KR100824422B1 - Method for desulphurising hydrocarbons containing thiophene derivatives - Google Patents

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

Selective desulphurization of thiophenol by-products contained in hydrocarbons {Method for desulphurising hydrocarbons containing thiophene derivatives}

The present invention relates to a desulfurization method for removing sulfur from hydrocarbons containing thiophenol by-products, and more particularly to a process for removing sulfur to obtain diesel oil, kerosene and gasoline from crude oil. In particular, it relates to a method for removing sulfur from crude oil containing a dibenzothiophenol compound.

Sulfur in petroleum fuels is considered to be a major cause of environmental problems today. In fact, as the fuel burns, sulfur is converted into various sulfur oxides, which turn into acids, contributing to the formation of acid rain.

In general, refiners use catalytic hydrodesulfurization with a catalyst to lower the sulfur content of the fuel.

According to the hydrodesulfurization method, diesel oil derived directly through distillation is hydrotreated under a hydrogen pressure corresponding to a temperature between 300 ° and 400 ° and a pressure of 30 bar to 100 bars (30 to 100.10 ⁵ Pascals), where the hydrogenation is cobalt. And metal sulfide components of VIb and Group V, such as molybdenum sulfide or nickel and molybdenum sulfide, and are made through a catalyst disposed in a fixed bed. Given the operating conditions and the hydrogen consumption, these processes are costly in terms of investment and function, especially if they are to produce low sulfur fuels. Therefore, in order to lower the initial sulfur content of fuel (1% by weight) from 0.05% to 0.005%, the reactor must be expanded four times or more, and the amount of hydrogen required for the reaction must be increased by 20% or more. In this process, it is more difficult to remove traces of sulfur if the sulfur belongs to molecules that do not react well, such as dibenzothiophenol containing alkyl at positions 4 or 4 and 6.

In Sweden, the United States, and particularly in California, the United States, the total sulfur content of diesel oil is already limited to 0.005% by weight. Such restrictions will be generalized within OECD countries in the future. In Europe, restrictions will be put in place in 2005 to ensure that the total sulfur content does not exceed 0.005% (by weight).

Unlike diesel oil, gasoline is not produced only in the direct distillation of crude oil, and because of its low sulfur content, it produces naphtha reforming, light naphtha isomerization, and isooctane. It can be obtained through alkylation of butane or propane, methoxylation of isobutylene, and cracking distillation (craking) of the products of vacuum distillation or residues in the atmosphere with a catalyst. It can also be obtained by. In particular, the final gasoline supplied through cracking distillation using a catalyst has a weight ratio of 20 to 60%. However, these volatiles contain up to 0.1% sulfur by weight. Therefore, a method similar to the hydrodesulfurization (reaction) method of diesel oil described above is widely used as a method for removing sulfur from gasoline produced by catalytic cracking distillation. At this time, the conditions of hydrogen pressure, space velocity and temperature should be more strictly applied. This method is not only costly, but it is impossible to reach a value of 0.005% to 0.03% of the total sulfur content, which is obtained through the conventional method of gasoline cracking distillation. In order to reduce the sulfur content, refiners have devised a method to decompose the sulfur compounds formed in the process by adding an additive to the catalyst used in the cracking distillation, in particular mercaptans and other sulfides. did. However, the effect of these additives is not only limited, but is almost ineffective for derivatives of benzothiophenol, especially where mercaptans and sulfides are removed prior to decomposition distillation.

According to the decomposition distillation method using a catalyst, in the case of gasoline containing the produced sulfur, hydrodesulfurization (reaction) is not only effective for the thiophenol compound, but also lowers the octane number of the gasoline. Hydrogen desulfurization (reaction) causes partial hydrogenation of olefins contained in the gasoline in the gasoline which is distilled and distilled. As the olefin disappears, the octane number of the gasoline decreases and thus the gasoline quality decreases. To compensate for this loss, it is possible to add other components to improve the octane number, or to reprocess the gasoline itself to improve the octane number. However, adding or reprocessing additives to improve the quality of gasoline adds more cost, thus limiting the use of hydrogen and eliminating sulfur compounds that do not react well such as benzothiophenol byproducts. Better to use

Selective oxidation of sulfur compounds belongs to a reprocessing process that can achieve this goal. Among these methods that have been developed to reduce sulfur contained in fuels to thiopetol by-products, organic peroxides or organic hydrogen peroxides such as hydrogen peroxide or organic peracid It has been considered that the catalyst is not applied at all to the oxidation by organic hydroperoxide, and it is also homogeneous using a catalyst mainly composed of an organometallic compound or an aqueous metal oxide. Catalytic reactions and oxidation methods have also been considered (US 3 668 117, US 3 565 793, EP 0 565 324, and publications 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).

When hydrogen peroxide in aqueous solution is added to molybdenum and tungsten-based metal catalysts to generate a reaction (heterogeneous catalyst), when the temperature is set to 60 ° or more, hydrogen peroxide, which is part of the oxidant decomposed by the catalyst, is excessively consumed.

Peroxide, a very powerful oxidant, is obtained by the reaction of hydrogen peroxide with carboxylic acids such as formic acid or acetic acid. The use of such peracids is generally less effective than hydrogen peroxide and less selective for sulfur compounds, as well as oxidizing olefins. .

As another method, the following methods of oxygen desulfurization in an organic environment have been proposed. First, a method of contacting a hydrocarbon containing a sulfur compound that does not easily react with a powdered metal oxide, and a second metal having a peroxide groupe in an aqueous solution or an organic solution together with a hydrocarbon containing a sulfur compound that does not react well. And a method of forming a compound. In the second method, irrespective of the presence of organic or aqueous peroxides, the organic or aqueous peroxides are added together with an alcoholic type of solvent or added to water. (See US 3 816 301, US 4 956 578, US 5 958 224)

Another method is shown in US Pat. No. 3,945,914. This method relates to the production of desulfurized hydrocarbon materials through three stages of treatment. The first step is to partially oxidize the sulfur compound by contact with a peroxide, through a metal catalyst belonging to a group of metals containing titanium, zirconium, molybdenum, tungsten, vanadium, tantalum, chromium and mixtures thereof. In the form of a supported solid. The support is not essential for the reaction. The second step involves other hydrocarbon materials containing these oxidized compounds, whether metal oxides or metal peroxides (nickel, molybdenum, cobalt, tungsten, iron, zinc, vanadium, copper, manganese, mercury and mixtures thereof). In contact with the metal component, the temperature conditions should be set between 250 ° and 730 ° and brought into contact under hydrogen pressure. The third step is to recover the desulfurized hydrocarbon material.

For all the above-mentioned methods, thiophenols are changed to sulfonated forms and / or forms containing sulfone groups. However, some of these compounds, although working at high temperatures, are relatively slow in reaction and take more than an hour to undergo global conversion, or otherwise highly concentrated oxidants often have to be used much more than the amount required for sulfur by-product oxidation. In the case of using other methods other than the above case, it is possible to work through several steps, but it requires a lot of time and requires a lot of equipment costs.

It is therefore an object of the present invention to propose a method of desulfurizing hydrocarbons, especially hydrocarbon bases containing thiophenol by-products, but without desulfurizing octane number or cetane number, and further desulfurizing while raising these values. It is done. The present invention relates in particular to the final treatment of hydrotreated diesel oil and the final treatment of kerosene, and to the final treatment of gasoline which is highly concentrated and thiophenol by-products which are less prone to hydrogenation reactions and are cracked and distilled through the catalyst.

The present invention also proposes a method that allows the same or higher oxidation levels to be reached compared to conventional processes, while limiting the reaction and separation time of sulfurized et oxidized compounds of desulfurized hydrocarbons.

Therefore, the present invention, whether or not refinery process, thiophenol contained in the hydrogenated tin from crude oil distillation process Selective desulfurization of compounds is targeted, which involves the oxidation of sulfur atoms of sulfone thiophenol via oxidants and catalysts, and the separation of the sulfonated compounds thus produced from the hydrocarbons. This process consists of two steps: In the first step, in an organic environment with a temperature of 40 °, a peroxide and peracid-based organic oxidant and a catalyst having a porosity of 0.2 to 4 ml / g and a special surface of 100 m ² / g or more are added to the heterogeneous catalysis. Oxidation / adsorption of sulfur compounds by The second step is to reactivate the catalyst used, characterized in that this reactivation step always follows the oxidation / adsorption step.

In the present invention, thiophenol by-products include benzothiophenol compounds, polybenzothiophenol compounds, and alkylated by-products, among which alkyldibenzothiophenol is an essential oil. The conversion process commonly used by technicians is not particularly well-reacted.

The advantage of the desulfurization process according to the invention is that the oxidation of the entire sulfur contained in the hydrocarbon is carried out at atmospheric pressure, and more particularly, the conversion of sulfone thiophenol by-products is made, and sulfone in the catalyst It is possible to adsorb sulfoxided compounds at the same time. In fact, most of the sulfones and sulfone oxides produced are immediately separated from hydrocarbons and the sulfones and sulfone oxides are precipitated in the catalyst in solid form in treated hydrocarbons or present in the form of sediments which can be filtered by conventional methods. The catalyst on which the sulfone oxides are absorbed becomes the "used catalyst". Dissolved sulfones can be extracted from the treated hydrocarbons. In addition, since the oxidation / adsorption process has no effect on the olefin, when the catalyst is subjected to decomposition and distillation of gasoline, there is no change in the octane number of the gasoline or the content of aromatics containing no sulfur. Furthermore, the use of the oxidation process according to the invention also increases the cetane of diesel oil.

Not only by theory, but by fact, the wider the special surface of the catalyst, the longer the catalyst is activated. In addition, sulfone type compounds and sulfone oxides are characteristically very strong polar characters, which are caught on the surface of the catalyst, and their position on the catalyst is located at approximately the level of the Lewis acid region. In addition, the larger the size of the micropores, the smaller the risk of clogging the catalyst micropores, and the longer the life of the catalyst during the oxidation cycle. In the present invention, in order to obtain sufficient activity of the catalyst, it is important to select a catalyst in which the special surface and the size of the micropores are the most appropriate combination, and thus the catalyst has the longest life and the best oxidation / adsorption. It can be effective.

When the desulfurization method according to the present invention is performed periodically, the oxidation / adsorption step and the reactivation step (of the catalyst) may be performed in the same reactor, or two steps may be performed in a state in which two or more reactors are arranged in parallel. fixed bed), but at the same time alternating with each other. Alternatively, two reactors with fluidized beds may be connected to each other by a catalyst bed, one for oxidation / adsorption and the other for reactivation.

When using a fixed bed, the first reactor comprising a catalyst fixed bed receives incoming hydrocarbons and oxidants, and the second reactor is configured to pass gaseous oxidant streams such as liquid effluents such as washing solvents or air or a mixture of air / nitrogen (N ² ) Accept for reactivation. At this time, the temperature of the catalyst layer is in an elevated state. If the efficiency of the catalyst in the oxidation / adsorption reactor drops to an amount not sufficient for oxidation and / or adsorption, the reactor changes its function.

When using a mobil bed, hydrocarbons enter the first reactor where oxidation occurs, and the catalyst is gradually pushed into the second reactor where the catalyst is reactivated in the second reactor and then sent back to the oxidation / adsorption reactor. Fluidized bed reactors are particularly well known in the reforming process and can be used in the desulfurization apparatus according to the invention. In this embodiment, a third reactor is used, which is installed between the two reactors prior to washing the used catalyst or prior to the combustion of the sulfone compound and separated sulfoxide oxides. This allows the removal of hydrocarbons from the catalyst.

Catalysts used in accordance with the present invention are silica, alumina, zirconium oxide, zirconium oxide, amorphous or crystalline aluminosilicate, aluminophosphate, silica-rich central porosity ( Mesopore) is selected from the group of supported catalysts consisting of solid silica alumina, active carbon and hydrated silicate, which can be used alone or in a mixed form. In the catalyst according to the present invention, it is preferable to use a support catalyst group composed of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese, cerium, and tungsten, and these metals are in the form of oxides. Or may be deposited on the surface of the media. In fact, it was observed that the synergistic effect of the metal produced with the support catalyst, that is, unexpectedly improved catalytic activity in the oxidation process of the thiophenol compound and the capture rate of sulfone compound and sulfur oxide in the catalyst micropores. None of the sulfone compounds and sulfur oxides were subsequently desorbed.

In the desulfurization process according to the invention, the catalyst comprises from 0% to 30% metal specific weight in oxide form on at least one supported catalyst. Preferred values are 0% to 20%.

Among supported catalysts composed of oxides that do not react well, gamma alumina, silica, and silica-containing mesoporous solid silicano alumina are preferred.

Among the supported catalysts, catalysts containing tungsten or titanium precipitated in the form of oxides on one or more of the supported catalysts or entering the support catalyst network are preferred, and the supported catalysts are selected from silicate, aluminum oxide, aluminosilicate, or Or a mixture of several.

According to the recommended desulfurization method of the present invention, the molar ratio of oxidant to total sulfur contained in the hydrocarbon is 2-20, and the preferred ratio is between 2-6.

According to the invention, the oxidant is selected from the compounds of the general formula R10OR2. Where R1 and R2 may be the same or different. The oxidizing agent may be substituted by 1) hydrogen, 2) a simplified or subdivided alkyl group containing 1 to 30 carbon atoms, 3) an aryl group or optionally an aryl motif with an alkyl group and R1 and R2 may be It is selected from three cases of alkylaryl groups which cannot be hydrogen.

 According to a preferred method, the oxidant of the general formula R10OR2 is selected from the group consisting of tertiary butyl hydroperoxide and ditertiary butyl peroxide.

As another oxidant according to the present invention, a peracid of the general formula R 3 COOOH may be selected, for example R 3 may be hydrogen or a simple or detailed alkyl group containing from 1 to 30 carbon atoms. These peracids are preferably selected from the group consisting of peracetogenic acid, peroxyformic acid, and perbenzoic acid.

According to the invention, the reactivation step of the catalyst is for removing the precipitate formed through washing or combustion.

For washing, a polar solvent of a group consisting of water, alkanol and alkylnitrile is used. At this time, alkanol contains 1 to 30 carbon atoms which may or may not be mixed with water, and alkylnitrile contains 1 to 6 carbon atoms. Preference is given to water, acetonitrile, methanol and mixtures thereof.

Upon combustion, the catalyst is at a maximum temperature of 800 ° and the preferred temperature is below 650 °. The pressure conditions during combustion are fluid between 10 ⁵ Pa and 10 ⁶ Pa and the preferred pressure is 10 ⁵ Pa to 2 * 10 ⁵ Pa. The catalyst is then exposed to a gaseous oxidant. As the gaseous oxidizing agent, all gas mixtures containing pure oxygen and oxygen, in particular oxygen and nitrogen mixtures and air itself can be used. The amount of oxygen in the nitrogen is adjusted to limit the generation of water vapor, and if the amount of water vapor is too high, side effects, especially when the support catalyst contains crystalline aluminosilica, such as zeolite or aluminophosphate By changing the structure of the catalyst micropores to make the micropore size small. In addition, this steam generation adjustment can be used to adjust the heat dissipation-related temperature changes of combustion.

In order to realize the method described above, a desulfurization apparatus comprising a first reactor and a second reactor can be used. The first reactor includes an oxidation catalyst and also includes a conduit through which hydrocarbons and oxidants enter and a conduit through which desulfurized hydrocarbons exit. The second reactor includes a conduit through which the solvent or gas oxide of the catalyst enters, and a conduit through which the combustion gas exits. Gas oxidants are used here as oxygen / air mixtures, atmospheric / nitrogen mixtures, oxygen / nitrogen mixtures.

If the apparatus comprises two reactors, these reactors can function as a fixed bed or a fluidized bed.

The third object of the invention is to use the desulfurization method described above in the final treatment of gasoline which has been catalytically distilled or to use the desulfurization method described above in the treatment of pre-hydrotreated diesel and kerosene for the best economics. It is.

The invention will be described in more detail below in conjunction with the accompanying drawings.

1 is a view showing that a desulfurization apparatus having two reactors alternately performs oxidation and catalyst reactivation functions.

FIG. 2 shows the apparatus comprising two reactors with fluidized beds, the first reactor carrying out an oxidation step, the second reactor carrying out a catalyst reactivation step, and a conduit into which the reactivated catalyst can be returned. It is attached to this system.

3A and 3B are graphs showing, over time, the total sulfur content of hydrocarbons treated according to the invention in Example III to be discussed later.

In FIG. 1 the apparatus comprises two reactors 1 and 2 and a catalyst located in a fixed bed. When reactor 1 performs oxidation, and reactor 2 performs catalytic reactivation, sulfur-containing hydrocarbons enter reactor 1 through conduit 3 and the oxidant is conduit 4 connected to the conduit. And enters through the triple valve 6a and the conduit 8a. The desulphurized hydrocarbon exits reactor 1 through conduit 9a and exits via conduit 10a via valve 7a.

Conduit 5, on the other hand, introduces a suitable solvent or gaseous oxidant into reactor 2, which enters the reactor via triple valve 6b and conduit 8b. The temperature of the catalyst bed is maintained at 500 ° while the reactor is in combustion. Solvents with sulfone recovered from the catalyst or combustion gases, mainly SO ₂ , CO and CO ₂ , are discharged into conduit 11a through conduit 9b, triple valve 7b and conduit 11b.

Catalytic When the reactivation operation is made and the catalytic activity of the reactor 1 becomes insufficient and becomes insufficient, the two reactors replace each other's functions. The hydrocarbon / oxidant mixture thus enters conduit 3a and enters reactor 2 via valve 6b. The desulfurized hydrocarbon exits through conduit 9b and exits into conduit 10a via valve 7b and conduit 10b.

Meanwhile, the solvent and gas oxidant introduced through the conduit 5 enter the reactor 1 via the conduit 3a, the valve 6a, and the conduit 8a.

The conduits 6a, 6b, 7a, 7b are replaced by their respective functions by a common procedure to enable the flow of the flow rate.

A filter is formed in one of the conduits 9a and 9b or one of the conduits 10a and 10b to recover the solid sulfone formed during the oxidation process and remaining in suspension in the hydrocarbon. This is advantageous. In these same conduits, it is better to add a sulfur separator equipped with a silicate or active alumina type adsorber on top of the filter to catch the sulfone still dissolved in the treated hydrocarbons. .

The apparatus of FIG. 2 comprises two reactors 20a and 20b arranged in series, each having a catalytic fluidized bed. Reactor 20a operates in oxidation mode and reactor 20b operates in catalyst reactivation mode. The apparatus of FIG. 2 also includes a propulsion device 30, which allows the catalyst to return from reactor 20b to reactor 20a.

The hydrocarbon enters reactor 20a through conduit 40 before the oxidant entered through conduit 50 is introduced. For example, reactor 20a may be selected from a funnel reactor in which a fluidized bed of catalyst may move under the reactor by gravity. Thus, when the desulphurized hydrocarbon exits through conduit 60, the catalyst enters reactor 20b via conduit 70 by gravity. Solvent and combustion gases are introduced into reactor 20b through conduit 80. In order to carry out catalyst reactivation through combustion, the temperature is raised to 500 ° and maintained. The solvent containing the combustion gas or sulfone is discharged through the conduit (100).

In general, the fluidized bed acts intermittently, so that the catalyst cannot move continuously. Therefore, it is advisable to install a solvent or nitrogen discharge device in the reactor 20b to remove the hydrocarbons prior to their washing and / or to remove the combustion gases through stripping reaction with nitrogen.

The reactivated catalyst exits reactor 20b and enters propeller 30 through conduit 110. This propulsion device may be a device propelled through an endless screw engaged with a pressurized gas or tooth. This propulsion unit lifts the reactivated catalyst and sends it through the conduit 120 to the reactor 20a.

In some specific implementations of such fluidized bed reactors, the two reactors 20a, 20b may be one unit that performs two separate functions.

The embodiment to be seen below shows the efficiency of the desulfurization method according to the present invention, and is not limited in scope.

Example I

This example is intended to show the effect of the desulfurization process according to the invention on the removal of dibenzothiophenol by-products remaining in partially desulfurized hydrocarbon bases.

Samples of the catalysts used were of two types, one of which was formed of only one supported catalyst, and the other of which was a composite of one or several metals injected. Table 1 below is a chart showing the special surface and porosity properties of each catalyst.

Table I

Catalyst sample Support catalyst Special surface area (m ² / g) Micropore size (angstrom) Metal oxide C ₁ SiO ₂ 160 252 - C ₂ SiO ₂ 140 300 WO ₃ C ₃ Gamma Al ₂ O ₃ 245 104 WO ₃ C ₄ Beta zeolite 470 30 TiO ₂ C ₅ Mesopore 1000 85 C ₆ Mesopore 830 70 MoO ₃ C ₇ Al ₂ O _3γ 210 95 WO ₃

Catalysts C2, C3 and C6 contain a metal salt (ammonium metatungstate) and ammonium hexamolybdate at 140 mg per gram of the supported catalyst through the wet method. After injection, it is dried and obtained by applying high temperature of 500 ° C.

Catalyst C ₄ can be obtained through the treatment of beta zeolite on commercially available titanium in accordance with the method specified in EP 0 842 114.

To test the oxidation activity of these catalysts over time, 20 ml of catalyst were injected into 150 ml of small-scale pilot reactor. Hydrogenated intermediate distillate containing 212 ppm of residual sulfur that does not react to hydrotreating and 1800 ppm of tertiary butyl hydroperoxide (tBHP) is added to ¹ h ^-1 space per hour (VVH). Pass through the catalyst at a temperature of 70 ° C. at atmospheric pressure. Samples are taken at regular intervals during the oxidation to determine the activity of the catalyst over time. A comparative sample corresponding to the case where only the catalyst was used without peroxide was experimented by designating T1.

Table 2 below shows the experimental results for the effect of these catalysts over time.

Table 2

Sample catalyst Total sulfur content over time (ppm) 2 hours 4 hours 5 hours 6 hours T ₁ C1 121 185 196 202 X ₁ C ₁ 49 46 48 49 X ₂ C ₂ 28 10 9 16 X ₃ C ₃ 30 28 23 27 X ₄ C ₄ 18 16 11 11 X ₅ C ₅ 35 32 38 35 X ₆ C ₆ 23 20 17 22 X ₇ C ₇ 34 31 25 31

Two hours after the action, these results indicate that the larger the pore size of the catalyst and the higher the specific surface area value, the lower the sulfur content of the treated hydrocarbon, except for the effect of the catalyst properties. In addition, it can be seen that the activity of the catalyst is also improved when the catalyst is composed of a metal oxide. On the other hand, after 24 hours, the sulfur content of the desulfurized hydrocarbon is slightly increased regardless of the catalyst, which is the time when the sulfon and sulfone oxides enter the catalyst micropores and the micropores start to be blocked.

Through this process, it became clear that the selection of a suitable catalyst for the desulfurization method of the present invention should be made in the search for an optimum compromise within the results according to the natural properties of the catalyst, the specific surface, and the micropore size.

Example II

In Example II, the effect of the catalyst on compound oxidation is determined.

As in Example I, experiments were carried out with catalysts C ₁ -C ₆ , with dibenzothiophenol compounds, in particular benzothiophenol (BT), dibenzothiophenol (DBT), 4- The formation of sulfones and sulfone oxides for 6-dimethyldibenzothiophenyl (DMBT) is observed via gas phase chromatography equipped with sulfur special sensors (SIEVERS method).

Table III below shows the experimental results.

Table III

catalyst Oxidizer Concentration (eqS) % Oxidation of sulfone BT DBT DBMT C ₁ 3 80 78 81 C ₂ 3 90 95 93 C ₃ 3 88 92 89 C ₄ 3 96 99 95 C ₅ 3 85 87 88 C ₆ 3 92 94 93

These results indicate that thiophenol byproducts that do not react well using a catalyst composed of a single support catalyst or a catalyst composed of metal in the form of a metal oxide placed in the support catalyst network or placed on the support catalyst in 90% or more of the reaction It can be seen that more than 80% can be converted to sulfone.

Example III

This example is intended to show the effect of adsorption of sulfone compounds and sulfone oxides over time and the effect of reactivation on oxidation / adsorption, as in oxidation, adsorption and reactivation procedures.

With catalyst C ₃ In the experimental conditions described in Example Ⅰ, experiments applying the tBHP 600ppm of a middle distillate product containing 44ppm sulfur after hydrotreating.

The results of oxidation / adsorption when the catalyst is still in full swing are shown in FIG. 3A. After 2 days, the total sulfur content of the hydrocarbons increases rapidly to approximate the initial level, which is not treated according to the invention.

The results in FIG. 3b show the sulfur content values in the same hydrocarbons when the same catalyst C ₃ was reactivated. The results obtained from the same catalyst reactivated are almost the same as those obtained from the active catalyst.

These two curves confirm the benefits of the process of the present invention, which alternately acts on oxidation / adsorption or reactivation with the same catalyst, in which the oxidation / adsorption time should naturally be tailored to the sulfur content.

Claims (20)

Thiophenols contained in hydrocarbons arising from the distillation of refined or unrefined crude oil, which refers to the process of oxidizing sulfur atoms of sulfone thiophenol to sulfone by adding an oxidizing agent and separating the sulfone compound from the hydrocarbon. In the method for selectively desulfurizing by-products, In the first step, in an organic environment of at least 40 ° C., a peroxide or peracid-based organic oxidant is used, or a porosity between 0.2 and 4 ml / g with a special surface area of 100 m ² / g or more ( oxidation / adsorption occurs through a heterogeneous catalyst composed of sulfur compounds using a catalyst having a porosity), In a second step, a process for selectively desulfurizing thiophenol by-products contained in hydrocarbons, wherein the catalyst used is always reactivated following the oxidation / adsorption step. The process of claim 1, wherein the oxidation / adsorption step and the reactivation step are carried out sequentially on the same reactor over the same catalyst. The hydrocarbon according to claim 1, wherein the oxidation / adsorption step and the reactivation step are performed simultaneously in two reactors (1, 2) arranged side by side and the function of each step is alternately substituted in each other in the two reactors. A method for selectively desulfurizing thiophenol byproducts contained in. The process of claim 1, wherein the oxidation / adsorption step and the reactivation step are carried out in two reactors 20a, 20b with fluidized beds, the two reactors being connected to each other by a catalyst bed, one performing an oxidation reaction, the other One is a method for selectively desulfurizing thiophenol by-products contained in hydrocarbons, characterized by performing a reactivation action. 5. The oxidant material according to any one of claims 1 to 4, wherein the oxidant material is selected from the group consisting of organic peroxides, organic hydroperoxides, and peracids. To selectively desulfurize thiophenol byproducts. The catalyst according to claim 1 or 2, wherein the catalyst is silica, alumina, zirconium oxide, zirconium oxide, amorphous or crystalline aluminosilicate, aluminophosphate, mesoporous A method for selectively desulfurizing thiophenol by-products contained in hydrocarbons, characterized in that it comprises one support catalyst selected from the group consisting of solids, active carbons, hydrated silicates or mixtures thereof. . 7. The catalyst of claim 6 wherein the catalyst comprises one metal selected from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese, tungsten, which is injected into or supported on a support catalyst network. A method for selectively desulfurizing thiophenol by-products contained in hydrocarbons, characterized by being in oxide form. The thiophenols contained in the hydrocarbon according to any one of claims 1 to 4, wherein the catalyst comprises in the form of oxides a metal in a weight ratio of 0 to 30%, more advantageously 0 to 20%. How to selectively desulfurize by-products. The catalyst according to any one of claims 1 to 4, wherein the catalyst is composed of a medium selected from gamma alumina, silica, and mesoporous solid silica alumina containing silica. Desulfurization method characterized in that. 7. The thiophenol by-product of the hydrocarbon is selected according to claim 6, wherein the support catalyst is selected from a catalyst in which tungsten is included in a support catalyst selected from silica and alumina alone or in a mixture. How to desulfurize as an enemy.  The molar ratio of the oxidizer to the total sulfur in the hydrocarbon is 2 to 20, more advantageously the molar ratio is between 2 and 6. A method for selectively desulfurizing thiophenol byproducts contained in hydrocarbons. 5. The oxidizing agent of claim 1, wherein the oxidant is a compound of the general formula R ₁ OOR ₂ , wherein R 1 and R 2 may be the same as or different from each other, wherein R 1 and R 2 are a first hydrogen atom, a second carbon atom. A method for selectively desulfurizing thiophenol by-products contained in hydrocarbons, which may be selected from the group of simplified or subdivided alkyl groups having from 1 to 30, wherein R1 and R2 cannot be hydrogen at the same time. 13. The thiophenol by-product contained in a hydrocarbon according to claim 12, wherein the oxidant is selected from the group consisting of tertiary butyl hydroperoxide and ditertiary butyl peroxide. How to selectively desulfurize. The oxidizing agent according to any one of claims 1 to 4, wherein the oxidizing agent is a peracid of formula R ₃ COOOH, wherein R3 is a simplified or subdivided alkyl group having 1 to 30 carbon atoms or hydrogen. Selectively desulfurizing thiophenol by-products contained in hydrocarbons. 15. The thiou contained in a hydrocarbon according to claim 14, wherein the oxidizing agent is selected from the group consisting of peracetogenic acid, peroxyformic acid, and perbenzoic acid. A method for selectively desulfurizing phenol byproducts. 5. Process according to any one of the preceding claims, characterized in that it performs the function of a catalyst reactivation step by removing the precipitate by washing or combustion. . Process for using the desulfurization method according to any one of claims 1 to 4 for hydrotreated diesel oil, kerosene and gasoline, in particular for gasoline produced through cracked distillation using a catalyst. delete delete delete

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