WO2008034885A1

WO2008034885A1 - Use of a material for extracting polyaromatic or neutral nitrogenous compounds from a mixture of hydrocarbons of the diesel boiling range

Info

Publication number: WO2008034885A1
Application number: PCT/EP2007/059998
Authority: WO
Inventors: Alain Favre-Reguillon; Marc Lemaire; Stéphane PELLET-ROSTAING; Xianzhi Fu; Xuxu Wang
Original assignee: Universite Claude Bernard Lyon I; Centre National De La Recherche Scientifique; Universite De Fuzhou
Priority date: 2006-09-21
Filing date: 2007-09-20
Publication date: 2008-03-27
Also published as: FR2906161A1; FR2906161B1

Abstract

The invention relates to the use of a material consisting of a solid support on which plane nitrogenous aromatic groupings carrying at least one positive charge associated with a counter-ion are immobilised, for extracting compounds which are inhibitors of catalytic reactions used in the treatment of hydrocarbon mixtures of the diesel boiling range, especially hydrodesulphurisation reactions, from a mixture of hydrocarbons having a boiling temperature in the diesel boiling range, by absorption, said compounds being selected from polyaromatic and neutral nitrogenous compounds. The invention also relates to a hydrotreatment method implementing such a use.

Description

USE OF MATERIAL FOR EXTRACTING NEUTRAL POLYAROMATIC OR NITROGEN COMPOUNDS FROM A MIXTURE OF HYDROCARBONS

OF THE BOILING RANGE OF DIESEL

The present invention relates to the technical field of hydrotreating of diesel. In particular, the subject of the present invention is the use of a solid support on which planar nitrogen-containing aromatic groups carrying at least one positive charge associated with a counterion for extracting, of a mixture of hydrocarbons are immobilized. which has a boiling point in the boiling range of diesel, catalytic reaction inhibiting compounds used in the treatment of hydrocarbon mixtures of the diesel boiling range, and in particular catalytic hydrodesulfurization reactions, chosen among polyaromatic compounds and neutral nitrogen compounds.

The presence of nitrogen compounds and polyaromatic compounds in petroleum fractions from the distillation of crude oils has long been demonstrated. D. Tourres, C. Langelier, D. Leborgne, in their article

"Analysis of Nitrogen Compounds in Petroleum Cylinders by Capillary Column and Specific Chemiluminescence Detection", Analusis Magazine,

1995, 23, N29 to M36 specifically studied the nitrogen compounds present. Nitrogen compounds and polyaromatic compounds are present in a distillation cup in varying amounts depending on the nature of the crude oil and the distillation temperatures thereof. Nitrogenous organic compounds are either basic, such as amines, anilines, pyridines, acridines, quinolines and their derivatives, or neutral such as pyrroles, indoles, carbazoles and their derivatives. The polyaromatic compounds belong in particular to the group of naphthalene, anthracene, phenanthrene, pyrene and their derivatives.

In recent years, deep desulphurisation of diesel fuel has attracted a lot of attention, due to the gradual reduction of legal sulfur content in most countries. Industrialized countries have set standards for diesel fuels, including maximum levels of sulfur. In addition, the specifications imposed on diesel fuel should be more stringent and harmonized, around the world, in the near future. It is actually proposed to lower the sulfur content that is allowed in gas oil to 10 ppm by weight from 2009 in Europe and 15 ppm by weight from 2006 in the United States. Under these circumstances, the development of a technology for ultra-deep desulfurization to remove most of the sulfur compounds in the diesel fractions becomes extremely important. In addition, oil reserves around the world are becoming heavier as a result of the depletion of traditional resources, increasing their levels of sulfur and nitrogen. The basic and neutral nitrogen compounds as well as the polyaromatics present are often responsible for the premature deactivation of certain catalysts commonly used in various refining processes, and in particular acid catalysts used in processes such as reforming, isomerization, catalytic cracking. These nitrogen compounds also have some inhibitory action on hydrotreatment reactions. Therefore, many methods have been developed specifically for reducing the content of hydrocarbon cuts in such nitrogenous compounds such as hydrodenitrogenation which is based on cracking reactions of nitrogen compounds in the presence of hydrogen. However, this process does not allow the sufficient removal of nitrogen compounds. In addition, when the sulfur content is to be lowered to less than 50 ppm sulfur, the conversions that are required involve desulfurization of substituted dibenzothiophenes, especially those in which the substituents are present on aromatic rings adjacent to the sulfur atom. heterocyclic. Such compounds are called sulfur compounds refractory. A typical example of such a compound is 4,6-dimethyldibenzothiophene (DMDBT). When high levels of desulfurization are achieved, the concentration of refractory sulfur compounds (such as DMDBT) is low and the polyaromatics and nitrogen compounds naturally present in the diesel fuel can inhibit the hydrodesulphurization process even when present in the process. very low concentrations by competitive adsorption and contribute to the difficulty of achieving stricter specifications. Therefore, these compounds are qualified as inhibitors of catalytic reactions used in the treatment of diesel boiling range hydrocarbon mixtures and / or hydrodesulfurization or poison reactions of hydrotreatment catalysts. As a result, their presence partially inhibits hydrodesulfurization reactions occurring during hydrotreatment. It has been shown that if such inhibitors are selectively removed from the feedstock and that feed containing fewer inhibitors is hydrotreated under typical commercial conditions used in existing refineries, then sulfur-containing refractory compounds can be more easily removed. by hydrotreating using conventional catalyst loading and process conditions (Koltai, T. et al., Appl.Catal.2002, 231, 253-261, Macaud, M. et al., Ind. Eng Chem Res. 2004, 43, 7,843 to 7,849).

It is therefore necessary to selectively remove polyaromatic compounds and nitrogen compounds, acting as inhibitors, prior to the hydrotreatment reactions, to provide fuels which have a satisfactory sulfur content.

The refining industry has demonstrated its ability to adapt hydrotreatment to stringent regulations by improving, among other things, catalytic activity. A complementary solution also developed has been to pre-treat the feedstock to be hydrotreated so as to remove nitrogen-containing compounds (N compounds), sulfur-containing refractory compounds (S compounds) and / or polyaromatics. By removing these compounds in this manner, it is possible to achieve extremely high conversions of the sulfur compounds in hydrocarbon mixtures of the diesel boiling range under moderate hydrotreating conditions. Basic nitrogen compounds are known as poisons from HDS reactions. Many techniques have been employed to eliminate them such as ion exchange resins as described by G. Marcelin et al. in Ind. Eng. Chem. Process. Of. Derv. (1986), 25, 747-756 or by liquid / liquid extraction. By way of example, US Pat. No. 3,719,587 describes the use of dilute sulfuric acid (0 to 10% by weight) to remove basic nitrogen compounds present in organic fillers. Unfortunately, hydrotreatment catalysts are not only poisoned by nitrogen compounds basic, but also by non-basic nitrogen compounds which are abundant in hydrocarbon mixtures of the diesel boiling range. Indeed, during HDS reactions these compounds can be converted into basic nitrogen compounds. For these reasons, a higher concentration of sulfuric acid has been used to eliminate almost all nitrogenous species. The patent application WO 2005/056733 describes the use of concentrated sulfuric acid (> 90% by weight) to remove heterocyclic compounds containing nitrogen. However, the use of concentrated sulfuric acid causes the loss of 10 to 20% of the sulfur compounds present in the feed and the mixture of hydrocarbons, washed with acid, obtained must be neutralized with a caustic solution and then washed to eliminate any residual caustic solution that makes the industrial process more complex.

The technique used in the patent application WO 03/078 545 uses a polymer mass having a polar function generating hydrogen bonds. Sulfur-containing, nitrogen-containing and aromatic compounds may also be adsorbed onto alumina, activated charcoal, silica, silica gel, zeolites and spent adsorbent as described in EP 1 454 976 A1, WO 99 67 345 and by Kim, JH et al. Catal. Today 2006, 111, 74-83, however the selectivity of these techniques is low. The technique used in the patent application FR 2 814 172 uses a polar polymer mass having electron acceptors. The nitrogen-containing compounds are selectively adsorbed, however, the high cost and low capacity of these materials limits their industrial use.

All these extraction methods generally make it possible to extract only a part of the inhibitors of the hydrotreatment reactions. The polyaromatic compounds and neutral nitrogen compounds are only partially extracted. It is, therefore, difficult to achieve the sulfur levels imposed by international standards.

In this context, one of the objectives of the invention is to find a new type of adsorbent for extracting neutral polyaromatic and / or nitrogen compounds which is very selective with respect to these compounds, and whose use can easily be be integrated into conventional processes and at a lower cost. Notably, the proposed adsorbent should be highly selective for inhibitors and should not eliminate the valuable components present in the hydrocarbon mixtures of the diesel boiling range or other non-inhibitory components present in hydrocarbon mixtures. from the boiling range of diesel.

The subject of the present invention is therefore the use of a material composed of a solid support on which are immobilized plane nitrogenous aromatic groups carrying at least one positive charge associated with a counter-ion, to extract, by adsorption, of a hydrocarbon mixture which has a boiling point in the boiling range of diesel, catalytic reaction inhibiting compounds used in the treatment of hydrocarbon mixtures of the diesel boiling range, and especially hydrodesulfurization reactions, chosen from polyaromatic compounds and neutral nitrogen compounds. Another subject of the invention relates to a process for treating a hydrocarbon mixture which has a boiling point in the boiling range of diesel which comprises the following stages: a) extracting, by adsorption, the mixture of hydrocarbons of the polyaromatic compounds and / or neutral nitrogen compounds, said compounds being inhibitors of the catalytic reactions used in the treatment of hydrocarbon mixtures of the diesel boiling range, and in particular catalytic hydrodesulfurization reactions, by contacting a mixture of hydrocarbons with a material composed of a solid support on which are immobilized planar azotic aromatic groups carrying at least one positive charge associated with a counter-ion; b) hydrotreating the hydrocarbon mixture obtained in step a) with a hydrotreatment catalyst.

According to another of its aspects, the subject of the invention is also a material composed of a solid support on which are immobilized nitrogenous planar aromatic groups carrying at least one positive charge associated with a counter-ion, characterized in that the nitrogenous aromatic groups are immobilized on the solid support by electrostatic interaction. The description which follows, with reference to the appended figures, makes it possible to better understand the invention.

Figure 1 schematically shows the various steps of a method of treating a petroleum cut, implementing a method according to the invention.

Figure 2 shows schematically different materials that can be used in the context of the invention.

FIGS. 3A and 3B show the total concentration and the% of nitrogen and sulfur obtained in a diesel solution as a function of the time of contact with a solid support (FIG. 3A with Resin 5 and FIG. 3A with Resin 4), according to the method according to the invention.

Figure 4 is a GC-MS analysis spectrum of the compounds extracted from a diesel feed according to the process according to the invention.

Figures 5 and 6 show the drilling curves obtained in Examples 5 and 6.

In the context of the invention, it is proceeded to a selective removal, in a petroleum fraction corresponding to the boiling range of diesel, inhibitors of the conversion of refractory sulfur compounds, then to a selective desulphurization according to a process of the invention. known hydrodesulphurization. The method according to the invention is illustrated in FIG.

Inhibitor compounds of the catalytic reactions used in the treatment of hydrocarbon mixtures of the diesel boiling range are compounds which cause premature deactivation of certain catalysts commonly employed in various refining processes, and in particular acid catalysts. used in processes such as reforming, isomerization, catalytic cracking or those which exhibit some inhibitory action of hydrotreatment reactions. Such inhibitory compounds, of the neutral nitrogen type, are generally pyrroles, indoles, carbazoles or a derivative thereof. The polyaromatic type inhibiting compounds are most often naphthalenes, anthracenes, phenanthrene, pyrenes or a derivative thereof.

The process according to the invention is therefore particularly suitable for the treatment of petroleum fractions from petroleum refining, which have a Boiling temperature in the range of diesel. In particular, such hydrocarbon mixtures have a boiling point of between 150 and 370 ^° C.

According to the invention, the extraction is carried out using a solid material, by solid / liquid extraction. The material is of course insoluble in the hydrocarbon mixture to be treated. This insolubility comes from the insolubility of the solid support in the hydrocarbon mixture. The solid support used is carrier in several locations, the couple: aromatic cationic nitrogen group cationic plane / counter-ion. Such planar azotic aromatic groups bearing at least one positive charge are preferably chosen from the cationic derivatives of imidazole, pyridine, pyrazole, quinoline, isoquinoline, acridine, 2,6-diaza-anthracene, thiazole or triazine. Each positive charge is associated with a counter-ion to ensure the neutrality of the material.

The solid support may, for its part, be chosen from polymeric matrices, porous or non-porous substrates such as silica, alumina or zeolites, activated carbons. The support may be in particulate or granular form or any form adapted to be disposed in an extraction device, and in particular a column. In particular, the material will be in the form of particles having an average diameter greater than 300 microns and in a preferred mode greater than 500 microns.

The immobilization of the aromatic cationic nitrogen / cation counterion pairs on the solid support can be done anyway appropriate. In particular, the nitrogenous aromatic groups may be immobilized on the solid support by covalent bonding, or by electrostatic interaction. In the latter case, it is the counter-ion A ^" which will then be bound to the solid support by covalent bonding Fig. 2 schematically illustrates various examples of the structure of the material that can be used In the case where the nitrogenous aromatic groups are coupled to the solid support by covalent bonding, the bond between the support and the nitrogenous aromatic group may be via a nitrogen atom of the aromatic group or via another atom of the aromatic group, such as the shows Figure 2. The immobilization by chemical grafting may be carried out by any coupling techniques well known to those skilled in the art, in particular described in "Synthesis years separations using functional polymers" Ed. DC Sherrington and P. Hodge, J. Wiley & Sons (1988). ), some of which are particularly illustrated in the examples that follow. Quaternization of polymeric mass comprising nitrogen groups which are covalently bound, such as polyvinylpyridines, is also a method for obtaining these types of material, which is particularly illustrated in the examples which follow. As a polymer matrix, it is possible, for example, to use polystyrene, its copolymers and their derivatives which allow a good contact with the hydrocarbon mixture which has a boiling point for diesel. The polymer matrix may be composed of an alternating or random copolymer.

In cases where the aromatic groups are immobilized by electrostatic interaction on a polymer matrix, it is possible to use a polymeric matrix comprising strong acid functions of formula:

The aromatic aromatic group carrying at least one positive charge is, for example, chosen from the groups:

wherein :

r is equal to 0, 1, 2 or 3,

- s is equal to 0, 1, 2 or 3,

m is 0, 1, 2, 3, 4 or 5, p is 0, 1, 2, 3 or 4,

t is 0, 1, 2, 3 or 4,

v is 0, 1, 2, 3, 4 or 5,

- x is 0, 1, 2, 3, 4, 5 or 6,

R 1, R 1 and R ₂ each represent, independently of one another, an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group,

R ', R' and R ' ₂ each independently represent an alkyl group comprising from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C 1 -C 6) Gaikylphenyl in which the aliphatic groups may carry 1 or 2 substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C 1 -C 6) alkoxy and the phenyl ring may carry one or more substituents selected from halogen, amino, amine, ammonium, cyano, (Ci-C-Oa Icoxy, (Cr

C ₆ ) alkyl,

- R "i and R" ₂ each independently represent a hydrogen atom, an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano group, an amino group, an amine group or an ammonium group.

The term "alkyl group" denotes a linear or branched saturated hydrocarbon group, for example methyl, ethyl, propyl, n- and t-butyl.

Alkyl means an alkyl group having 1 to 6 carbon atoms.

By alkenyl group is meant an alkyl group as defined above unsaturated having at least one double bond.

Alkoxy group denotes an O-alkyl group. By Cr -C -Oalkoxy group is meant an alkoxy group having 1 to 4 carbon atoms. Halogen atom denotes a chlorine, fluorine, bromine or iodine atom.

The term "aminated group" denotes alkylamines or dialkylamines, the alkyl groups being as defined above and comprising from 1 to 6 carbon atoms. Optionally, the alkyl groups can be linked together to form a cyclic amine. By way of example of such amine groups, mention may be made of the methylamine, ethylamine, dimethylamine diethylamine, piperidine and piperazine groups.

In the definition of the substituents R ', R' ₁ and R ' _{2 /} by group (Cr COalkylphenyl, denotes a phenyl group bonded to the heterocycle, by an alkylene chain comprising 1 to 4 carbon atoms.

The aromatic heterocycle may carry one or more identical or different R (R 1 or R ₂ ) groups.

In the case where the aromatic groups, and in particular those above, are immobilized by covalent bond, on a support, for example of polymeric type, the (s) counter-ion (s) will be the conjugate base partially or totally deprotonated an inorganic or organic acid. This counterion can, for example, represent CI ^" , F ^' or Br ^" , CI ^' being particularly preferred.

By way of example of materials that can be used in the context of the invention, mention may be made of the following polymer matrices:

The materials as defined above, composed of a solid support on which the planar azotic aromatic groups carrying at least one positive charge are immobilized by electrostatic interaction form an integral part of the invention. The hydrotreating step (HDS) (step b)) can be carried out by any conventional hydrotreatment process. Such a process reacts the hydrocarbon mixture, in the presence of a catalyst, with hydrogen at elevated temperature and pressure. This step in particular improves the appearance and smell of the hydrocarbon mixture and reduce its sulfur content. The hydrotreatment stage will also be able to utilize new improvements in catalytic processes, new approaches and emerging technologies for ultra-deep desulphurization of diesel boiling range products. For more details on conventional hydrotreatment processes, reference may be made to Song, C. Catal. Today 2003, 86, 211-263. The pretreatment step (step a)) aimed at reducing the content of neutral nitrogen compounds and polyaromatics can be carried out in different ways. In particular, the contacting between the hydrocarbon mixture and the solid material can be effected by means of a column flow, a stirred tank or a hydroclone. The extraction conditions that can be used depend on the material used and the hydrotreatment feeds. For example, the extraction is carried out at a temperature between 0 and 300 ⁰ C and, in particular, between 20 and 100 ⁰ C, and under a pressure between 10 ⁵ and 50.10 ⁵ Pa, preferably at atmospheric pressure. In some cases, the inhibitor removal efficiency or viscosity may be optimized by raising or lowering the temperature or changing the contact time. However, the temperature, of course, must not be higher than the boiling point of the treated diesel fuel, nor lower than the freezing temperature or the flow temperature of the diesel fuel. The weight ratio of the hydrocarbon mixture to the material will be adapted by those skilled in the art and may, for example, be at least 1 and preferably greater than or equal to 3. The duration of the adsorption stage or cycle is determined by the ability of the material used to adsorb the inhibitors of the diesel fuel supply. Preferably, the contact time and the number of stages of the process will be defined so as to obtain a residual nitrogen content in the hydrocarbon mixture, after adsorption and removal of the material, less than 200 ppm by weight, of preferably less than 100 ppm by weight and preferably less than 20 ppm by weight. At this level of nitrogen in the treated fuel, the subsequent hydrodesulfurization (HDS) is greatly facilitated, and sulfur levels lower than 50 ppm, 20 ppm or even 10 ppm according to the regulations in force, can be achieved under moderate conditions. conventional method. The degree to which the inhibitors are removed will depend on the material used and the cost of the removal process.

According to a preferred variant of the process according to the invention, the step a) of adsorption with a material is preceded by a preliminary step of hydrotreating the hydrocarbon mixture. This prior hydrotreatment step is carried out by contacting the hydrocarbon mixture with a hydrotreatment catalyst and hydrogen under hydrotreatment conditions. The product from this first step is preferably depleted to remove light fractions, ammonia and hydrogen sulfide, and then fed to the material to undergo the adsorption step.

Products of the boiling range of diesel may also have undergone, before the adsorption phase, a first treatment to remove basic nitrogen compounds, either by liquid / liquid extraction with inorganic or organic acids or by using acidic ion exchange resins. After separation, the hydrocarbon mixture having a boiling point in the boiling range of the diesel free of basic nitrogen compounds will then be subjected to the adsorption step with the material. After this step of adsorbing the inhibitors, the subsequent hydrodesulphurization (HDS) will achieve very low sulfur levels, below 50 ppm, 20 ppm or 10 ppm according to the regulations in force, under conventional moderate process conditions. HDS. According to another advantageous characteristic, the hydrocarbon feedstock can be divided into a fraction which has a high content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds and a fraction which has a low content of compounds. Sulfur-containing, nitrogen-containing and / or polyaromatic, for example by distillation, only the fraction which has a high content of sulfur-containing, nitrogen-containing and / or polyaromatic-containing compounds is introduced as a feedstock into the feedstock. the adsorption step. After contact of the material with the products of the diesel boiling range, the material containing inhibitors is separated from the hydrocarbon mixture and the material is then advantageously subjected to a regeneration process using conventional equipment. This regeneration can be carried out in various ways. The regeneration can be carried out by distillation of the adsorbed inhibitor compounds or by using water vapor. Regeneration can also be performed in a column, using a suitable solvent as eluent. The eluent may be for example an aromatic solvent such as benzene, toluene or xylene. The eluent may also be a polar solvent such as methanol or ethanol. The eluent can also be an oil cut entirely desulphurized and denatured. It should be noted, and this is a substantial advantage of the invention, that the methods described above make it possible to isolate and recover the nitrogenous compounds extracted from the treated hydrocarbon fraction. These compounds, in particular nitrogenous heterocyds, can be valorised in various ways, for example in fine chemistry or for modifying the properties of fuels intended for use by consumers. Isolated inhibitors can be destroyed by incineration or in some cases they can serve as sources of chemicals. According to another advantageous characteristic, the hydrocarbon feedstock which is contained in the pore volume of the columns during the alternations between the adsorption and the regeneration can be washed with a hot gas such as, for example, nitrogen air or water vapor. In the latter case, the separations can be carried out by decantation. Advantageously, the adsorption step is carried out in at least one adsorption plant while the regeneration stage is implemented in at least one other adsorption plant, whereby the two installations of adsorption operate alternately in an adsorption phase and a regeneration phase.

According to another advantageous characteristic, the regeneration can be carried out under operating conditions that are different from those of the adsorption and, in particular, at a lower pressure and at a higher temperature to facilitate regeneration.

The following examples serve to illustrate the invention and are not limiting in nature.

In order to evaluate the elimination of diesel fuel inhibitors prior to the implementation of a hydrotreatment process, a model fuel and a standard diesel feed have been contacted in various ways with several adsorbent materials according to the invention.

A model fuel is prepared by dissolving 179 mg (1.07 mmol) of carbozole and 86 mg (0.47 mmol) of dibenzothiophene in 100 g of a toluene / heptane mixture (80/20 by weight). The nitrogen content and the sulfur content of the solution are each 150 ppm by weight.

An Arabian Light direct distillation product, whose relevant properties are summarized in Table 1, was used as a standard diesel feed.

Table 1: Composition and physical properties of Arabian Light diesel

The basic nitrogen compounds are removed from the Arabian Light direct distillation product as follows: 25 g of IR 120 acid resin are contacted with 250 g of Arabian light diesel oil fraction in a glass reactor equipped with mechanical agitation. After stirring for 20 hours at 400 rpm at room temperature, the resin is removed by filtration and a petroleum fraction free of basic nitrogen compounds comprising 150 ppm of nitrogen and 13240 ppm of sulfur is recovered.

The sulfur and nitrogen concentrations were respectively analyzed by fluorescence and chemiluminescence on an Antek 9000 range nitrogen / sulfur analyzer equipped with a robotic liquid sampler. Gas chromatography-mass spectrometry (GC-MS) analyzes were performed on an Agilent 5973N mass spectrometer equipped with a CPSsil cb / low bleed MS CP5-78-61 Variant column. The ion exchange resins commercially available under the names

Amberjet 1200 H1, Amberlyst 36 dry and Amberjet 4200 Cl (Rohm and Haas), Reillex PVP 402 and Reillex HPQ (Reilly Industries) and Merrifield resin (Fluka 63868) were used. The commercial resins are placed in a column and washed successively (1 L / 100 mL resin) with deionized water, MeOH, deionized water and 1.0N NaOH. The resins are then washed. with deionized water until the pH of the eluent is neutral. For this, a solution of 1.0 N HCl (1 L / 100 mL resin) is passed over the column which is then washed with deionized water until the pH of the eluent is neutral. Total anion exchange capacity (CEAT) is determined for commercial resins using a Bchner-dried resin by back-dosing standard solutions of NaOH and is reported in Table 2 as milli-equivalents per gram of dry resin. In the case of Merrifield resin, the method described by GS Lu J. Org. Chem. 1981, 46, 3433-3436 was used. The ion exchange resins and Merrifield resin (Fluka # 63868) are then washed (1 L / 100 mL resin) with MeOH, acetone and toluene. The resins are then stored in toluene. Table 2: Characteristic of commercial resins

Name Structure Particle size CEAT

Amberlyst 36 dry 600 μ m> 5.4 meq./g

Amberjet 4200 Cl 700 μ m 1.7 meq./g ± 0.2

PVP 402 80-250 μ m 6.6 meq./g ± 0.2

HPQ 250-600 μ m 4.1 meq./g ± 0.2

Merrifield 300-800 μ m 5.5 mmol Cl / g

The Merrifield resin was converted according to SCHEME 1 below. The adsorbents used were prepared by direct quaternization of the commercially available N-methylimidazole or pyridine with the Merrifield resin according to the method described by Z.-T. Wang stall. Helv. Chim. Acta 2005, 88, 986 to 989.

SCHEME 1

Commercial resins Amberlyst 1200 H and Amberlyst A35 are converted according to SCHEME 2 below. The adsorbents used were prepared by reaction with a 1-alkyl-3-methyldimidazolium chloride or 1-alkylpyridinium chloride in 1,1,2-trichloroethane. The suspension is stirred in a rotary evaporator at ambient temperature for 2 hours and then at 100 ^° C. for 2 hours. About half of the 1,1,2-trichloroethane is evaporated under reduced pressure and then filtered hot on sinter. The resin is washed with dichloromethane and then with acetone. SCHEME 2

The Reillex PVP 402 resin has been quaternized according to the following SCHEME 3

SCHEME 3

The resins obtained have the characteristics mentioned in Table 3 below. Table 3

Structure Name Particle resin size

Resin 1,300-800 μ m

Resin 2,300-800 μ m

Resin 3,600 μ m

Resin 4,600 μ m

Resin 5 80-250 μ m

Example 1

Study of the adsorption of neutral nitrogen compounds by resins from the model fuel in discontinuous equilibrium sorption studies. 1.5 g of Bichner-dried resin are used, placed in glass bottles and 6 g of a toluene / heptane mixture (80/20 by weight) are added in the bottle, which is then mechanically shaken. 20 ⁰ C with a vibrax 100 (Bioblock) for 24 hours to reach the balance of adsorption. Then, the resulting solution is analyzed on a nitrogen / sulfur analyzer of the Antek 9000 range. The% of nitrogen and sulfur extractions obtained are given in Table 4. The N / S selectivity is calculated by carrying out the ratio of the calculated distribution for the resin.

Table 4: Comparison of the extraction with the ion exchange resins using the model fuel comprising 150 ppm N (carbazole) and 150 ppm S (dibenzothiophene). Resin / fuel mass ratio: 1/4, 24 h at 20 ^° C.

Example 2

Study of the adsorption of neutral nitrogen compounds by resins from Arabian Light diesel in discontinuous equilibrium sorption studies. The procedure is as in Example 1, the extraction being carried out on Arabian Light diesel and not on the model fuel. The% of nitrogen and sulfur extractions obtained are given in Table 5.

Table 5: Comparison of extraction with ion exchange resins using Arabian Light diesel (105 ppm N and 13 240 ppm S). Resin / diesel mass ratio: 1/4, 24 h at 20 ⁰ C

Example 3 Kinetic Extraction Study from Arabian Light Diesel

100 g of Arabian Light diesel are added to 25 g of Buchner-dried resin in a double-jacketed glass reactor under mechanical stirring using a PTFE stirrer at 300 rpm at 20 ° C. The resulting solution of Arabian Light diesel is analyzed as a function of time on an Antek 9000 Series nitrogen / sulfur analyzer (Figure 3A and 3B).

Figure 3A shows the total concentration and the% of nitrogen and sulfur obtained in the Arabian Light diesel phase as a function of time, by carrying out the extraction with Resin 5. Figure 3B represents the total concentration and the% of nitrogen and sulfur obtained in the Arabian Light diesel phase as a function of time, carrying out extraction with Resin 4. Example 4

Regeneration Resin 5.

Resin 5, obtained in Example 3, is regenerated by washing with pentane to remove the adsorbed inhibitors and then with methanol. 0.43 g (0.4%) of brown oil is obtained, after removal of methanol under vacuum. This oil is analyzed by GC-MS whose spectrum of analysis is given in Figure 4.

EXAMPLE 5 The elution behavior of sulfur compounds and nitrogen compounds was studied by adsorption experiments at 60 ^° C. on a column with Resin 5, using the model fuel. Leakage of S compounds occurs from 0.5 column volume and N compound leakage occurs after 4 column volumes as shown in Figure 5.

Example 6

The study of Example 5 is carried out with the Arabian Light diesel. The drilling curve is shown in Figure 6. The leakage of S compounds occurs from 0.5 column volume and for the nitrogen compounds, the ratio of the nitrogen concentration to the initial concentration (C / Ci) is equal to 0.5 after 2.5 column volumes.

Claims

1 - Use of a material composed of a solid support on which are immobilized aromatic nitrogenous planar groups carrying at least one positive charge associated with a counterion, to extract by adsorption, a mixture of hydrocarbons which has a boiling point in the boiling range of diesel, catalytic reaction inhibiting compounds used in the treatment of hydrocarbon mixtures of the diesel boiling range, and in particular hydrodesulfurization reactions, selected from polyaromatic compounds and neutral nitrogen compounds. 2 - Use according to claim 1 characterized in that the planar azotic aromatic groups carrying at least one positive charge are chosen from cationic derivatives of imidazole, pyridine, pyrazole, quinoline, isoquinoline, acridine, 2,6-diaza- anthracene, thiazole or triazine.

3 - Use according to claim 1 or 2 characterized in that the solid support is selected from polymeric matrices, porous or non-porous substrates such as silica, alumina or zeolites, activated carbons.

4 - Use according to one of claims 1 to 3 characterized in that the planar azotic aromatic groups carrying at least one positive charge are immobilized on the solid support by covalent bonding. 5 - Use according to one of claims 1 to 3 characterized in that the planar azotic aromatic groups carrying at least one positive charge are immobilized on the solid support by electrostatic interaction.

6 - Use according to claim 5 characterized in that the aromatic planar groups carrying at least one positive charge are chosen from the groups:

)

wherein :

r is equal to 0, 1, 2 or 3,

- s is 0, 1, 2 or 3, - m is 0, 1, 2, 3, 4 or 5,

p is 0, 1, 2, 3 or 4,

t is 0, 1, 2, 3 or 4,

v is 0, 1, 2, 3, 4 or 5,

x is 0, 1, 2, 3, 4, 5 or 6; R 1, R 1 and R 2 each independently represent an alkyl group having from 1 to 6 carbon atoms; alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group,

R ', R' and R ' ₂ each independently represent an alkyl group comprising from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C 1 -C 6) Alkylphenyl radicals in which the aliphatic groups may carry 1 or 2 substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C 1 -C 4) alkoxy groups and the phenyl ring may carry one or more substituents selected from halogen, amino, amine, ammonium, cyano, (C 1 -C ₆ ) -alkoxy, (C 1 -C ₆ ) alkyl,

- R "i and R" ₂ each independently represent a hydrogen atom, an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano group, an amino group, an amine group or an ammonium group. 7 - Use according to claim 5 or 6 characterized in that the planar aromatic groups carrying at least one positive charge are immobilized by electrostatic interaction on a polymer matrix of formula:

8 - Use according to claim 1, 2 or 3 characterized in that the material is chosen from the following polymer matrices:

9 - Use according to one of claims 1 to 8 characterized in that the neutral nitrogen compounds extracted are selected from pyrroles, indoles, carbazoles and their derivatives. 10 - Use according to one of claims 1 to 9 characterized in that the extracted polyaromatic compounds belong to the group of naphthalene, anthracene, phenanthrene, pyrene and their derivatives. 11 - Process for the treatment of a hydrocarbon mixture having a boiling point in the boiling range of diesel which comprises the following steps: a) extracting by adsorption, the hydrocarbon mixture, polyaromatic compounds and / or neutral nitrogen compounds, said compounds being inhibitors of catalytic reactions used in the treatment of hydrocarbon mixtures of the diesel boiling range, and especially of the hydrodesulphurization reactions, by bringing the mixture of hydrocarbons with a material composed of a solid support on which are immobilized nitrogenous planar aromatic groups carrying at least one positive charge associated with a counter-ion; b) hydrotreating at least a portion of the hydrocarbon mixture obtained in step a) with a hydrotreatment catalyst.

12 - Treatment process according to claim 11 characterized in that the planar azotic aromatic groups carrying at least one positive charge are chosen from cationic derivatives of imidazole, pyridine, pyrazole, quinoline, isoquinoline, acridine, 2,6- diaza-anthracene, thiazole or triazine.

13 - Process according to claim 11 or 12 characterized in that the solid support is selected from polymeric matrices, porous or non-porous substrates such as silica, alumina or zeolites, activated carbons.

14 - Treatment process according to one of claims 11 to 13 characterized in that the planar azotic aromatic groups carrying at least one positive charge are immobilized on the solid support by covalent bonding.

15 - Process of treatment according to one of claims 11 to 14 characterized in that the planar azotic aromatic groups carrying at least one positive charge are immobilized on the solid support by electrostatic interaction. 16 - Treatment process according to claim 15, characterized in that the aromatic planar groups carrying at least one positive charge are chosen from the groups:

h)

in which: - r is equal to 0, 1, 2 or 3,

- s is 0, 1, 2 or 3,

m is 0, 1, 2, 3, 4 or 5,

- p is 0, 1, 2, 3 or 4, - 1 is 0, 1, 2, 3 or 4, - v is 0, 1, 2, 3, 4 or 5, x is equal to at 0, 1, 2, 3, 4, 5 or 6,

R 1, R 1 and R 2 each independently represent an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a group cyano, amino, amine or ammonium,

R ', R' and R ' ₂ each independently represent an alkyl group comprising from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C 1 -C 6) Alkylalkyl groups in which the aliphatic groups may carry 1 or 2 substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C 1 -C 6) alkoxy groups and The phenyl ring may carry one or more substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ),

C ₆ ) alkyl,

17 - Treatment process according to claim 15 or 16 characterized in that the aromatic groups are immobilized by electrostatic interaction on a polymer matrix of formula:

18 - Treatment process according to claim 11, 12 or 13 characterized in that the material is chosen from the following polymer matrices:

19 - Treatment process according to one of claims 11 to 18 characterized in that it also comprises a step of separating the hydrocarbon mixture of the material, and a step of regeneration of the material. 20 - Treatment process according to one of claims 11 to 19 characterized in that step a) is preceded by a prior step of extraction of the hydrocarbon mixture of basic nitrogen compounds inhibitors of catalytic reactions used in the treatment hydrocarbon mixtures from the diesel boiling range.

21 - Treatment process according to one of claims 11 to 20 characterized in that step a) is preceded by a step of hydrotreating the hydrocarbon mixture and / or a division step into a fraction which has a high content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds and a fraction which has a low content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds, for example by distillation, alone the fraction which has a high content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds being subjected to step a).

22 - Treatment process according to one of claims 11 to 21 characterized in that step a) is carried out at a temperature between 0 and 300 ⁰ C and, in particular, between 20 and 100 ⁰ C, and under a pressure between 10 ⁵ and 50.10 ⁵ Pa.

23 - Method according to one of claims 11 to 22, characterized in that the ratio by weight of the hydrocarbon mixture on the material is at least 1 and preferably greater than or equal to 3.

24 - Treatment method according to one of claims 11 to 23 characterized in that the neutral nitrogen compounds extracted are selected from pyrroles, indoles, carbazoles and their derivatives.

25 - Treatment process according to one of claims 11 to 24 characterized in that the extracted polyaromatic compounds belong to the group of naphthalene, anthracene, phenanthrene, pyrene and their derivatives.

26 - Process according to one of claims 11 to 25 characterized in that step a) is carried out, so as to obtain a residual nitrogen content in the hydrocarbon mixture, after adsorption and removal of the material, less than 200 ppm by weight, preferably less than 100 ppm by weight and preferably less than 20 ppm by weight. 27 - Material composed of a solid support on which are immobilized nitrogenous planar aromatic groups carrying at least one positive charge associated with a counterion, characterized in that the nitrogenous aromatic groups are immobilized on the solid support by electrostatic interaction . 28 - Material according to claim 27, characterized in that the planar azotic aromatic groups bearing at least one positive charge are chosen from cationic derivatives of imidazole, pyridine, pyrazole, quinoline, isoquinoline, acridine, 2,6-diaza- anthracene, thiazole or triazine.

29 - Material according to claim 27 or 28 characterized in that the solid support is selected from polymeric matrices, porous or non-porous substrates such as silica, alumina or zeolites, activated carbons.

30 - Material according to one of claims 27 to 29, characterized in that the planar aromatic groups carrying at least one positive charge are chosen from the groups:

wherein :

r is equal to 0, 1, 2 or 3,

- s is 0, _1/2 or 3,

m is 0, 1, 2, 3, 4 or 5,

- p is 0, 1, 2, 3 or 4, - 1 is 0, 1, 2, 3 or 4, v is 0, 1, 2, 3, 4 or 5,

- x is 0, 1, 2, 3, 4, 5 or 6,

R 1, R 1 and R ₂ represent, independently of one another, an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising

1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group,

R ', R' and R ' ₂ each independently represent an alkyl group comprising from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C 1 -C 6) C4) alkylphenyl in which the aliphatic groups may carry 1 or 2 substituents chosen from halogen atoms, amino, amine, ammonium, cyano, (C ₁ -C ₄ ) alkoxy groups and the phenyl ring may carry one or more substituents chosen from halogen atoms, amino, amino, ammonium, cyano, (Ci-COalcoxy, (Cl- _C6) alkyl,

- R "i and R" ₂ each independently represent a hydrogen atom, an alkyl group comprising from 1 to 6 carbon atoms, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano group, an amino group, an amine group or an ammonium group. 31 - Material according to one of claims 27 to 30 characterized in that the planar aromatic groups carrying at least one positive charge are immobilized by electrostatic interaction on a polymer matrix of formula:

32 - Material according to one of claims 27 to 30 chosen from the following polymer matrices: