrictions, including from gasoline and diesel fractions derived from gas condensate.

Ionic liquids have become an alternative to classic solvents due to their unique properties. They are not combustible, not volatile, i.e. have a negligible vapor pressure, are thermally stable, non-toxic, conduct electric current in a wide range of potentials.

The selection criteria for the ionic liquid for extraction are its melting point (below 50 ° C) and the solubility of hydrocarbons in IL (less than 1%). The following ionic liquids containing cations can be used for this purpose: alkylimidazolium, alkylpyridinium, polyalkylammonium, alkylpiperidinium and anions: tetrafluoroborate, hexafluorophosphate, triflate, bis (triflate) imide, nitrate, acetate, chloride, hydrosulfate. The most suitable for the chosen purpose are IL based on the substituted cation of imidazolium and pyridinium and the anions of tetrafluoroborate, hexafluorophosphate and hydrosulfate.

The following are examples of carrying out the invention with reference to the accompanying figures.

Examples of the invention and the implementation of the purpose

Methodology

The following ionic liquids were used as an extractant: 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide (IL 1); 3-octyl-1-methylimidazolium tetrafluoroborate (IL 2); 3-butyl-1-methylimidazolium tetrafluoroborate (IL 3); 3-octylmethylimidazolium triflate (IL 4); 3-octyl-1-methylimidazolium hexafluorophosphate (IL 5); 1-butylpyridinium hydrosulfate (IL 6).

The content of total elemental sulfur in the initial gasoline fraction was determined by energy dispersive X-ray fluorescence spectrometry according to GOST R 51947 on a Spectroscan instrument (NPO SPECTRON, RF). Example 1

IL 1 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, the partial oxidizing agent in the form of a solid Lewis super-acid - antimony pentafluoride ^* with a concentration of 0.1 mmol / l in an aqueous solution of propionic acid in the range of values was added in the same ratio pH from 4.5 to 6.5, and tungsten oxide (VI) ^** with a concentration of 2.0 mmol / l (or without the addition of oxide) was stirred on a magnetic stirrer in a closed vessel when heated, up to 40-60 ° C, within 0.33 hours. The gasoline fraction was separated by decantation, cooled to room temperature, remaining Noe sulfur content measured according to GOST 51947 on the device "Spectroscan".

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, perbenzoic acid, as well as peroxynaphthenic acid, etc. can be used as a partial oxidizing agent.

** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1.0 or higher can be used as a catalyst. up to 4.0 mmol / l.

Example 2

IL 2 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, the partial oxidizing agent - supertrifluoroacetic acid ^* with a concentration of 0.1 mmol / L in an aqueous solution of acetic acid in the pH range from 4.5 was added in the same ratio up to 6.5, and vanadium (V) oxide with a concentration of 3.5 mmol / L ^** (or without the addition of oxide) was stirred on a magnetic stirrer in a closed vessel when heated, 30-60 ° C for 0.50 hours The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was measured according to GOST 51947 on the device "Spectroscan".

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, and fluorosulfonic acid can be used as a partial oxidizing agent acid, peracetic acid, perbenzoic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc.

Example 3

IL 3 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, supertrifluoroacetic acid ^* with a concentration of 0.1 mmol / L in an aqueous solution of butyric acid was added in the same ratio in the pH range from 4.5 to 6, 5, and molybdenum (VI) oxide with a concentration of from 1.0 to 4.0 mmol / L ^** (or without the addition of oxide) was stirred on a magnetic stirrer in a closed vessel when heated to a temperature of 25-45 ° С, for 0 , 33 h. The gasoline fraction was separated by decantation, cooled at room temperature, the residual sulfur content was measured according to GOST P 51947 on the Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, perbenzoic acid, as well as peroxynaphthenic acids, antimony pentafluoride, etc. can be used as a partial oxidizing agent.

Example 4

IL 4 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, peroxynaphthenic acid ^* with a concentration of 0.1 mmol / L in an aqueous solution of acetic acid in the pH range from 4.5 to 6 was added. 5 and vanadium (V) oxide with a concentration of 3.5 mmol / L ^** (or without the addition of oxide) were mixed on a magnetic stirrer in a closed vessel at heating to a temperature of 30-40 ° C for 0.50 hours. The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was measured according to GOST R 51947 on a Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, perbenzoic acid, supratrifluoroacetic acid, antimony pentafluoride, etc. can be used as a partial oxidizing agent.

Example 5

IL 5 was taken in a volume ratio of 1: 10–1: 5 with the gasoline fraction to be purified, and superbenzoic acid ^* with a concentration of 0.1 mmol / L was added in the same ratio as a partial oxidizing agent in an aqueous solution of heptanoic acid in the pH range from 4, 5 to 6.5, and molybdenum (VI) oxide with a concentration of 1.0 to 4.0 mmol / L ^** (or without the addition of oxide), was stirred on a magnetic stirrer in a closed vessel when heated to a temperature of 30-60 ° C , within 0.33 hours. The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was measured according to GOST R 51947 on a Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, supertrifluoroacetic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc. can be used as a partial oxidizing agent.

** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1.0 or higher can be used as a catalyst. up to 4.0 mmol / l. Example 6

IL 6 was taken in a volume ratio of 1: 10–1: 5 with the gasoline fraction to be purified, the peracetic acid phase ^{* was} added in the same ratio ^* with a concentration of OD mmol / L in an aqueous solution of acetic acid in the pH range from 4.5 to 6.5 and tungsten oxide with a concentration of 2.0 mmol / L ^** (or without the addition of oxide) was stirred on a magnetic stirrer in a closed vessel when heated to 40-60 ° C for 0.50 hours. The gasoline fraction was separated by decantation, cooled to room temperature. temperature, residual sulfur content was measured according to GOST R 51947 on the instrument "Spectrum Scan ".

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, superfluorosulfonic acid, supertrifluoroacetic acid, superbenzoic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc. can be used as a partial oxidizing agent.

** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1.0 or higher can be used as a catalyst. up to 4.0 mmol / l. Example 7

IL 1 was taken in a volume ratio of 1: 10–1: 5 with the gasoline fraction to be purified, peracetic acid ^{* was} added ^* in an alkaline alcohol solution in the pH range from 8.5 to 1.5, where ethanol-propanol was used as the alcohol the mixture in a volume ratio of 1: 1 ^** , and as alkali - an aqueous solution of sodium hydroxide with a concentration of 0.01-0.03 mol / l, and vanadium oxide (V) with a concentration of 3.5 mmol / l ^*** ( or without the addition of oxide), was stirred on a magnetic stirrer in a closed vessel when heated to a temperature of 40-70 ° C and for 0.50 h. to Benzinov the southern fraction was separated by decantation, cooled to room temperature, the residual sulfur content was determined according to GOST R 51947 on a Spectroscan instrument.

Note: * Ozone in a comparable molar ratio, hydrogen peroxide, superfluorosulfonic acid, supertrifluoroacetic acid, superbenzoic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc. can be used as a partial oxidizing agent.

** Methanol, ethanol, propanol and isopropanol, butanol and its isomers, pentanol and its isomers, hexanol and its isomers, heptanol and its isomers, octanol and its isomers, nonanol and its isomers, decanol and can be used as alcohol. its isomers.

*** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1, or more, can be used as a catalyst. 0 to 4.0 mmol / L.

Example 8

IL 2 was taken in a volume ratio of 1: 10–1: 5 with the gasoline fraction to be purified, super trifluoroacetic acid ^{* was} added in the same ratio ^* in an alkaline-alcohol solution in the pH range from 8.5 to 11.5, where alcohol was used methanol-ethanol mixture in a volume ratio of 1: 1 ^** , and as alkali - an aqueous solution of sodium hydroxide with a concentration of 0.01-0.03 mol / l, and molybdenum oxide (VI) oxidation with a concentration of 1.0 mmol / l *** (or without the addition of oxide), was stirred on a magnetic stirrer in a closed vessel when heated to a pace 40–70 ° С for 0.33 h. The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was determined according to GOST R 51947 on a Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio can be used as a partial oxidizing agent, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, supertrifluoroacetic acid, superbenzoic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc.

** Methanol, ethanol, propanol and isopropanol, butanol and its isomers, pentanol and its isomers, hexanol and its isomers, heptanol and its isomers, octanol and its isomers, nonanol and its isomers, decanol and can be used as alcohol. its isomers. *** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1, or more, can be used as a catalyst. 0 to 4.0 mmol / L.

Example 9

IL 3 was taken in a volume ratio of 1: 10-1: 5 with cleaned gasoline

*

fraction, was added in the same ratio of peroxynaphthenic acid in an alkaline alcohol solution in the pH range from 8.5 to 1 1.5, where pentyl and isopentyl alcohol were used as alcohol in a volume ratio of 1: 1 ^** , and as alkalis - an aqueous solution of potassium hydroxide with a concentration of 0.01-0.03 mol / l, and a metal oxide of tungsten (VI) highly oxidized with a concentration of 2.0 mmol / l ^*** (or without the addition of oxide), was mixed on a magnetic stirrer in a closed vessel when heated to a temperature of 40-70 ° C for 1.00 hours. Gasoline the fraction was separated by decantation, cooled to room temperature, the residual sulfur content was determined according to GOST R 51947 on a Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, supertrifluoroacetic acid, superbenzoic acid, as well as antimony pentafluoride, etc. can be used as a partial oxidizing agent.

Example 10 IL 4 was taken in a volume ratio of 1: 10–1: 5 with the gasoline fraction to be purified, added in the same ratio superbenzoic acid ^* in an alkaline-alcohol solution in the pH range from 8.5 to 11.5, where alcohol was used hexanol-1 and heptanol-1 in a volume ratio of 1: 1 ^** , and as alkali - an aqueous solution of sodium hydroxide with a concentration of 0.01-0.03 mol / l, and molybdenum (VI) oxide with a high degree of oxidation with a concentration 2.0 mmol / l ^*** (or without the addition of oxide), and stirred on a magnetic stirrer in a closed vessel under heating to those perature 40-70 ° C for 0.66 hours. The gasoline fraction is separated by decanting, allowed to cool to room temperature, the residual sulfur content was determined according to GOST 51947 on the device "Spectroscan".

Note:

Example 11

IL 5 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, antimony pentafluoride ^{* was} added in an alkaline alcohol solution in the pH range from 8.5 to 1.5, where methanol was used as alcohol ^** and, as an alkali, an aqueous solution of potassium hydroxide and manganese oxide (VII) with a concentration of 2.5 mmol / L ^*** (or without the addition of oxide) were stirred on a magnetic stirrer in a closed vessel when heated to a temperature of 40-70 ° C for 0.66 hours. The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was determined according to GOST R 51947 on the Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, supertrifluoroacetic acid, superbenzoic acid, as well as peroxynaphthenic acid, etc. can be used as a partial oxidizing agent.

*** Vanadium (V) oxide, molybdenum (VI) oxide, chromium (VI) oxide, manganese (VII) and (V) oxides and other transition metal oxides in higher oxidation states with a concentration of 1.0 or higher can be used as a catalyst. up to 4.0 mmol / l.

Example 12

IL 6 was taken in a volume ratio of 1: 10-1: 5 with the gasoline fraction to be purified, superfluoroacetic acid ^{* was} added in the same ratio ^* in an alkaline alcohol solution in the pH range from 8.5 to 11.5, where alcohol was used ethanol ^** , and as alkali - an aqueous solution of hydroxide with a concentration of 0.01-0.03 mol / L, and tungsten oxide with a concentration of 2.0 mmol / L ^*** (or without the addition of oxide), was stirred on a magnetic stirrer in a closed vessel when heated to a temperature of 40-70 ° C for 1.50 hours. The gasoline fraction was separated by decantation, cooled to room temperature, the residual sulfur content was determined according to GOST R 51947 on a Spectroscan instrument.

Note:

* Ozone in a comparable molar ratio, hydrogen peroxide, perfluorosulfonic acid, peracetic acid, supertrifluoroacetic acid, as well as peroxynaphthenic acid, antimony pentafluoride, etc. can be used as a partial oxidizing agent. ** Methanol, ethanol, propanol ol-1 and iso-propanol, butanol-1 and its isomers,, pentanol-1 and its isomers, hexanol-1 and its isomers, heptane ol-1 and its isomers can be used as alcohol , octanol-1 and its isomers, nonanol-1 and its isomers, decanol-1 its isomers are alcohols.

Table 2 presents the best experimental results. In all cases, there was a decrease in total elemental sulfur from 15 to 20 times with the receipt of fuels that meet the new European standards EURO-4 and EURO-5.

Table 2. The results of the purification of gasoline fractions from sulfur-containing compounds.

Thus, the present experimental data demonstrated that after the processing of motor fuels by this method, the total number of sulfur-containing compounds decreased by 15-20 times, whereas in the prototype described in US7001504, the reduction of sulfur-containing substances in one extraction step was up to 10-15%.

Claims

CLAIM

1. A method of purifying motor fuels based on oil and gas condensate fractions from sulfur-containing compounds, including the extraction of sulfur-containing compounds from fuel into an ionic liquid, partial oxidation of extracted sulfur-containing compounds under the action of a catalyst in an alcohol-alkaline solution or in an acidic aqueous solution, and separating the hydrocarbon fraction from the ionic liquids, characterized in that:

using an ionic liquid consisting of: a cation selected from the group of alkylimidazolium, alkylpyridinium, polyalkylammonium, alkylpiperidinium, and an anion selected from the group of tetrafluoroborate, hexafluorophosphate, trifluoromethyl sulfonate (triflate), bis (trifluoromethyl sulfonyl) imide, nitrate, nitrate, nitrate, nitrate, nitrate

the ionic liquid is taken in a volume ratio of 1: 10-1: 5 to the fuel to be purified, a catalyst in solution is used, containing at least one metal and / or metal oxide in the highest oxidation state with a concentration of from 1.0 to 4.0 mmol / l, the metal is selected from the group of transition metals, including molybdenum, vanadium, tungsten, manganese, chromium,

mechanical mixing is carried out in a closed vessel at a temperature not exceeding the boiling point of the fuel.

2. The method according to claim 1, characterized in that after separation of the hydrocarbon fraction, the ionic liquid is regenerated with the possibility of subsequent reuse.

3. The method according to claim 2, characterized in that the regeneration is carried out in an aqueous-soda solution by adding stoichiometric amounts of an oxidation-catalytic mixture.

4. The method according to claim 1, characterized in that they use an ionic liquid that has a melting point below 50 ° C, and the solubility of hydrocarbons in said ionic liquid is less than 1%.

5. The method according to claim 1, characterized in that said ionic liquid is selected from the group consisting of 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide, 3- octyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium tetrafluoroborate, 3-octyl-1-methylimidazolium triflate, 3-octyl-1-methylimidazolium hexafluorophosphate and 1-butylpyridinium hydrosulfate.

6. The method according to claim 1, characterized in that they use an alcohol-alkaline solution, which is a mixture of an aqueous solution of alkali and alcohol in a volume ratio of 1: 1; 12; 1: 5: 1: 10 and 1:20.

7. The method according to claim 6, characterized in that said alkali is selected from the group comprising sodium hydroxide and potassium hydroxide.

8. The method according to claim 6, characterized in that they use an alkaline alcohol solution containing at least one monobasic organic alcohol with a carbon atom number from 1 to 10.

9. The method according to claim 1, characterized in that they use an acidic aqueous solution, which is an aqueous acid solution with a pH in the range from 4.5 to 6.5.

10. The method according to claim 9, characterized in that they use an acidic aqueous solution containing at least one monobasic organic acid with a carbon atom number from 1 to 7.

11. The method according to claim 1, characterized in that the partial oxidation is carried out by a partial oxidizing agent selected from the group consisting of ozone, hydrogen peroxide, superacid, peroxides of organic acids and superacids.

12. The method according to claim P, characterized in that said super acid is selected from the group consisting of antimony pentafluoride and fluorosulfonic acid.

13. The method according to claim 11, characterized in that the said organic acid peroxide is selected from the group comprising supertrifluoroacetic acid, superfluorosulfonic acid, superbenzoic acid, peracetic acid.

14. The method according to PP, characterized in that the said partial oxidizing agent is taken in a volume ratio of 1: 10-1: 5 to the fuel to be cleaned.

15. The method according to claim 1, characterized in that the cleaning process is carried out from 0.2 to 1.5 hours

16. The method according to p. 3, characterized in that they use a soda-water solution for regeneration, which is an aqueous solution of sodium carbonate with a concentration of from 0.94 to 1.88 mol / L.

17. The method according to claim 1, characterized in that the said oil and gas condensate fractions are selected from the group comprising gasoline fractions, diesel fractions, naphtha, atmospheric, vacuum and cracked gas oils, stable gas condensate.

18. The method according to claim 1, characterized in that said sulfur-containing compounds are compounds selected from the group consisting of elemental sulfur, hydrogen sulfide, thiols (mercaptans), thiophenols, sulfides (thioethers), disulfides, cyclic sulfides (thiocyananes), alkylaryl sulfides, mercaptides, sulfur-containing compounds with condensed rings (bi- and polycyclic), including thiophenes, thiophanes, benzothiophenes, dibenzothiophenes, sulfones and sulfonic acids.