EP1346009A1

EP1346009A1 - Method and device for desulphurising hydrocarbons containing thiophene derivatives

Info

Publication number: EP1346009A1
Application number: EP01994923A
Authority: EP
Inventors: Pédro DA SILVA; Edmond Payen; Jean-Yves Carriat; Marc Bisson
Original assignee: TotalFinaElf France SA
Current assignee: Total Marketing Services SA
Priority date: 2000-12-28
Filing date: 2001-12-20
Publication date: 2003-09-24
Anticipated expiration: 2021-12-20
Also published as: FR2818990B1; DE60107602T2; FR2818990A1; DE60107602D1; KR100824422B1; ES2234930T3; EP1346009B1; KR20030065585A; US20060180501A1; JP2004517193A; ATE283905T1; WO2002053683A1

Abstract

The invention relates to a selective desulphurisation method for thiophene derivatives contained in the hydrocarbons emitted from the distillation of crude oil, refined or not, consisting in oxidising the atoms of thiophene sulphur in sulphone in the presence of an oxidising agent and separating the sulphonated compounds from said hydrocarbons. This inventive method comprises at least one first stage involving the oxidation/absorption by heterogeneous catalysis of the sulphurous compounds in an organic environment, at a temperature of at least 40?C, at atmospheric pressure in the presence of an organic oxidiser from the family of peroxides and peracids, in the presence of a catalyst having a specific surface area greater than 100 m2/g and a porosity varying from 0.2 to 4 ml/g, and a second stage wherein the used catalyst is regenerated.

Description

DESULFURIZATION PROCESS AND DEVICE

OF HYDROCARBONS CHARGED WITH THIOPHENIC DERIVATIVES.

The present invention relates to a process and a device for the desulfurization of hydrocarbons, in particular for the desulfurization of fuel bases for gas oils, kerosene and gasolines. It relates in particular to the desulfurization of fuel bases loaded with dibenzothiophene compounds.

The presence of sulfur in fuels constitutes a problem considered today as major for the environment. In fact, by combustion, the sulfur is converted into various sulfur oxides, which can transform into acids, thus contributing to the formation of acid rain.

Typically, refineries use catalytic hydrodesulfurization processes to lower the sulfur content of fuels. Thus, the gas oils coming directly from the distillation are hydrotreated between 300 and 400 ° C, under a hydrogen pressure varying between 30 and 100 bars (30 to 100.10 ⁵ Pa), in the presence of a catalyst placed in a fixed bed and constituted metal sulfides of groups VIb and VIII deposited on alumina, for example cobalt and molybdenum sulfides or nickel and molybdenum sulfides. Given the operating conditions and the hydrogen consumption, these processes can be costly in investment and in operation, in particular if it is sought to produce fuels with a very low sulfur content. Thus, to desulfurize a fuel initially containing 1% by weight of sulfur, up to a sulfur content of between

0.05 and 0.005% by weight, the size of the reactor can be multiplied by 4 and the quantity of hydrogen necessary for the reaction must be increased by approximately 20%. It is particularly difficult, by such methods, to remove traces of sulfur, especially if the sulfur belongs to refractory molecules such as dibenzothiophene alkylated in position 4, or 4 and 6.

In some countries such as Sweden, the United States, especially California, and others, the total sulfur content of diesel oils is already limited to 0.005% by weight. This limitation could be generalize over time in OECD countries. For Europe, this target of 0.005% by weight of total sulfur should be reached in 2005.

Unlike gas oils, gasolines do not only come from the direct distillation of crude oil, these gasolines being then slightly sulfur-containing, but can also be obtained by several processes such as the reforming of naphthas, the isomerization of light naphthas, alkylation butane or propane producing Tisooctane, the methoxylation of isobutene and the catalytic cracking of distillates under vacuum or atmospheric residues. In particular, catalytic cracking provides between 20 and 60% by weight of the final gasoline. These essences contain up to 0.1% by weight of sulfur. It is therefore common to desulfurize gasolines from catalytic cracking by methods similar to those described for the hydrodesulfurization of gas oils, for which the operating conditions are more severe in hydrogen pressure, space velocity and temperature. These processes, although costly, do not however make it possible to conventionally reach total sulfur contents, in these cracking essences, of between 0.005 and 0.03% by weight. Although, to reduce this sulfur content, refiners have imagined adding to the cracking catalyst additives decomposing the sulfur compounds formed during the process, in particular mercaptans and sulphides, these additives have only one effect limited, or even zero, on benzo thiophenic derivatives, even when the mercaptans and sulphides have been eliminated before cracking. In the case of catalytic cracking gasolines that generate sulfur in gasolines, hydrodesulfurization is not only ineffective with respect to thiophenic compounds, but it is also destructive with respect to the octane number of l petrol. In fact, during the hydrodesulfurization reaction, there is partial hydrogenation of the olefins contained in these cracked gasolines, their disappearance resulting in a drop in the octane number of the gasoline and therefore a deterioration in the quality of gasoline. To compensate for this loss, it is possible to introduce other constituents to improve this index or to reprocess the essence itself to increase this index. Adding an additive or reprocessing to improve the quality of the gasoline strikes its cost price, and it is therefore advantageous to have a treatment process allowing direct elimination refractory sulfur compounds, such as benzothiophenic derivatives, by limiting the use of hydrogen.

Methods for the selective oxidation of sulfur compounds are part of the treatment methods capable of achieving this goal. Among the methods and processes developed to reduce the amount of sulfur present in fuels in the form of thiophene derivatives, oxidation with organic peroxides, organic hydroperoxides, hydrogen peroxide and organic peracids, has been considered either without catalyst, either by homogeneous catalysis in the presence of catalysts based on organometallic compounds or metal oxides in the aqueous phase (see US 3,668,117, US 3,565,793, EP 0 565 324 and the publications of TA KOCH, KR KRAUSE, L EMANZER, H. MEHDIZADEH, JM ODOM, SK SENGUPTA, New J. Chem., 1996, 20, 163-173 and FM COLLINS, AR LUCY, C. SHARP, J. of Molecular Catalysis A: Chemical 117 (1997) 397-403).

For the processes using metal catalysts based on molybdenum and tungsten in the presence of hydrogen peroxide in aqueous solution (heterogeneous catalysis), the operation is carried out at temperatures above 60 ° C. and there is overconsumption of peroxide. hydrogen, part of this oxidant being broken down by the catalyst used. The peracids used, very powerful oxidants, obtained by reaction of hydrogen peroxide and a carboxylic acid such as formic acid or acetic acid, are generally less effective than hydrogen peroxide and less selective with respect to -vis sulfur compounds and can oxidize in particular olefins.

Other processes for oxidesulfurization in an organic medium have been proposed: they consist in bringing metal oxides into powder form or in forming metal compounds comprising peroxo groups in aqueous or organic solutions with the hydrocarbons containing these refractory sulfur-containing compounds , in the presence or not of organic or aqueous peroxides, these being introduced with an alcohol type solvent or in water (see US 3,816,301, US 4,956,578, US 5,958,224). Another method, described in US Pat. The first step is to oxidize at least partially the sulfur-containing compounds by contacting with peroxides, in the presence of metal catalysts containing metals from the group comprising titanium, zirconium, molybdenum, tungsten, vanadium, tantalum, chromium and their mixtures, in liquid form or solid possibly supported, the supports not being essential for the reaction. The second step consists in bringing the hydrocarbon material containing these oxidized compounds into contact with another metallic component, metallic oxide or peroxide (metals of the group comprising nickel, molybdenum, cobalt, tungsten, iron, zinc, vanadium , copper, manganese, mercury and their mixtures), at a temperature varying from 250 to 730 ° C, under hydrogen pressure. The third step is to recover the desulfurized hydrocarbon material

In all these methods and processes, the thiophene derivatives are transformed into their sulfonated and / or sulfonic form.

However, for some of these compounds, even if one works at high temperature, the reaction is relatively slow and the total conversion is not reached in less than an hour, otherwise by using very high concentrations of oxidant, often very greater than the quantities necessary for the oxidation of the sulfur derivatives. In other cases, it is possible to work in several stages, but which are costly in time and in unit monitoring.

The present invention therefore aims to propose a process for the desulfurization of hydrocarbons, in particular those used as fuel bases containing thiophenic derivatives, without reducing the octane number index or the cetane number, sometimes even with an increase in these indices. It particularly relates to the finishing treatment of hydrotreated gas oils, kerosene and catalytic cracking gasolines, highly concentrated in thiophenic derivatives refractory to hydrogenations.

The invention further aims to propose such a process which makes it possible to reach oxidation levels identical, if not superior, to the known processes, while limiting the reaction and separation times of the sulfur-containing compounds oxidized from the desulfurized hydrocarbons.

The subject of the present invention is therefore a process for the selective desulfurization of the thiophenic compounds contained in the hydrocarbons from the distillation of crude oil, refined or not, consisting in oxidizing thiophenic sulfur atoms to sulfonates in the presence of an oxidizing agent and a catalyst, and in separating the sulfonated compounds obtained from said hydrocarbons, this process being characterized in that it comprises at least a first oxidation / adsorption step by heterogeneous catalysis of the sulfur-containing compounds, in an organic medium, at a temperature of at least 40 ° C., in the presence of an organic oxidant from the family of peroxides and peracids and in the presence of a catalyst with a specific surface greater than 100 m ² / g and a porosity varying from 0.2 to 4 ml / g, and a second stage of regeneration of the spent catalyst, the stage of regeneration always following the oxidation / adsorption step.

In the context of the present invention, the term “thiophene derivatives” means benzothiophenic, polybenzothiophenic compounds and their alkylated derivatives, among which the alkyldibenzothiophenes, which are particularly refractory to the conversion processes usually used by refiners.

The method according to the invention has the advantage, on the one hand, of ensuring at atmospheric pressure an oxidation of all the sulfur contained in the hydrocarbons and more selectively a conversion of the thiophenic derivatives into sulfonates, and this in the context of 'a simple industrial process, and, on the other hand, to simultaneously adsorb these sulfoxide compounds on the catalyst. Indeed, the separation of the hydrocarbons from most of the sulfonates and sulfoxides formed is immediate, the latter being found in solid form deposited on the catalyst or in the form of filterable deposit by means known per se, in the treated hydrocarbons. This catalyst, on which these sulfoxidized compounds have been absorbed, constitutes the "spent catalyst". It is possible to extract the sulfones possibly dissolved in the treated hydrocarbons. Furthermore, this oxidation / adsorption has no effect on olefins, which does not modify, in catalytic cracking gasolines, the octane number or the content of non-sulfur aromatic compounds. The oxidation process according to the invention also improves the cetane number of gas oils.

Without being limited by theory, it has appeared that the greater the specific surface of the catalyst, the more active it is. long time. In addition, the sulfonated and sulfoxidized type compounds having a strongly polar character, they are maintained at the surface of the catalyst, probably at the level of the Lewis acid sites of the catalyst. Likewise, the larger the pore size, the less the pores of the catalyst are likely to clog quickly, and the longer the longevity of the catalyst during the oxidation cycle. For the present invention, it is a question of selecting the catalyst which has the best compromise in specific surface area and in pore size to obtain sufficient activity and this for as long as possible to be the most effective in oxidation / adsorption.

When the process is carried out continuously intermittently, the oxidation / adsorption and regeneration steps can be carried out in the same reactor or simultaneously in reactors arranged in parallel and operating alternately for one or other of the fixed bed stages, or in at least two moving bed reactors connected to each other by the catalytic bed, one being dedicated to oxidation / adsorption, the other to regeneration.

In a fixed bed, the first reactor containing a fixed bed of catalyst receives the flows of hydrocarbons and oxidant and the second receives, for the regeneration of the catalyst, liquid effluents, for example a washing solvent, or oxidizing gaseous effluents , like air or an air / N2 mixture, the temperature of the catalytic bed being raised. These reactors change function when the efficiency of the catalyst in the oxidation / adsorption reactor is no longer sufficient for oxidation and / or adsorption.

In a moving bed, the hydrocarbons are brought into the first reactor where the oxidation takes place, the catalyst being progressively pushed towards the second reactor, where it is regenerated before being returned to the oxidation / adsorption reactor. Movable bed reactors, well known in particular in the field of reforming, can be used in this device. In this embodiment, a third reactor is used, disposed between the first two reactors and making it possible to remove the hydrocarbons from the used catalyst before washing it or carrying out the combustion of the trapped sulfonated and sulfoxidized compounds.

The catalysts used according to the present invention are chosen from the supports of the group consisting of silicas, aluminas, zirconia, amorphous or crystalline aluminosilicates, aluminophosphates, silicic and silicoaluminated mesoporous solids, active carbon and clays, these supports being used alone or as a mixture. In the catalysts of the invention, these supports can be advantageously used as metal supports from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese, cerium and tungsten, these metals in the form of oxides which can be introduced into the network of the support or deposited on the surface of the support. In fact, a synergistic effect of the metal with the support has been observed, that is to say an unexpected increase in the activity of the catalyst with regard to the oxidation of the thiophenic compounds and, in parallel, an increase in the trapping of the compounds sulfonated and sulfoxidized in the pores of the catalyst, without any of them being subsequently desorbed. In the process according to the invention, the catalyst contains from 0 to

30% by weight of metal in the form of oxide on at least one support. Preferably, the catalyst contains from 0 to 20% of metal in the form of oxide.

Among the supports made up of refractory oxides, gamma aluminas, silicas, mesoporous silicic and silicoaluminous solids are preferred.

Among the supported catalysts, preference is given to catalysts containing tungsten or titanium in the form of oxide deposited on a support or introduced into the network, this support being chosen from silicas, aluminas and aluminosilicates, alone or as a mixture.

In a preferred embodiment of the process, the oxidizing molar / total sulfur ratio contained in the hydrocarbons is between 2 and 20, and preferably between 2 and 6.

According to the invention, the oxidants are chosen from the compounds of general formula R1OOR2, in which R1 and R2 are identical or different, chosen from hydrogen, linear or branched alkyl groups, comprising from 1 to 30 carbon atoms and the aryl or alkylaryl groups, the aryl unit of which is optionally substituted by alkyl, Ri and R _{2 groups} which cannot simultaneously be hydrogen. In a preferred embodiment, the oxidant of formula R10OR2 is chosen from the group consisting of tert-butyl hydroperoxide and ditertiobutylperoxide.

Other oxidants of the invention, the peracids of formula R3COOOH, are chosen such that R3 is hydrogen or a linear or branched alkyl group comprising from 1 to 30 carbon atoms. They are preferably chosen from the group consisting of peracetic acid, performic acid and perbenzoic acid.

In the process of the invention, the regeneration step of the catalyst consists in removing, by washing or by combustion, the deposits formed.

For washing, a preferably polar solvent from the group consisting of water is used, the linear or branched alkanols comprising from 1 to 30 carbon atoms, alone or in mixture with water, the alkyl nitriles comprising from 1 to 6 carbon atoms. Water, acetonitrile, methanol and mixtures thereof are preferred.

By combustion, the catalyst is brought to a temperature of at most 800 ° C, preferably to a temperature less than or equal to 650 ° C, under a pressure varying from 10 ⁵ Pa to 10 ⁶ Pa, and preferably from 10 ⁵ Pa at 2.10 ⁵ Pa, in the presence of an oxidizing gas. By oxidizing gas is meant pure oxygen and all mixtures of gases containing oxygen, in particular mixtures of oxygen and nitrogen and the air itself. The amount of oxygen in the nitrogen is adjusted so as to limit the formation of water vapor, an excessively large amount of water vapor having the secondary effect of modifying the structure of the pores of the catalyst with reduction in their volume, especially when it contains crystalline aluminosilicates as support, such as zeolites or aluminophosphates. This adjustment also makes it possible to control the temperature variations linked to the exothermicity of the combustion.

A second object of the invention is a device for implementing the process defined above, this device comprising at least a first reactor containing an oxidation catalyst and comprising inlet pipes for the hydrocarbons and the oxidant and an outlet pipe for desulphurized hydrocarbons, and optionally a second reactor comprising inlet pipes for solvent or oxidizing gas from the catalyst, with a view to regenerating the latter, and a combustion gas outlet pipe. By oxidizing gas is meant here the oxygen / air, air / nitrogen and oxygen / nitrogen mixtures.

When the device comprises two reactors, the reactors can operate in a fixed bed or in a mobile bed. A third object of the invention is the application of the process defined above to the specific finishing treatment of gasolines from catalytic cracking or also to the treatment of gas oils which have been previously hydrotreated and of kerosene, for a better economy of the process. The invention will be described below in more detail with reference to the accompanying drawings. In these drawings:

FIG. 1 is a diagram of a device with two reactors operating alternately in oxidation and in regeneration of the catalyst; FIG. 2 is a diagram of a device comprising two moving bed reactors, the first corresponding to the oxidation step, the second to the catalyst regeneration step, a return line of the regenerated catalyst being added to the system ;

Figures 3-1 and 3-2 show curves illustrating the total sulfur content, as a function of time, of the hydrocarbons treated according to the invention in Example III below.

The device of FIG. 1 comprises two reactors 1 and 2 loaded with a catalyst arranged in a fixed bed. When the reactor 1 operates in oxidation and that the reactor 2 operates in regeneration, the line 3 brings to the reactor 1 the sulfur-containing hydrocarbon charge, into which the oxidant has been introduced via the line 4, the three-way valve 6a and the line 8a . The stream of desulphurized hydrocarbons leaves the reactor 1 via line 9a and rejoins the line 10a for evacuating desulphurized hydrocarbons via the three-way valve 7a.

In parallel, line 5 brings to reactor 2 either an appropriate solvent or an oxidizing gas, via the three-way valve 6b and line 8b. When the reactor is operating in combustion, the temperature of the catalytic bed is maintained at 500 ° C. The solvent containing the sulfonates recovered from the catalyst or the combustion gases, mainly SO ₂ , CO and CO ₂ , are removed via the line 9b, the three-way valve 7b and line 11b in line l ia.

When the regeneration of the catalyst is done and the activity of the catalyst of reactor 1 becomes insufficient, the function of the two reactors is switched. Thus, the hydrocarbon / oxidant mixture takes the line 3a and the valve 6b to enter the reactor 2. The desulphurized hydrocarbons are evacuated through the line 9b and are directed to the evacuation line 10a via the valve 7b and the line 10b. In parallel, the solvent or the oxidizing gas arriving via line 5 is directed into the reactor 1 via line 3a, valve 6a and line 8a. The solvent or the oxidation gases are brought back into the evacuation pipe 1a via the pipe 9a and the valve 7a.

The valves 6a, 6b, 7a and 7b can be exchanged according to a common process to allow the circulation of the proposed flows.

One can advantageously place on one of the lines 9a or 9b, or even 10a or 10b, a filter for recovering the solid sulfonates formed during the oxidation, which remain in suspension in the hydrocarbons. It is advantageous to add on these same pipes, downstream of these filters, sulfur traps equipped with absorbents of the silica or activated alumina type, to trap the sulphonates still dissolved in the treated hydrocarbons.

The device of FIG. 2 comprises two reactors 20a and

20b, arranged in series, each containing a movable catalyst bed, the reactor 20a operating in oxidation mode and the reactor 20b operating in regenerative mode, and a propulsion device 30 allowing the catalyst to return from the reactor 20b to the reactor 20a.

The hydrocarbons are brought via line 40 into reactor 20a, after having been doped with the oxidant via line 50. For example, reactor 20a can be chosen from funnel reactors, the moving bed of the catalyst moving by gravity towards the lower part of the reactor. Thus, while the desulphurized hydrocarbons are evacuated via line 60, the catalyst is pushed by gravity into reactor 20b via line 70. The solvent or the combustion gas are introduced via channel 80 into reactor 20b. To perform regeneration by combustion, the temperature is increased and maintained at 500 ° C. The solvent loaded with sulphonates or the combustion gases are evacuated via line 100.

As, generally, these moving beds operate intermittently, the catalyst not moving continuously, it is advantageous to have on the reactor 20b a solvent or nitrogen purge allowing the elimination of the hydrocarbons before washing, and / or elimination of combustion gases by nitrogen stripping.

At the outlet of the reactor 20b, the regenerated catalyst is led via the line 110 to the device 30. This device can be a device powered by pressurized gas or a worm. It returns the regenerated catalyst via line 120 to reactor 20a.

In certain particular embodiments of these mobile reactors, the reactors 20a and 20b can be part of the same unit having two separate stages. The examples below aim to illustrate the effectiveness of the process of the invention, without limiting its scope. EXAMPLE I

The present example aims to describe the effectiveness of the process according to the invention with regard to the elimination of the dibenzothiophene derivatives present in the bases for partially desulfurized fuels.

The catalyst samples used are of two types, the catalysts formed from a single support and those with one or more metals deposited by impregnation. Table 1 below gives the specific surface and porosity characteristics of each of them.

TABLE I

Catalysts C2, C3 and Ce were obtained by wet impregnation of a metal salt, respectively ammonium metatungstate and ammonium hexamolybdate, at a content of 140 mg of metal per gram of support, then dried and finally calcined at a temperature of 500 ° C.

Catalyst C ₄ was obtained by treatment of a commercial titanium beta zeolite according to the procedure described in patent EP 0 842 114. To test the activity of these catalysts in oxidation as a function of time, the following was introduced into a 150 ml micropilot 20 ml of catalyst. A charge of middle distillates is circulated on the catalyst after hydrotreatment, containing 212 ppm of residual sulfur refractory to hydrotreatment, doped with 1800 ppm of tert-butyl hydroperoxide (tBHP), at an hourly space speed (WH) of ¹ h ^-1 - under atmospheric pressure, at a temperature of 70 ° C. Samples are taken regularly during the oxidation to measure the activity of the catalyst over time. A comparative sample called Ti, corresponding to the use of catalyst alone without peroxide, is also followed.

In Table II below are given the results of efficiency of these catalysts over time.

TABLE II

After two hours of operation, these results confirm that, apart from the effect due to the nature of the catalyst, the larger the pore size of the catalyst and the specific surface area, the lower the sulfur content of the treated hydrocarbons. It can also be seen that the activity of the catalyst increases when it is made up of a metal oxide with support. On the other hand, after 24 hours, whatever the catalyst, a slight increase in the sulfur content of the desulphurized hydrocarbons is observed, which may correspond to the start of clogging of the pores of the catalyst, the sulfonates and sulfoxides being attached thereto. .

By this process, it is clear that the choice of a catalyst for the process of the invention is the result of a compromise between the nature of the catalyst, its specific surface and the size of the pores thereof.

EXAMPLE II

In this Example, the efficiency of the catalyst is measured as a function of the oxidation of the compounds.

The procedure is as in Example I, with the catalysts Ci - Ce and the formation of sulfones and sulfoxides is monitored with respect to the dibenzothiophene compounds, in particular benzothiophene (BT), dibenzothiophene (DBT) and 4.6 dimethyldibenzothiophene (DMBT). ), by gas chromatography equipped with a specific sulfur detector (SIEVERS method).

Table III below collates the results obtained.

TABLE III

These results show that there is conversion of at least 80% of the refractory thiophenic derivatives into sulfonates, with catalysts consisting of the only support, and more than 90%, with catalysts consisting of supports and of at least one metal. in the form of metallic oxide inserted into the network of the support or deposited on the support.

Example III

The present example aims to show, in parallel with the oxidation, the effect as a function of time of the adsorption of the sulfonated and sulfoxidized compounds on the oxidation / adsorption and regeneration sequences, and the efficiency of the regeneration operation with respect to to oxidation / adsorption.

The operation is carried out with the catalyst C3 under the operating conditions described in Example I on a middle distillate containing 44 ppm of sulfur after hydro treatment, and in the presence of 600 ppm of tBHP.

The results of the oxidation / adsorption are given in Figure 3-1, when the catalyst is fresh. After two days, the total sulfur content in the hydrocarbons rises substantially to the initial value, in the absence of the treatment according to the invention. The results in Figure 3-2 correspond to the monitoring of the sulfur content of these same hydrocarbons when this same catalyst C3 regenerated by combustion was used. The results obtained on a fresh catalyst are almost identical to those obtained on this same regenerated catalyst. These two curves show the advantage of the process of the invention which proposes an alternative operation of the same catalyst in oxidation / adsorption or in regeneration, the time of oxidation / adsorption naturally having to be adapted to the sulfur content.

Claims

CLAIMS 1 - Process for the selective desulfurization of thiophenic derivatives contained in hydrocarbons resulting from the distillation of crude oil, refined or not, consisting in oxidizing the thiophenic sulfur atoms to sulfonates in the presence of an oxidizing agent and in separating the sulfonated compounds from said hydrocarbons , this process being characterized in that it comprises at least a first oxidation / adsorption step by heterogeneous catalysis of the sulfur-containing compounds, in an organic medium, at a temperature of at least 40 ° C., in the presence of an organic oxidant of the family of peroxides and peracids and in the presence of a catalyst with a specific surface greater than 100 m ² / g and a porosity varying from 0.2 to 4 ml / g, and a second stage of regeneration of the spent catalyst, the regeneration step always following the oxidation / adsorption step. 2 - Process according to claim 1, characterized in that the oxidation / adsorption and regeneration steps are carried out successively in the same reactor on the same catalyst.

3 - Process according to claim 1, characterized in that the oxidation / adsorption and regeneration steps are carried out simultaneously in reactors (1, 2) arranged in parallel and operating alternately for one and the other of the steps .

4 - Process according to claim 1, characterized in that the oxidation / adsorption and regeneration steps are carried out in two moving bed reactors (20a, 20b) connected to each other by the catalytic bed, the one being dedicated to oxidation, the other to regeneration.

5 - Method according to one of claims 1 to 5, characterized in that the oxidizing agent is chosen from the group consisting of organic peroxides, organic hydroperoxides and peracids.

6 - Method according to one of claims 1 and 2, characterized in that the catalyst comprises a support chosen from the group consisting of silicas, aluminas, zirconia, amorphous or crystalline aluminosilicates, aluminophosphates, mesoporous solids, active carbon, clays and their mixtures.

7 - Process according to claim 6, characterized in that the catalyst contains at least one metal chosen from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese and tungsten, this metal being introduced into the network of the support or deposited in the form of oxide on the support.

8 - Method according to one of claims 1 to 7, characterized in that the catalyst contains from 0 to 30% by weight and, preferably, from 0 to 20% by weight of metal in the form of oxide.

9 - Method according to one of claims 1 to 8, characterized in that the catalyst consists of at least one support chosen from gamma alumina, silica and mesoporous silicic and silicoaluminated solids. 10 - Method according to one of claims 1 to 9, characterized in that the supported catalyst is chosen from catalysts containing tungsten on a support chosen from silicas and aluminas, alone or as a mixture.

11 - Method according to one of claims 1 to 10, characterized in that the oxidizing molar / total sulfur ratio in the hydrocarbons varies from 2 to 20, and preferably from 2 to 6.

12 - Method according to one of claims 1 to 11, characterized in that the oxidant is a compound of general formula R1OOR2, in which Ri and R2 are chosen identical or different from the group consisting of the hydrogen atom and the alkyl groups, linear or branched, comprising from 1 to 30 carbon atoms, Ri and R ₂ cannot simultaneously be hydrogen.

13 - Process according to claim 12, characterized in that the oxidant is chosen from the group consisting of tertiobutyl hydroperoxide and ditertiobutyl peroxide.

14 - Method according to one of claims 1 to 13, characterized in that the oxidant is a peracid of formula R3COOOH, in which R3 is hydrogen or a linear or branched alkyl group comprising from 1 to 30 carbon atoms. 15 - Process according to claim 14, characterized in that the oxidant is chosen from the group consisting of peracetic acid, performic acid and perbenzoic acid.

16- Method according to one of claims 1 to 15, characterized in that the catalyst regeneration step consists in eliminating the deposits formed by washing or by combustion.

17 - Device for implementing the method according to one of claims 1 to 16, this device comprising at least a first reactor containing an oxidation catalyst and comprising inlet pipes for hydrocarbons and the oxidant and an outlet pipe for desulfurized hydrocarbons, and a second reactor comprising inlet pipes for solvent or oxidizing gas from the catalyst, in particular view of regenerating it, and a combustion gas outlet pipe.

18 - Device according to claim 17, characterized in that it comprises two fixed bed reactors (1, 2) comprising common means for introducing effluents into the reactors and a circuit for distributing the flows of hydrocarbons, oxidants and regeneration effluents from one or other of the reactors, according to the mode of operation in oxidation or in regeneration thereof.

19 - Device according to claim 17, characterized in that it comprises at least two moving bed reactors (20a, 20b) arranged in series, one operating in oxidation mode the other in regeneration mode, and a circulation loop catalyst bringing the regenerated catalyst back to the oxidation reactor.

20 - Application of the method according to one of claims 1 to 16 to the desulfurization of hydrotreated gas oils, kerosene and gasolines, in particular gasolines from catalytic cracking.