EP2794522A1

EP2794522A1 - Method for isomerizing an aromatic c8 fraction in the presence of a catalyst containing an euo zeolite and a specific binder

Info

Publication number: EP2794522A1
Application number: EP12813395.6A
Authority: EP
Inventors: Emmanuelle Guillon; Eric Sanchez
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2011-12-20
Filing date: 2012-11-20
Publication date: 2014-10-29
Also published as: FR2984308B1; ZA201403956B; WO2013093222A1; US9828311B2; FR2984308A1; US20140364668A1

Abstract

The invention relates to a method for isomerizing an aromatic fraction comprising at least one aromatic compound having eight carbon atoms per molecule, which comprises contacting said fraction with at least one catalyst including at least one metal of Group VIII of the periodic table of the elements, at least one zeolite support including a zeolite selected from among the zeolites having an EUO and MOR structure type, taken alone or in a mixture, and at least one matrix, such that the specific surface area of the matrix in the zeolite support of said catalyst is between 5 and 200 m2/g.

Description

PROCESS FOR ISOMERIZING AN AROMATIC C8 CUT IN THE PRESENCE OF A CATALYST BASED ON A EUO ZEOLITE AND A PARTICULAR BINDER

Field of the invention

The present invention relates to the isomerization of an aromatic cut containing at least one aromatic compound with eight carbon atoms per molecule for the production of xylenes and in particular para-xylene. The present invention relates more particularly to a method of isomerization of an aromatic filler comprising at least one aromatic compound with eight carbon atoms per molecule to maximize the production of para-xylene, said isomerization process using a catalyst comprising at least one Group VIII metal supported on a particular zeolite support. The present invention also relates to the process for preparing said catalyst.

State of the art

The catalytic isomerization formulations of xylenes known to those skilled in the art are generally based on a zeolite and a Group VIII metal shaped with a binder, often aluminum. Among the zeolites used in isomerization of aromatic C8 cuts, there is ZSM-5, used alone or mixed with other zeolites, such as mordenite. These catalysts are described in particular in US Pat. No. 4,467,129, US Pat. No. 4,482,773 and EP-B-13,617. Other catalysts mainly based on mordenite have been described, for example, in US Pat. A-4,723,051, US-A-4,665,258 and FR-A-2,477,903. More recently, it has been proposed a catalyst based on a zeolite of structural type EUO (EP-A1-923 987). The patent application WO-A-2005/065 380 describes the use of a zeolite of MTW structural type in isomerization of xylenes and ethylbenzene. Application WO2010 / 000652 describes the use of a catalyst consisting of zeolite ZSM-12 and an aluminum binder, having a pore volume greater than 0.6 m ³ / g and a specific surface area greater than 250 m ² / g .

Object and interest of the invention

The present invention relates to a method for isomerizing an aromatic section containing at least one aromatic compound having eight carbon atoms per molecule comprising contacting said section with at least one catalyst comprising at least one metal of group VIII of the periodic classification of the elements, at least one zeolite support comprising a zeolite chosen from zeolites of structure type EUO and MOR, taken alone or as a mixture and at least one matrix, such that the specific surface area of the matrix in the zeolitic support of said catalyst is between 5 and 200 m ² / g.

It has surprisingly been found that a catalyst, in the form of extrudates, balls, or trilobates comprising at least one metal of group VIII of the periodic table of elements, at least one zeolite support comprising a zeolite chosen among the zeolites of structure type EUO and MOR, taken alone or as a mixture and at least one matrix, such as the specific surface of the matrix in the zeolitic support of said catalyst is between 5 and 200 m ^z / g leads to improved catalytic performances in terms of activity when used in a process for isomerizing an aromatic cut comprising at least one compound aromatic compound with eight carbon atoms per molecule. In particular, such a catalyst is more active towards the desired products, namely xylenes and in particular paraxylene, than a catalyst of the state of the art.

Description of the invention

Summary of the invention

The present invention relates to a method for isomerizing an aromatic section containing at least one aromatic compound having eight carbon atoms per molecule comprising contacting said section with at least one catalyst comprising at least one metal of group VIII of the periodic classification of the elements, at least one zeolite support comprising a zeolite chosen from zeolites of structural type EUO and MOR, taken alone or as a mixture and at least one matrix, such that the specific surface of the matrix in the zeolitic support of said catalyst is between 5 and 200 m ² / g.

In a preferred manner according to the invention, the specific surface of the matrix in the zeolitic support of said catalyst is between 20 and 160 m ² / g, more preferably between 50 and 160 m ² / g.

The catalyst according to the invention advantageously comprises 1 to 90% by weight of zeolite of structure type EUO and / or MOR relative to the total weight of the catalyst. According to the invention, the zeolite of structural type EUO is chosen from zeolites EU-, TPZ-3, ZSM-50 or their mixture, preferably the zeolite of structural type EUO is zeolite EU-1. According to the invention, the structural type zeolite MOR is Mordenite. Advantageously, the zeolite used in the zeolitic support of the catalyst is a mixture of zeolite EU-1 and Mordenite.

The catalyst according to the invention advantageously comprises a metal content (aux) group VIII between 0.01 and 4% by weight relative to the total weight of the catalyst.

In a variant according to the invention, said catalyst additionally comprises at least one metal chosen from metals of groups IIIA, IVA and VIIB, said metal (s) in a content of less than or equal to 2% by weight relative to the total weight of the catalyst. The present invention also relates to a process for preparing the catalyst according to the invention comprising at least the following steps:

i) the synthesis of at least one zeolite of structure type EUO and / or MOR,

ii) preparing a zeolitic support by shaping said zeolite with at least one matrix iii) the deposition of at least one metal of group VIII of the periodic table of elements on the zeolitic support resulting from stage ii) of shaping

According to the process of the invention, step i) of synthesis of the zeolite is advantageously followed by at least one calcination step and at least one ion exchange step carried out before the step ii) of implementation. form.

According to the process of the invention, the shaping step ii) is followed by a drying step carried out at a temperature of between 100 and 150 ° C. for a period of between 5 and 20 hours in an oven and then a calcination step carried out at a temperature between 250 ° C and 750 ° C for a period of between 1 and 8 hours.

The isomerization process of the feedstock according to the invention, in particular an aromatic cut containing at least one aromatic compound having eight carbon atoms per molecule, is advantageously used with the catalyst according to the invention at a temperature of 300.degree. 500 ° C, a hydrogen partial pressure of 0.3 to 1.5 MPa, a total pressure of 0.45 to 1.9 MPa and a feed space velocity, expressed in kilograms of feed introduced per kilogram of catalyst and per hour from 0.25 to 30 hr ^-1 .

Detailed description of the invention

The present invention relates to a method for isomerizing an aromatic section containing at least one aromatic compound having eight carbon atoms per molecule comprising contacting said section with at least one catalyst comprising at least one metal of group VIII of the classification periodic element, at least one zeolite support comprising a zeolite selected from zeolites of structural type EUO and MOR, taken alone or in mixture and at least one matrix, such that the specific surface of the matrix in the zeolite support of said catalyst is included between 5 and 200 m ² / g.

In a variant of the process according to the invention, the specific surface area of the matrix in said zeolitic catalyst support is between 5 and 200 m ² / g, preferably between 20 and 160 m ² / g, more preferably between 50 and 200 m ² / g. and 160 m ² / g, still more preferably between 50 and 150 m ² / g. According to the invention, the zeolite used in the zeolite support of the catalyst used in the process according to the invention is chosen from zeolites of structural type EUO and MOR, taken alone or as a mixture. Preferably, the zeolite of structural type EUO is chosen from zeolites EU-, TPZ-3 and ZSM-50, taken alone or as a mixture and more preferably, the EUO-structural zeolite is EU-1 zeolite. According to the invention, the structural type zeolite MOR is Mordenite. In a variant according to the invention, the zeolite used in the zeolitic support of the catalyst is a mixture of zeolite EU-1 and mordenite.

Advantageously, the catalyst according to the invention comprises 1 to 90% by weight of zeolite with structure type EUO and / or MOR, preferably 3 to 80% and even more preferably 4 to 60% by weight of zeolite with structure type EUO and / or or MOR with respect to the total weight of the catalyst. The catalyst according to the invention advantageously comprises a content of Group VIII metal (s) of between 0.01 and 4% by weight, preferably 0.05 to 2.0% by weight relative to the total weight of the catalyst.

According to the invention, the total pore volume of the catalyst measured by nitrogen adsorption is between 0.5 cm ³ / g and 1.5 cm ³ / g.

Preferably, the catalyst according to the invention has a macroporous volume of less than 0.1 cm ³ / g, preferably less than 0.05 cm ³ / g, the pore volume being defined as being the pore volume having a size greater than 50 nm.

According to the invention, the mean diameter of the mesopores of the catalyst measured according to the BJH method (d Vmeso / 2) is greater than 8 nm, preferably greater than 10 nm, preferably greater than 12 nm, the mesopores being understood as being the pores of size between 2 and 50 nm. The average diameter of the macropores of the catalyst measured according to the BJH method (d Vmacro / 2) is greater than 60, preferably between 70 and 200 nm, more preferably between 70 and 150 nm.

Characterization techniques

The specific surface is defined by the specific surface area B. ET. determined by nitrogen adsorption in accordance with ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the Journal of the American Society, 60, 309, (1938). Nitrogen adsorption was determined by the Barrett-Joyner-Halenda model (BJH) The nitrogen adsorption-desorption isotherm according to the BJH model is described in the journal "The Journal of American Society", 73, 373, (1951) written by EPBarrett, LGJoyner and PPHalenda. Nitrogen adsorption volume means the volume measured for P / P ₀ = 0.99, pressure for which it is assumed that nitrogen has filled all the pores. The average nitrogen desorption diameter is defined as a diameter such that all the pores smaller than this diameter constitute 50% of the pore volume (Vp) measured on the desorption branch of the nitrogen isotherm.

The present invention also relates to the process for preparing the catalyst according to the invention. The catalyst according to the invention is prepared according to a process comprising at least the following stages:

i) the synthesis of at least one zeolite of structure type EUO and / or MOR,

ii) preparing a zeolitic support by shaping said zeolite with at least one matrix

iii) the deposition of at least one metal of group VIII of the periodic table of elements on the zeolitic support resulting from stage ii) of shaping

Step i) synthesis of the zeolite

The zeolites used according to the invention are crystalline solids which comprise silicon and at least one element T selected from the group formed by aluminum, iron, gallium and boron, preferably from the group formed by aluminum and boron, and more preferably aluminum; with an overall Si / T atomic ratio greater than 5. The zeolites used according to the invention are preferably in acid form, such that the Na / T ratio is less than 15%, preferably less than 10%, more preferably less than 5%.

Zeolites with structure type EUO and / or MOR described are well known in the prior art and their porous structure and topography is defined in P'Atlas of Zeolite Framework Types ", Ch. Baerlocher, WM Meier, DH Olson, ^7th edition , 2007) EUO-type zeolites have a one-dimensional (10MR) mean pore network with 12-tetrahedral (12MR) side pockets The MOR zeolites have a large-pore (2MR) one-dimensional lattice.

The mode of preparation of the various zeolites is also well known to those skilled in the art. In general, the methods for preparing such zeolites comprise the mixing in an aqueous medium of a silicon source, a source of a T element such as aluminum, a source of an alkali metal and a nitrogenous organic compound acting as a structurant. The zeolite EU-1, described in the European patent application EP-A-0 042 226, is prepared using, as structuring agent, either the alkylated derivative of a polymethylene α-ω diammonium or a degradation product of said derivative. or else precursors of said derivative. The zeolite TPZ-3, described in European Patent Application EP-A-0 051 318, is prepared using the same family of structurant as that used to synthesize zeoiite EU-1. It is in particular described the use of the compound 1, 6- Ν, Ν, Ν, Ν ', Ν', Ν'-hexamethylhexamethylenediammonium. Zeolite ZSM-50, described in EP 0 159 845 and US-A-4,640,829, is prepared by using as structurant the dibenzyldimethylammonium derivative (DBDMA).

Also, for the implementation of said step i) for preparing the zeolite of the EUO structural type according to the invention, one skilled in the art will usefully refer to one or the other of the references cited above describing the preparing such zeolites.

The synthesis of Mordenite is described by Meier et al (Kristallogr 115 (1961)). Kim et al (Zeolites 11 (1991) 745) which describe the synthesis of zeoiite Mordenite in the absence of a nitrogenous organic structurant, using a mixture of sodium hydroxide, sodium aluminate and silica.

According to the invention, the specific surface of the zeolite resulting from stage i) is advantageously greater than 250 m ² / g, preferably greater than 350 m ² / g. Preferably, the zeolite from step i) according to the invention is entirely microporous. Preferably, step i) of synthesis of the zeolite is followed by at least one calcination step and at least one ion exchange step carried out before the shaping step ii).

Calcination step of the zeolite resulting from step i) Said step of calcining under air flow of the zeolite resulting from said step i) is intended to eliminate the organic structuring agent present in the microporosity of said zeolite, by for example, the cation R 1 R 2 3 -N ⁺ - (CH ₂ ) _n - N ⁺ - R 4 R 5 R 6, preferably 1, 6 Ν, Ν, Ν, Ν ', Ν', Ν'-hexamethylhexamethylene diammonium when the zeolite synthesized during said step i) is zeolite EU-1. According to the invention, the zeolite calcination step resulting from said step i) is advantageously carried out at a temperature of between 150 and 600 ° C, preferably between 200 and 600 ° C, more preferably between 250 and 550 ° C for a period of between 1 and 48 hours, preferably for a period of between 1 and 30 hours.

Ion exchange step on the zeoiite from step i) calcined

According to the invention, the zeolite can also undergo after calcination of the zeolite from step i) at least one ion exchange step. The ion exchange (s) subsequent to said calcination In dry air stream it is possible to remove at least partly, preferably almost completely, the alkaline cation, in particular sodium, optionally present in the cationic position in the zeolite in its crude synthetic form. According to the invention, each ion exchange step is carried out at a temperature preferably between 20 and 150 ° C for a duration advantageously between 2 hours and 10 hours. Said ion exchange step is according to the invention carried out by at least one NH 4 NO 3 solution or ammonium acetate solution.

Step ii) of preparing a zeolite support by shaping the zeolite synthesized with at least one matrix.

The method for preparing the catalyst according to the invention is continued by carrying out the step ii) of shaping the zeolite with at least one matrix. According to the invention, the step ii) of shaping the zeolite is carried out on the zeolite synthesized according to step i) which has or has not undergone calcination and / or one or more ion exchanges. These last two operations can be performed after step ii) of shaping the zeolite.

The implementation of said step ii) of shaping of said zeolite of structural type EUO and / or MOR according to the invention is carried out using a matrix chosen from clays, magnesia, aluminas, silicas titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, silica-aluminas and coal or a mixture of at least two of these compositions. Preferably, the matrix is an alumina. The shaping according to said step ii) consists more particularly in kneading the zeolite chosen from the structural types EUO and / or MOR, in a wet matrix gel, preferably alumina. Said wet matrix gel is generally obtained by mixing at least one acid and a matrix powder for a period of time necessary to obtain a good homogeneity of the dough and then forming an object that can be used in a catalytic reactor.

A matrix powder is a predominantly solid compound and preferably an oxide or hydrate. A hydrate and, more preferably, an aluminum hydrate are preferably used. The loss on ignition of this hydrate will be greater than 15%. The alumina powders chosen according to the invention include commercial aluminas, such as TH, TM, Pural or Disperal grades from Sasol. The shaping can be performed using shaping techniques known to those skilled in the art, such as for example: extrusion, coating, spray drying or pelletizing. For example, by passing said dough thus obtained through a die to form extrudates of diameter advantageously between 0.4 and 4 mm. The shaping can also be carried out in the presence of the various constituents of the catalyst and extrusion of the obtained mineral paste, by pelletizing, shaped into beads at the rotating bezel or drum, drop coagulation, oil-drop, oil- up, or any other known method of agglomeration of a powder containing alumina and optionally other ingredients selected from those mentioned above.

The catalysts used according to the invention are in the form of spheres or extrusions. However, it is advantageous that the catalyst is in the form of extrudates with a length of between 4 and 9 mm and more particularly between 2 and 5 mm. The shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings. The cylindrical shape is preferably used, but any other shape may be used.

Furthermore, these supports used according to the present invention may have been treated as is well known to those skilled in the art by additives to facilitate the shaping and / or to improve the final mechanical properties of the supports. . By way of example of additives, there may be mentioned in particular cellulose, carboxymethylcellulose, carboxyethyl cellulose, tall oil, xanthan gums, surfactants, flocculating agents such as polyacrylamides, carbon black, starches, stearic acid, polyacrylic alcohol, polyvinyl alcohol, biopolymers, glucose, polyethylene glycols, etc.

Extrusion can be performed by any conventional tool, commercially available. The paste resulting from the mixing is extruded through a die, for example using a piston or a single screw or twin extrusion screw. This extrusion step can be performed by any method known to those skilled in the art.

The adjustment of the characteristic porosity of the zeolite supports according to the invention, and in particular the specific surface area, is partially carried out during this step of shaping the support particles and any type of matrix known to man is suitable for invention. Without being exhaustive, influential shaping parameters are the water content, the acid level, the mixing time. Water can be added or removed to adjust the viscosity of the extrusion paste. This step can be performed at any stage of the kneading step.

The acid content added to the kneading before shaping is less than 30%, preferably between 0.5 and 30%, more preferably between 0.5 and 20% by weight of the mass. anhydrous zeolite and matrix, preferably alumina engaged in the synthesis. Nitric acid is preferred.

Optionally, it is also possible to add a base to neutralize the paste during the shaping after mixing in the presence of acid, for example ammonia, at a content of between 1 and 50% by weight. anhydrous zeolite and matrix, preferably alumina engaged.

The mixing time is advantageously between 5 minutes and 120 minutes, preferably between 5 minutes and 90 minutes, even more preferably between 5 and 60 minutes. Zeolite can be added at any time during mixing.

Traces of impurities may be present in the matrix used according to the invention, for example Na, Fe, Si or sulfur. Their content is preferably limited. According to the invention, the traces of sulfur are less than 0.2% by weight, the traces of Na ₂ 0 are less than 0.01% by weight, and the traces of Si0 ₂ and Fe ₂ 0 _{3 are} less than 0.02% by weight relative to the mass. total of the matrix.

Advantageously, the zeolite associated with the matrix, also called zeolite support in the context of the present invention, is in the form of beads, extrudates or trilobés, advantageously in the form of extrudates or trilobés, more preferably under trilobed form.

In a variant of the process according to the invention, an element such as tin, cerium or phosphorus can be advantageously introduced during the shaping step ii), for example by comalaxing Advantageously, the catalyst according to the invention The invention comprises 1 to 90% by weight of zeolite of structural type EUO and / or MOR, preferably 3 to 80% and even more preferably 4 to 60% by weight of zeolite of structural type EUO and / or MOR, the matrix constituting the 100% complement.

The specific surface of the zeolite support of the catalyst depends on the amount of zeolite present in the zeolite support. It is equal to the sum of the specific surfaces of the 2 constituents matrix and zeolite, weighted by their mass within the zeolitic support. The choice of the matrix used in the invention is such that, after the shaping step ii), the specific surface area of the matrix in the zeolite support is between 5 and 200 m ² / g, preferably between 20 and 160 m ² / g, more preferably between 50 and 160 m ² / g, more preferably between 50 and 150 m ² / g. The BET specific surface area of the matrix is obtained by subtracting the specific surface area of the EUO and / or MOR zeolite (included in the weighted zeolite support of the introduced mass) from the total specific surface area of the zeolitic support of the catalyst. The specific surface of the zeolite support is measured at the end of the zeolite support drying and calcination step subsequent to the shaping step ii).

Drying and calcination after step ii) shaping. According to the process of the invention, the shaping step ii) is advantageously followed by a drying step and then a calcination step. In this case, the drying step is advantageously carried out at a temperature of between 100 and 150 ° C. for a period of between 5 and 20 hours in an oven and the calcination step is advantageously carried out at a temperature of between 250 ° C. and 750 ° C for a period of between 1 and 8 hours. It may be advantageous to carry out this calcination step in the presence of water vapor.

Step iii) depositing at least one Group VIII metal on the zeolite support

According to the invention, the process for the preparation of the catalyst is continued by the implementation of step iii) which consists in introducing at least one metal of group VIII of the periodic table of elements onto the zeolitic support prepared in step ii).

Advantageously, said group VIII metal is selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably from noble metals platinum, palladium , nickel, iridium and very preferably among palladium and platinum, taken alone or as a mixture. Even more preferably, said group VIII metal is platinum.

Advantageously, the catalyst according to the invention comprises a content of Group VIII metal (s) of between 0.01 and 4% by weight, preferably 0.05 to 2.0% by weight relative to the total weight of the catalyst.

According to step iii), the deposition of said Group VIII metal (s) on the zeolitic support can be carried out by the dry impregnation technique, the technique of impregnation by excess or by ion exchange, preferably, step iii) is carried out by the technique of dry impregnation or ion exchange and more preferably by ion exchange. When several metals are introduced, they can be introduced either all in the same way or by different techniques.

All group VIII metal precursors are suitable for the deposition of one or more Group VIII metals (ux) on the zeolitic support. In particular, for any noble metal of group VIII, it is possible to use ammonia compounds or compounds such as, for example, ammonium chloroplatinate, platinum dicarboxylic dichloride, hexahydroxyplatinic acid, palladium or palladium nitrate. Platinum is advantageously introduced in the form of hexachloroplatinic acid. The introduction of the Group VIII noble metal is preferably carried out by impregnation with an aqueous or organic solution of one of the metal compounds mentioned above. Among the organic solvents that can be used, mention may be made of paraffinic, naphthenic or aromatic hydrocarbons containing, for example, from 6 to 12 carbon atoms per molecule, and halogenated organic compounds containing, for example, from 1 to 12 carbon atoms per molecule. For example, n-heptane, methylcyclohexane, toluene and chloroform may be mentioned. Solvent mixtures can also be used. During step iii) of deposition of the Group VIII metal on the zeolite support resulting from the shaping step ii), the control of certain parameters implemented, in particular the nature of the precursor of the metal (s) (ux) of the group VIII used (s) and / or the impregnation technique, can guide the deposit of (es) said (s) metal (ux) mainly on the matrix or on the zeolite or statistically on the zeolite-matrix set namely the entire zeolitic support.

Thus, to introduce the group VIII metal (s), preferably platinum and / or palladium, predominantly on the matrix, it is possible to carry out anionic exchange with hexachloroplatinic acid and / or hexachloropalladic acid, in the presence of a competing agent, for example hydrochloric acid. This deposit is preferably followed by calcination, for example at a temperature between 350 and 550 ° C and for a period of between 1 and 4 hours. With such precursors, the group VIII metal (s) is (are) predominantly deposited on the matrix and the said metal (s) exhibit good dispersion and stability. good macroscopic distribution through the catalyst grain.

It is also conceivable to deposit the group VIII metal (s), preferably platinum and / or palladium, by cation exchange so that said metal (s) is (in particular) ) t mainly deposited on the zeolite. Thus, in the case of platinum, the precursor may for example be chosen from:

ammonia compounds such as tetrammine platinum (II) salts of formula

Pt (NH ₃ ) X 2, hexammine platinum (IV) salts of formula Pt (NH 3) 6X; platinum (IV) halogenopentammine salts of formula (tX (NH 3) s) X 3 _; platinum N-tetrahalogenodiamine salts of formula PtX4 (NH3) 2; and

halogenated compounds of formula H (Pt (acac) 2X);

X being a halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, X being preferably chlorine, and "acac" representing the acetylacetonate group (of formula C5H7O2), derived from acetylacetone . With such precursors, the group VIII metal (s) is (are) deposited predominantly on the zeolite and the said metal (s) present (s) a good dispersion and a good macroscopic distribution through the catalyst grain. According to the invention, step iii) of depositing the Group VIII metal on the zeolitic support is preferably carried out by ion exchange with hexachloroplatinic acid.

In another variant of the process according to the invention, step iii) comprises the further deposition of at least one additional metal selected from the metals of groups NIA, IVA and VIIB. Said metal chosen from the metals of groups IIIA, IVA and VIIB is advantageously chosen from gallium, indium, tin and rhenium, preferably from indium, tin and rhenium.

In such a case, the catalyst according to the invention advantageously comprises the said metal (s) in a content less than or equal to 2% by weight relative to the total weight of the catalyst. Preferably, this content is between 0.01 and 2%, preferably between 0.05 and 1.0% by weight relative to the total weight of the catalyst.

In the case where the catalyst used in the isomerization process of the invention also contains at least one additional metal selected from the metals of groups IIIA, IVA and VIIB, all the techniques of deposition of such a metal known from the skilled in the art and all the precursors of such metals may be suitable. Group VIII metal (s) and Group IIIA, IVA and VIIB metal (s) may be added either separately or simultaneously in at least one unit step. When at least one Group IIIA, IVA and VIIB metal is added separately, it is preferred that it be added after the Group VIII metal.

The additional metal selected from the metals of groups NIA, IVA and VIIB may be introduced via compounds such as, for example, the chlorides, bromides and nitrates of metals of groups IIIA, IVA and VIIB. For example, in the case of indium, nitrate or chloride is advantageously used, and in the case of rhenium, perrhenic acid is advantageously used. In the case of tin, tin chlorides SnCl ₂ and SnCl ₄ are preferred. The additional metal chosen from the metals of groups IIIA, IVA and VIIB may also be introduced in the form of at least one organic compound chosen from the group consisting of the complexes of said metal, in particular the metal polyketone complexes and the hydrocarbylmetals such as alkyls, cycloalkyls, aryls, alkylaryls and arylalkyls. In the latter case, the introduction of the metal is advantageously carried out using a solution of the organometallic compound of said metal in an organic solvent. Compounds can also be used organohalogenated metal. As organic compounds of metals, there may be mentioned in particular tetrabutyltin, in the case of tin, and triphenylindium, in the case of indium.

In addition, intermediate treatments such as, for example, calcination and / or reduction may be applied between the successive deposits of the different metals.

The preparation of the catalyst according to the invention is advantageously terminated by calcination, preferably at a temperature of between 250 ° C. and 600 ° C., for a duration of between 0.5 and 10 hours. The calcination is preferably preceded by drying, for example in an oven, at a temperature of between 25 ° C. and 250 ° C., preferably between 40 ° C. and 200 ° C. Said drying step is preferably conducted during the rise in temperature necessary to effect said calcination. It is possible to carry out a preliminary reduction of the ex situ catalyst, under a stream of hydrogen, for example at a temperature of 450 ° C. to 600 ° C., for a period of 0.5 to 4 hours.

It may be advantageous according to the invention to recalcine the catalyst after reduction, in the presence of air and optionally in the presence of water vapor according to the teachings of patent applications FR0702941 and FR0702943. The deposition of said Group VIII metal (s) is advantageously carried out in such a way that the dispersion of said metal (s), determined by chemisorption, is from 50% to 100% preferably from 60% to 100% and even more preferably from 70% to 100%. The deposition of said Group VIII metal (s) is also advantageously carried out so as to obtain a good distribution of said metal (s) in the shaped catalyst. This distribution is characterized by its profile obtained by microprobe of Castaing. The ratio of the concentrations of each element of group VIII to the heart of the grain with respect to the edge of this same grain, defined as the distribution coefficient, is advantageously from 0.6: 1 to 1, 34: 1, preferably from 0 to , 7: 1 to 1, 3: 1.

In the case where the catalyst does not contain sulfur, a reduction of the metal in hydrogen is advantageously carried out in situ before injection of the feedstock.

In the case where the catalyst used in the invention contains sulfur, the sulfur is introduced on the shaped catalyst, calcined, containing the metal or metals mentioned above, either in situ before the catalytic reaction, or ex situ. Possible sulphurisation occurs after the reduction. In the case of in situ sulfurization, the reduction, if the catalyst has not been reduced beforehand, occurs before the sulfurization. In the case of an ex situ sulphurization, reduction is carried out and then sulphurization. The Sulfurization is carried out in the presence of hydrogen using any sulphurizing agent well known to those skilled in the art, such as, for example, dimethyl sulphide or hydrogen sulphide. For example, the catalyst is treated with a dimethyl sulfide-containing filler in the presence of hydrogen, with a concentration such that the sulfur / metal atomic ratio is 1.5. The catalyst is then maintained for about 3 hours at about 400 ° C under hydrogen flow prior to feed injection. In the case where the catalyst used in the invention contains sulfur, the sulfur content in the catalyst is such that the ratio of the number of sulfur atoms to the number of metal atoms of the group VIII deposited is up to 2: 1, preferably from 0.5: 1 to 2: 1. Use of the catalyst according to the invention

The isomerization process according to the invention comprises contacting an aromatic section containing at least one aromatic compound having eight carbon atoms per molecule with at least said catalyst described above in the present description.

According to the process of the invention, said aromatic cut comprises in particular either only a mixture of xylenes, or only ethylbenzene, or a mixture of xylene (s) and ethylbenzene. Said isomerization process according to the invention is generally carried out according to the following operating conditions:

a temperature of 300 ° C to 500 ° C, preferably 320 ° C to 450 ° C and even more preferably 340 ° C to 430 ° C;

a hydrogen partial pressure of 0.3 to 1.5 MPa, preferably 0.4 and 1.2 MPa and more preferably 0.7 to 1.2 MPa;

a total pressure of 0.45 to 1.9 MPa, preferably 0.6 to 1.5 MPa; and

a feed space velocity, expressed in kilograms of feed introduced per kilogram of catalyst per hour, from 0.25 to 30 h ^-1 , preferably from 1 to 10 h ^-1 and more preferably from 2 to 6 h ^"1 .

The examples which follow illustrate the invention without limiting its scope.

Example 1 Preparation of an EU-1 Zeolite

The raw material used is a synthetic crude zeolite EU-1, comprising the organic structuring agent namely 1, 6 Ν, Ν, Ν, Ν ', Ν', Ν'-hexamethylhexamethylene diammonium and which has an Si / Si atomic ratio. A global AI equal to 15.3 and a weight content of sodium corresponding to an atomic ratio Na / Al (in%) equal to 30.8. This zeolite was synthesized according to teaching of EP-B1 -0.042.226. For the preparation of such a zeolite, the reaction mixture has the following molar composition: 60 SiO ₂ : 10.6 Na ₂ O: 5.27 NaBr: 1.5 Al ₂ O ₃ : 19.5 Hexa-Br ₂ : 2777 H ₂ O. Hexa-Br ₂ being 1, 6 Ν, Ν, Ν, Ν ', Ν', Ν'-hexamethylhexamethylene diammonium, bromine being the counter-ion. The reaction mixture is placed in an autoclave with stirring (300 rpm) for 5 days at 180 ° C.

This EU-1 zeolite is first subjected to so-called dry calcination at 550 ° C. under a flow of dry air for 24 hours so as to eliminate the organic structurant. The solid obtained is then subjected to four ion exchanges in a solution of 10N NH 4 NO 3 at about 100 ° C. for 4 hours for each exchange. The solid thus obtained is referenced EU-1 (1) and has an overall Si / Al atomic ratio = 15.3 and an atomic ratio Na / Al = 0.51%.

The zeolite EU-1 thus prepared has a BET surface area of 410 m ² / g.

Example 2 (non-compliant): Preparation of catalyst A comprising an EU-1 zeolite The EU-1 zeolite (1) obtained in Example 1 is then shaped by extrusion with a commercial alumina gel (Pural SB3 from Sasol) so as to obtain, after drying at a temperature of 100 ° C. for 1 night and calcination in dry air carried out at a temperature of 450 ° C. for 4 hours, the support S1 which contains, by weight, 8% of zeolite EU-1 and 92% alumina.

The support S1 has a specific surface area of 266 m ² / g.

The porosity characteristics of the matrix are:

- Specific surface = 233 m ² / g

- Pore volume = 0.51 cm ³ / g

- Average diameter of mesopores = 8 nm

This support S1 is subjected to anion exchange with hexachloroplatinic acid in the presence of hydrochloric acid as a competing agent, so as to deposit 0.3% by weight of platinum based on the weight of the catalyst. The wet solid is then dried at 120 ° C for 12 hours and calcined under a dry air flow rate at 500 ° C for one hour.

Catalyst A thus obtained contains, by weight, 8% of EU-1 zeolite, 91.7% of alumina and 0.3% of platinum.

Example 3 (in conformity): Preparation of catalyst B comprising an EU-1 zeolite

The EU-1 zeolite (1) obtained in Example 1 is then shaped by extrusion with a commercial alumina gel (Pural TH100 from Sasol) so as to obtain, after drying at a temperature equal to 100 ° C. for 1 night and calcination under dry air at a temperature equal to 450 ° C. for 4 hours, the support S 2 which contains, by weight, 8% of EU-1 zeolite and 92% of alumina.

The support S2 has a specific surface of 180 m ² / g

The porosity characteristics of the matrix are:

- Specific surface = 147 m ² / g

- Pore volume = 1, 02 cm ³ / g

- Mean diameter of the mesopores = 10 nm

This support S2 is subjected to anion exchange with hexachloroplatinic acid in the presence of hydrochloric acid as a competing agent, so as to deposit 0.3% by weight of platinum based on the weight of the catalyst. The wet solid is then dried at 120 ° C for 12 hours and calcined under a dry air flow rate at 500 ° C for one hour.

The catalyst B thus obtained contains, by weight, 8% of EU-1 zeolite, 91.7% of alumina and 0.3% of platinum.

EXAMPLE 4 Evaluation of the Catalytic Properties of Catalysts A and B in Isomerization of Ethylbenzene The charge to be isomerized, placed in contact with catalyst A and catalyst B, respectively, consists solely of ethylbenzene.

The operating conditions of the isomerization are as follows:

temperature: 400 ° C .;

total pressure: 9 bar (1 bar = 0.1 MPa);

hydrogen partial pressure: 7.5 bar.

charge: ethylbenzene

feeding space velocity, expressed in kilograms of feed introduced per kilogram of catalyst per hour, equal to 8.7 h ^-1, The catalytic properties of catalysts A and B for the isomerization of ethylbenzene are successively evaluated. Each of the catalysts is reduced under hydrogen for 4 hours at 480 ° C. before injection of the charge.

The catalysts were evaluated in terms of ethylbenzene conversion and selectivity to xylenes. The selectivity to xylenes is calculated using the yield of xylenes produced. The yield of xylenes is determined from the mass percentage of the xylenes produced, obtained by analysis of each effluent. The conversion of ethylbenzene is the percentage of ethylbenzene consumed. Table 1: Conversion of ethylbenzene and selectivity to xylenes on catalysts A, B

The results presented in Table 1 show that the catalyst B leads to a much better catalytic performance in terms of ethylbenzene conversion than that obtained using the catalyst A. Moreover, the catalyst B according to the invention leads to a selectivity in xylenes improved compared to that obtained with the catalyst A, consequently the catalyst B according to the invention leads to a yield of xylenes much higher than the yield of xylenes obtained with the comparative catalyst A, the yield of xylenes being the product of the conversion of ethylbenzene by selectivity to xylenes.

Claims

WO 2013/093222 PCT / FR2012 / 000474 »t H 18 CLAIMS

A process for isomerizing an aromatic section containing at least one aromatic compound having eight carbon atoms per molecule comprising contacting said section with at least one catalyst comprising at least one metal of group VIII of the periodic table. elements, at least one zeolite support comprising a zeolite chosen from zeolites of structure type EUO and MOR, taken alone or as a mixture and at least one matrix, such that the specific surface of the matrix in the zeolitic support of said catalyst is between and 200 m ² / g.

2. The method of claim 1 wherein the specific surface of the matrix in the zeolitic support of said catalyst is between 20 and 160 m ² / g.

3. The method of claim 1 or 2 wherein the specific surface of the matrix in the zeolitic support of said catalyst is between 50 and 160 m ² / g.

4. Method according to one of the preceding claims wherein said catalyst comprises 1 to 90% by weight of zeolite structural type EUO and / or MOR with respect to the total weight of the catalyst.

5. Method according to one of the preceding claims wherein the zeolite of structural type EUO is selected from zeolites EU-1, TPZ-3, ZSM-50 or their mixture.

6. Process according to claim 5, in which the zeolite of structure type EUO is zeolite EU-1.

7. Process according to one of the preceding claims, in which the zeolite of structural type MOR is Mordenite.

8. Process according to one of the preceding claims, in which the zeolite used in the zeolitic support of the catalyst is a mixture of zeolite EU-1 and Mordenite.

9. Method according to one of the preceding claims wherein said catalyst comprises a metal content (aux) Group VIII between 0.01 and 4% by weight relative to the total weight of the catalyst.

10. Method according to one of the preceding claims wherein said matrix is selected from clays, magnesia, aluminas, silicas, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, silica-aluminas and charcoal or a mixture of at least two of these compositions.

11. The method of claim 10 wherein the matrix is an alumina.

12. Method according to one of the preceding claims wherein said catalyst further comprises at least one metal selected from the metals of groups IIIA, IVA and VIIB, said (s) metal (s) in a lower content or equal to 2% by weight relative to the total weight of the catalyst.

Process for the preparation of the catalyst according to claims 1 to 12, comprising at least the following steps:

i) the synthesis of at least one zeolite of structure type EUO and / or O,

14. The method of claim 13 wherein the step i) of synthesis of the zeolite is followed by at least one calcination step and at least one ion exchange step carried out before the step ii) of implementation. form.

15. The method of claim 13 or 14 wherein the shaping step ii) is followed by a drying step carried out at a temperature between 100 and 150 ° C for a period of between 5 and 20 hours in an oven then a calcination step carried out at a temperature between 250 ° C and 750 ° C for a period of between 1 and 8 hours.

16. The process as claimed in one of the preceding claims, in which the isomerization process is carried out at a temperature of 300 ° C. to 500 ° C., a hydrogen partial pressure of 0.3 to 1.5 MPa, total pressure of 0.45 to 1, 9 MPa and a feed space velocity, expressed in kilogram of feed introduced per kilogram of catalyst and per hour of 0.25 to 30 h ^-1 .