FR2906161A1 - USE OF A MATERIAL FOR EXTRACTING NEUTRAL POLYAROMATIC OR NITROGEN COMPOUNDS FROM A MIXTURE OF HYDROCARBONS IN THE DIESEL BOILING RANGE - Google Patents

Abstract

The subject of the present invention is the use of a material composed of a solid support on which are immobilized planar nitrogen-containing aromatic groups carrying at least one positive charge associated with a counter-ion, for extracting, by adsorption, a mixture of hydrocarbons having a boiling point in the boiling range of diesel, catalytic reaction inhibiting compounds used in the treatment of hydrocarbon mixtures in the boiling range of diesel, and particularly reactions hydrodesulfurization, selected from polyaromatic compounds and neutral nitrogen compounds, and a hydrotreatment process using such a use.

Description

The present invention relates to the technical field of hydrotreatment

  diesels. 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 hydrodesulphurization 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 paper Analysis of Nitrogen Compounds in Capillary-Gated Petroleum Cylinders and Specific Detection by Chemiluminescence, Analusis Magazine, 1995, 23, N29 to M36 More precisely studied the compounds nitrogen 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, worldwide, in the near future. It is indeed proposed to lower the sulfur content that is allowed in the gasoline 10 ppm by weight from 2009 in Europe and 15 ppm by weight from 2006 in the United States. In these circumstances, the development of ultra-deep desulfurization technology 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 to reduce the content of hydrocarbon cuts in such nitrogen compounds such as hydrodenitrogenation which relies 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 level is to be lowered to less than 50 ppm sulfur, the conversions that are required involve desulphurization of substituted dibenzothiophenes, especially those in which the substituents are present on aromatic rings adjacent to the hydrogen atom. heterocyclic sulfur. 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 hydrodesulfurization process even when present at very low concentrations by competitive adsorption and contribute to the difficulty of achieving stricter specifications. Therefore, these compounds are described as inhibitors of the catalytic reactions used in the treatment of hydrocarbon mixtures of the diesel boiling range and / or the hydrodesulphurization or poison reactions of the catalyst catalysts. hydrotreating. 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 current refineries, then refractory sulfur compounds may be more readily available. removed by hydrotreating using conventional catalyst feeds and process conditions (Koltai, T. et al., Appl.Catal.2002, 231, 253-261, Macaud, M. et al., Eng. Res 2004, 43, 7 843-7 849).

It is therefore necessary to selectively remove the polyaromatic compounds and nitrogen compounds, acting as inhibitors, prior to the hydrotreating reactions, to provide fuels which have a satisfactory sulfur content. The refining industry has demonstrated its ability to adapt hydrotreating 15 to stringent regulations by improving, in particular, catalytic activity. An additional solution also developed was to pre-treat the feedstock to be hydrotreated so as to remove the nitrogen-containing compounds (N compounds), the sulfur-containing refractory compounds (S compounds) and / or the 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 hydrotreatment conditions. Basic nitrogen compounds are known as poisons from HDS reactions. Many techniques have been employed to remove 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 basic nitrogen compounds, 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 nitrogen-containing heterocyclic compounds. 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 can also be adsorbed onto alumina, activated charcoal, silica, silica gel, zeolites and spent adsorbent as described in EP 1 454,976 A1, the patent 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 2 814 272 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 polyaromatic compounds and / or neutral nitrogen compounds which is very selective with respect to these compounds, and whose use can easily 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 diesel boiling range hydrocarbon mixtures or other non-inhibitory components present in the blends. hydrocarbons in 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 nitrogenous planar aromatic groups carrying at least one positive charge associated with a counter-ion, for extracting, by adsorption , a hydrocarbon mixture having a boiling point in the boiling range of diesel, catalytic reaction inhibiting compounds used in the treatment of hydrocarbon mixtures of the boiling range of diesel, and in particular hydrodesulfurization reactions chosen from polyaromatic compounds and neutral nitrogen compounds. Another object 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 steps: a) extracting, by adsorption, the mixture 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 hydrodesulphurization reactions, by bringing the mixture of hydrocarbons into contact with a material composed of a solid support on which are immobilized plane nitrogen-containing 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.

FIG. 1 schematically represents the various steps of a process for treating a petroleum cut, implementing a method according to the invention. Figure 2 schematically shows 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. FIGS. 5 and 6 show the drilling curves obtained in Examples 5 and 6. Within the scope of the invention, selective removal of the inhibitors in a petroleum fraction corresponding to the boiling range of the diesel is carried out. conversion of sulfur-containing refractory compounds, followed by selective desulphurization according to a known hydrodesulfurization process. The process according to the invention is illustrated in FIG. 1. By inhibiting 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 used in various refining processes, and particularly 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 method according to the invention is therefore particularly suitable for the treatment of petroleum fractions from petroleum refining, which have a boiling point in the range of diesel. In particular, such hydrocarbon mixtures have a boiling point of between 150 and 370.degree. 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 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 lum and in a preferred mode greater than 500 m.

The immobilization of the aromatic cationic nitrogen / cation counterion moieties on the solid support may in any case be 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 counterion K which will then be bound to the solid support by covalent bonding. Figure 2 illustrates schematically different structural examples 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, as shown in Figure 2.

The immobilization by chemical grafting may be carried out by any coupling technique well known to those skilled in the art, in particular in Synthesis and Separations Using Functional Polymers Ed. DC Sherrington and P.Hodge, J. Wiley & Sons (1988) some of which are illustrated in the following examples. 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 the polymer matrix, it is possible, for example, to use polystyrene, its copolymers and their derivatives which allow 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 polymeric matrix, it is possible to use a polymeric matrix comprising strong acid functional groups of formula: SO 3 H or the aromatic aromatic group carrying at least one positive charge is, for example , chosen from the groups: (R) and R 2 (R 1) p R 2) R 2 R 2 (R 1) p R 2) in which: r is equal to 0, 1, 2 or 3, s is equal to at 0, 1, 2 or 3, - m is 0, 1, 2, 3, 4 or 5, 5 - pestal at 0, 1,2,3 or 4, - test equal to 0, 1,2,3 or 4, - v is equal to 0, 1, 2, 3, 4 or 5, - x is 0, 1, 2, 3, 4, 5 or 6, R, R1 and R2 each represent independently of each other , 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' 1 and R 2 each independently represent an alkyl group having from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C1-C4) alkylphenyl groups in which the aliphatic groups may carry 1 or 2 substituents chosen from halogen atoms, amino, amine and ammonium groups, cyano, (C1-C4) alkoxy and the phenyl ring may carry one or more substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C1-C4) alkoxy, (C1-C6) alkyl groups. - R "1 and R" 2 each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 4 carbon atoms , a halogen atom, a cyano, amino, amine or ammonium group. By alkyl group, denotes a linear or branched saturated hydrocarbon group, for example methyl, ethyl, propyl, n- and t-butyl ... By group (C1-C6) alkyl, denotes an alkyl group comprising from 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 group (C1-C4) alkoxy, denotes an alkoxy group comprising from 1 to 4 carbon atoms.

By halogen atom is meant a chlorine, fluorine, bromine or iodine atom. The term "amine 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 (C1-C4) alkylphenyl, 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 bonding, on a support, for example of polymeric type, the counterion (s) will be the conjugate base, partially or totally deprotonated with an inorganic or organic acid. This counterion can, for example, represent Cl-, F or Br, with Cl- being particularly preferred. By way of example of materials which can be used in the context of the invention, mention may be made of the following polymeric matrices: ## STR1 ## 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 hydrotreatment 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. Step 10 of hydrotreating will also be able to utilize new improvements in catalytic processes, new approaches and emerging technologies for ultra-deep desulfurization 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)) to reduce 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 C and, in particular, between 20 and 100 C, and under a pressure of between 105 and 50.105 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 capacity 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. 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 of less than 50 ppm, 20 ppm or even 10 ppm according to the regulations in force, can be reached under conditions moderate conventional processes. 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 inhibitor adsorption step, the subsequent hydrodesulphurization (HDS) will make it possible to reach very low levels of sulfur, lower than 50 ppm, 20 ppm or 10 ppm according to the regulations in force, under moderate conventional conditions. HDS process.

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-containing compounds and a fraction which has a content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds, 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 feedstock; in 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 and ethanol. The eluent can also be a fully desulphurized and nitrogenized petroleum cutter. 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, particularly nitrogenous heterocycles, can be recovered in various ways, for example, in fine chemistry or for modifying the properties of fuels 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, 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 step is carried out in at least one other adsorption plant, whereby both Adsorption plants operate alternately in an adsorption phase and a regeneration phase. According to another advantageous characteristic, the regeneration can be carried out under operating conditions which are different from those of the adsorption and, in particular, at a lower pressure and at a higher temperature to facilitate the regeneration. The following examples serve to illustrate the invention and are not limiting in nature. In order to evaluate the removal of inhibitors of diesel fuels prior to the implementation of a hydrotreatment process, a model fuel and a standard diesel filler were 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 Density (at 293 L) (g / L) 852 Sulfur (ppm)> 13000 Aromatic (% by weight) 32 25 2906161 16 Basic nitrogen compounds are removed from the distillation product Direct Arabian Light as follows: 25g of IR 120 acid resin are contacted with 250 g of Arabian light diesel oil cut 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 Series nitrogen / sulfur analyzer equipped with a robotic liquid sampler. Gas chromatographic-mass spectrometry (GC-MS) analyzes were performed on an Agilent 5973N mass spectrometer equipped with a CP5sil 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) have been used. The commercial resins are placed in a column and washed successively (1 L / 100 mL resin) with deionized water, MeOH, deionized water and 1.0 N NaOH. 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 Buchner-dried resin by back-dosing standard solutions of NaOH and is reported in Table 2 as milliequivalents per gram of resin. dried. In the case of Merrifield resin, the method described by G. S. 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 * SO3H 600 pm> 5.4 meq./g * n * Amberjet 4200 Cl * n 700 pm 1.7 meq./g 0.2 PVP 402 80-250 pm 6.6 meq./g 0.2 HPQ n 250-600 pm 4.1 meq./g 0.2 cc- * Merrifeld * n 300-800 pm 5.5 mmol Cl The Merrifield resin was converted according to SCHEME 1 below. The adsorbents used were prepared by directly quaternizing the commercially available N-methylimidazole or pyridine with the Merrifield resin according to the method described by Z.-T. Wang and a /. Helv. Chim. Acta 2005, 88, 986 to 989. SCHEME 1 Cl 10 Amberlyst 1200 H and Amberlyst A35 commercial resins are converted according to SCHEME 2 below. The adsorbents used were prepared by reaction with a chloride of 1-alkyl-3-methyldimidazolium or 1-alkylpyridinium in 1,1,2-trichloroethane. The suspension is stirred in a rotary evaporator at room 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.

EXAMPLE 2 The Reillex PVP 402 resin was quaternized according to the following SCHEME 3: ## STR2 ## The resins obtained have the characteristics mentioned in Table 3 hereof. -after. Table 3 Name of the Structure Resin Resin Size Resin 1 * n elCI- 300-800 pm * N + Resin 2 * * 300-800 pm SCResin n 3 * n * N ± 600 pm S03 Resin 4 * n * 600 pm _ N + Example 1 Study of the adsorption of neutral nitrogen compounds by resins from the model fuel in batch equilibrium sorption studies . 1.5 g of Buchner-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. at 20 C with vibrax 100 (Bioblock) for 24 hours to reach the adsorption equilibrium. 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 performing the ratio of the coefficients. 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 Name and structure% extraction N% extraction S N / S selectivity resin Resin 5 91 13 71 Amberjet 4200 Cl 16 2 8 Resin 1 85 8 58 Merrifield 12 12 1 Resin 2 89 10 67 Amberjet 1200 H1 2 3 0.8 2906161 22 Example 2 Study of 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 the 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 C Resin name% extraction N% extraction S Selectivity N / S Resin 5 60 11 12 Resin 2 35 7 6 Merrifeld 23 16 1.5 Amberjet 4200 Cl 6 1 4 Amberjet 1200 H1 3.9 4.9 0.8 Example 3 Extraction kinetic study from Arabian Light diesel 100 g of Arabian Light diesel are added to 25 g of Buchner-dried resin in a reactor double-jacketed glass with 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 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 of 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 CGSM whose spectrum of analysis is given in FIG. 4. EXAMPLE 5 The elution behavior of sulfur compounds and nitrogen compounds was studied by means of adsorption experiments at 60 C on 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 Arabian Light diesel. The drilling curve is shown in Figure 6. The leakage of S compounds occurs from 0.5 column volume and for nitrogen compounds the ratio of the nitrogen concentration to the initial concentration (C / C 1) is equal at 0.5 after 2.5 column volumes.

Claims (32)

  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 following groups: ## STR2 ## R 'R' (R) r (R (R 1) p R 2) R2 ' Where R is 0, 1, 2 or 3, - s is equal to 0, 1, (R1) p R2) t R '2906161 26 (R1) m R2) v (Ik) R' R) m 2 or 3, 5 m is equal to 0, 1, 2, 3, 4 or 5, - pestal to 0, 1,2,3 or 4, - t is equal to 0, 1, 2, 3 or 4, vestal to 0, 1 , 2,3,4 or 5, where x is 0, 1,2,3,4, or 6, 10 -R, R1 and R2 are each, independently of one another, an alkyl group having from 1 to 6 carbon atoms, carbon, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group, -R ', R'1 and R'2 each independently represent one of the another, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 1 to 6 carbon atoms or (C 1 -C 4) alkylphenyl in which the aliphatic groups They 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, the amino, amine, ammonium, cyano, (C 1 -C 4) alkoxy, (C 1 -C 6) alkyl, R "1 and R" 2 groups each represent, independently of one another, a hydrogen atom, a alkyl group comprising 1 to 6 carbon atoms, an alkoxy group comprising 1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group. 2906161 27   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 polymeric matrix of the formula: SO 3 H or 10   8 - Use according to claim 1, 2 or 3 characterized in that the material is selected from the following polymer matrices: cr N + ~ SC; ~ N (1) (2) (3) n 1 N-1 S0 3 CI- (4) (5)   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. 2906161 28   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. 5   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 hydrodesulphurization reactions, by contacting the hydrocarbon mixture. 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 - Process of treatment according to claim 11 characterized in that the planar azotic aromatic groups carrying at least one positive charge 20 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, active coals.   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. 5 2906161 29   16 - Treatment process according to claim 15, characterized in that the aromatic planar groups carrying at least one positive charge are chosen from the following groups: ## STR1 ## (R (R 1) p R 2) R 1) p R 2) R 'R' 2 (R 1) m R 2) v R) m in which: - r is equal to 0, 1, 2 or 3, - s is equal to 0, 1, 2 or 3; , - is equal to 0, 1, 2, 3, 4 or 5, - pestal to 0, 1,2,3 or 4, - t is equal to 0, 1, 2, 3 or 4, 10 - is invested at 0, 1, 2, 3 , 4 or 5, x is 0, 1, 2, 3, 4, 5 or 6, - R, R 1 and R 2 each independently represent an alkyl group having from 1 to 6 atoms carbon, an alkoxy group comprising from 1 to 4 carbon atoms, a halogen atom, a cyano group, amino group, amine group or ammonium group; R ', R' 1 and R '2 represent, independently, one on the other, an alkyl group comprising from 1 to 6 carbon atoms, an alkenyl group comprising from 1 to 6 carbon atoms or (C1-C4) alkylphenyl groups in which the aliphatic groups are The compounds may have 1 or 2 substituents selected from halogen atoms, amino, amine, ammonium, cyano, (C 1 -C 4) alkoxy groups and the phenyl ring may have one or more substituents selected from halogen, the amino, amine, ammonium, cyano, (C1-C4) alkoxy, (C1-C6) alkyl, -R "1 and R" 2 groups each independently of one another represent a d hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a cyano, amino, amine or ammonium group.   17 - Treatment process according to claim 15 or 16 characterized in that the aromatic groups are immobilized by electrostatic interaction on a polymeric matrix of formula: SO3H or   18 - Treatment process according to claim 11, 12 or 13 characterized in that the material is selected from the following polymeric matrices: n + N (1) N N N self (4) 1 ci (5)   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. 2906161 32   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 of 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-containing compounds and a fraction which has a low content of sulfur-containing, nitrogen-containing and / or polyaromatic compounds, for example by distillation, only the fraction which has a high content of sulfur-containing, nitrogen-containing and / or polyaromatic-containing 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 C and, in particular, between 20 and 100 C, and under pressure between 105 and 50.105 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 20 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 - Treatment 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. 2906161 33   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 . 5   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 10 is chosen 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 aromatic planar groups carrying at least one positive charge are chosen from the following groups: (R) r (R 15 2906161 34 (R)) p 1 R (R 1) p R 2) t 1 R 'R' (R 1) m R 2) v R 'R) m in which: - r is equal to 0, 1, 2 or 3, 5 - s is equal to 0, 1, 2 or 3, - is equal to 0, 1,2,3,4 or 5, - is equal to 0, 1,2,3 or 4, - equal to 0, 1, 2,3 or 4, v = 0, 1, 2, 3, 4 or 5, where 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 atoms carbon, an alkoxy group comprising 1 to 4 carbon atoms, a halogen atom, a cyano group, an amino group, an amine group or an ammonium group, -R ', R'1 and R'2 each independently represent one of the other, an alkyl group having 1 to 6 carbon atoms, an alkenyl group of 1 to 6 carbon atoms or (C 1 -C 4) alkylphenyl in which the groups lipoids 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, amine, ammonium, cyano, (C 1 -C 4) alkoxy, (C 1 -C 6) alkyl, -R "1 and R" 2 are each, independently of one another, a hydrogen atom, an alkyl group, comprising 1 to 6 carbon atoms, an alkoxy group comprising 1 to 4 carbon atoms, a halogen atom, a cyano group, amino, amine or ammonium. 20   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 polymeric matrix of formula: SO3H or 2906161 36   32 - Material according to one of claims 27 to 30 selected from the following polymer matrices: NN- (3) se (4) 5