FR3083134A1 - CATALYST BASED ON 1-VINYL-2-PYRROLIDONE AND / OR 1-ETHYL-2-PYRROLIDONE AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS - Google Patents

Abstract

The subject of the invention is a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element from group VIII, at least one element from group VIB, and an organic compound of formula (I) in which R1 is chosen from a vinyl group and an ethyl group.

Description

The invention relates to a catalyst additive using an organic compound, its preparation method and its use in the field of hydrotreating and / or hydrocracking.

Usually, the purpose of a hydrotreatment catalyst for hydrocarbon fractions is to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to produce a petroleum product with the required specifications (sulfur content, aromatic content, etc.). for a given application (automotive fuel, petrol or diesel, heating oil, jet fuel).

Conventional hydrotreatment catalysts generally comprise an oxide support and an active phase based on metals of groups VIB and VIII in their oxide forms as well as phosphorus. The preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, followed by drying and calcination which makes it possible to obtain the active phase in their oxide forms. Before their use in a hydrotreatment and / or hydrocracking reaction, these catalysts are generally subjected to sulfurization in order to form the active species.

The addition of an organic compound to the hydrotreatment catalysts to improve their activity has been recommended by those skilled in the art, in particular for catalysts which have been prepared by impregnation followed by drying without subsequent calcination. These catalysts are often called "additive dried catalysts".

Numerous documents describe the use of different ranges of organic compounds as additives, such as nitrogen-containing organic compounds and / or oxygen-containing organic compounds.

In the family of organic compounds containing oxygen, the use of optionally etherified mono, di- or polyalcohols is described in documents WO96 / 41848, WO01 / 76741, US4012340, US3954673, EP601722 and

W02005 / 035691.

There are also several patents which claim the use of carboxylic acids (EP1402948, EP0482817). In particular, in document EP0482817, citric acid, but also tartaric, butyric, hydroxyhexanoic, malic, gluconic, glyceric, glycolic, hydroxybutyric acids have been described. The specificity lies in the drying which must be carried out at a temperature below 200 ° C.

The prior art more rarely mentions additives comprising ester functions (EP1046424, W02006 / 077326).

Document US2014 / 0353213 describes the use of lactams, cyclic esters (of the lactone type) or cyclic ether (of the oxacycloalkanes type).

Whatever the compounds chosen, the modifications induced do not always make it possible to increase the performance of the catalyst sufficiently to meet the specifications concerning the sulfur and / or nitrogen contents of the fuels. In addition, it is often very complicated to carry out their industrial deployment as the methods are complex to implement.

Consequently, it is essential for catalyst manufacturers to find new hydrotreatment and / or hydrocracking catalysts with improved performance.

summary

The invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and at least one compound of formula (I)

O

- Ri (i) in which R 1 is chosen from a vinyl group and an ethyl group.

The Applicant has indeed found that the use of a compound of formula (I) as an organic additive on a catalyst containing at least one element of group VIII and at least one element of group VIB, makes it possible to obtain a hydrotreatment and / or hydrocracking catalyst showing improved catalytic performance.

Indeed, the catalyst according to the invention shows an increased activity compared to the non-additive catalysts and to the known dry additive catalysts. Typically, thanks to the increase in activity, the temperature necessary to reach a desired sulfur or nitrogen content (for example 10 ppm of sulfur in the case of a diesel charge, in ULSD or Ultra Low Sulfur Diesel mode depending on the Anglo-Saxon terminology) can be lowered. Likewise, stability is increased, since the cycle time is extended thanks to the necessary temperature reduction.

According to a variant, the content of element of group VIB is between 5 and 40% by weight expressed as metal oxide of group VIB relative to the total weight of the catalyst and the content of element of group VIII is between 1 and 10% by weight expressed as group VIII metal oxide relative to the total weight of the catalyst.

According to one variant, the molar ratio element of group VIII to element of group VIB in the catalyst is between 0.1 and 0.8.

According to a variant, the catalyst also contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P ₂ O ₅ relative to the total weight of the catalyst and the phosphorus molar ratio to the group element VIB in the catalyst is greater than or equal to 0.05.

According to a variant, the content of compound of formula (I) is between 1 and 45% by weight relative to the total weight of the catalyst.

Alternatively, the catalyst further contains an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur.

According to this variant, the organic compound (s) is (are) chosen from a compound comprising one or more chemical functions chosen from a carboxylic, alcohol, thiol, thioether, sulfone, sulfoxide function, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, amide or the compounds including a furan cycle or sugars.

According to this variant, the organic compound other than the compound of formula (I) is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5 (hydroxymethyl) -2 -furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2furaldehyde, ascorbic acid, butyl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, acetate 2-ethoxyethyl, 2butoxyethyl acetate, 2-hydroxyethyl acrylate le, 1,3-dimethyl-2-imidazolidinone, 1,5pentanediol, 1- (2-hydroxyethyl) -2-pyrrolidinone, 1- (2-hydroxyethyl) -2,5pyrrolidinedione, 5-methyl-2 (3H) -furanone, 1-methyl-2-piperidinone and 4 aminobutanoic acid.

Alternatively, the catalyst is at least partially sulfurized.

The invention also relates to processes for preparing the catalyst according to the invention as described in the claims.

The invention also relates to the use of the catalyst according to the invention in a process for hydrotreating and / or hydrocracking of hydrocarbon fractions.

In the following, groups of chemical elements are given according to CAS Classification (CRC Handbook of Chemistry and Physics, CRC press publisher, editor DR Lide, 81 ^th Edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.

Hydrotreatment is understood to mean reactions including in particular hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and aromatic hydrogenation (HDA).

Detailed description of the invention

Catalyst

The invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and at least one organic compound of formula (I) such as described below.

The catalyst according to the invention can be a fresh catalyst, that is to say a catalyst which has not been used as a catalyst before in a catalytic unit and in particular in hydrotreating and / or hydrocracking.

The catalyst according to the invention can also be a rejuvenated catalyst. By a rejuvenated catalyst is meant a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and / or hydrocracking and which has been subjected to at least one stage of partial or total elimination of coke for example by calcination (regeneration). This regenerated catalyst is then added with at least one compound of formula (I) to obtain the rejuvenated catalyst. This rejuvenated catalyst can contain one or more other organic additive (s) which can be added before, after or at the same time as the compound of formula (I).

The hydrogenating function of said catalyst, also called active phase, is provided by at least one element from group VIB and by at least one element from group VIII.

The preferred group VIB elements are molybdenum and tungsten. The preferred group VIII elements are non-noble elements and in particular cobalt and nickel. Advantageously, the hydrogenating function is chosen from the group formed by the combinations of the elements cobalt-molybdenum, nickelmolybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenumungsten.

In the case where a significant activity in hydrodesulfurization, or in hydrodenitrogenation and in hydrogenation of aromatics is desired, the hydrogenating function is advantageously ensured by the association of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum may also be advantageous. In the case of fillers of the distilled vacuum type or heavier, combinations of the cobalt-nickel-molybdenum type can be advantageously used.

The total content of elements of group VIB and of group VIII is advantageously greater than 6% by weight expressed as oxide relative to the total weight of the catalyst.

The content of group VIB element is between 5 and 40% by weight, preferably between 8 and 35% by weight, and more preferably between 10 and 30% by weight expressed as metal oxide of group VIB relative to the total weight of the catalyst.

The content of group VIII element is between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight expressed as metal oxide of group VIII relative to the weight total catalyst.

The molar ratio of group VIII element to group VIB element in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0.5.

The catalyst according to the invention advantageously also comprises phosphorus as a dopant. The dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase.

The phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed as P ₂ O ₅ relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight expressed as P2O5, and so very preferred between 0.3 and 11% by weight expressed as P2O5.

The phosphorus molar ratio on the element of group VIB in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.01 and 0.9 and very preferably between 0.15 and 0.8.

The catalyst according to the invention, with or without phosphorus, can advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.

When the catalyst contains boron or fluorine or a mixture of boron and fluorine, the content of boron or fluorine or a mixture of the two is preferably between 0.1 and 10% by weight expressed as boron oxide and / or in fluorine relative to the total weight of the catalyst, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight.

The catalyst according to the invention comprises a support based on alumina or silica or silica-alumina.

When the support for said catalyst is based on alumina, it contains more than 50% by weight of alumina relative to the total weight of the support and, in general, it contains only alumina or silica-alumina such as defined below.

Preferably, the support comprises alumina, and preferably extruded alumina. Preferably, the alumina is gamma alumina.

The alumina support advantageously has a total pore volume of between 0.1 and 1.5 cm ³ .g ' ¹ , preferably between 0.4 and 1.1 cm ³ .g' ¹ . The total pore volume is measured by mercury porosimetry according to standard ASTM D4284 with a wetting angle of 140 °, as described in the work Rouquerol F.; Rouquerol J.; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academic Press, 1999, for example using an Autopore III ™ model device from the Micromeritics ™ brand.

The specific surface of the alumina support is advantageously between 5 and 400 m ² .g ' ¹ , preferably between 10 and 350 m ² .g' ¹ , more preferably between 40 and 350 m ² .g ' ¹ . The specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above.

In another preferred case, the support for said catalyst is a silica-alumina containing at least 50% by weight of alumina relative to the total weight of the support. The silica content in the support is at most 50% by weight relative to the total weight of the support, most often less than or equal to 45% by weight, preferably less than or equal to 40%.

Sources of silicon are well known to those skilled in the art. By way of example, mention may be made of silicic acid, silica in powder form or in colloidal form (silica sol), tetraethylorthosilicate Si (0Et) 4.

When the support of said catalyst is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support and, in general, it contains only silica.

According to a particularly preferred variant, the support consists of alumina, silica or silica-alumina.

The support can also advantageously also contain from 0.1 to 50% by weight of zeolite relative to the total weight of the support. In this case, all sources of zeolite and all associated preparation methods known to those skilled in the art can be incorporated. Preferably, the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and more preferably, the zeolite is chosen from the group FAU and BEA, such as the zeolite Y and / or beta, and particularly preferably such as the USY and / or beta zeolite.

The support can also contain at least part of metal (metals) VIB and VIII, and / or at least part of dopant (s) including phosphorus and / or at least part of (s) organic compound (s) containing oxygen (the compound of formula (I) or other) and / or nitrogen and / or sulfur which have been introduced outside of the impregnations (introduced for example during support preparation).

The support is advantageously in the form of balls, extrudates, pellets or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.

The catalyst according to the invention also comprises at least one compound of formula (I)

O

- Ri (i) in which R 1 is chosen from a vinyl group and an ethyl group.

The compound of formula (I) is chosen from 1-vinyl-2-pyrrolidinone and 1 -ethyl-2pyrrolidinone which correspond respectively to the following formulas (a) and (b):

The presence of at least one compound of formula (I) on the catalyst makes it possible to observe an increased activity compared to the non-additive catalysts and to the known dry additive catalysts. The catalyst can comprise one or more compounds of formula (I), in particular two compounds of formula (I). The content of compound (s) of formula (I) on the catalyst according to the invention is between 1 and 45% by weight, preferably between 2 and 30% by weight, and more preferably between 3 and 25% by weight relative to the total weight of the catalyst. During the preparation of the catalyst requiring a drying step, the drying step or steps following the introduction of the compound of formula (I) is (are) carried out at a temperature below 200 ° C. so as to preferably preserve at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of the compound of formula (I) introduced calculated on the basis of the carbon remaining on the catalyst.

The compound of formula (I) can be obtained from the traditional chemical industry with generally high purities.

The catalyst according to the invention may comprise, in addition to the compound of formula (I), another organic compound or a group of organic compounds known for their role as additives. The function of additives is to increase the catalytic activity compared to non-additive catalysts. More particularly, the catalyst according to the invention may also comprise one or more organic compounds containing oxygen other than the compound of formula (I) and / or one or more organic compounds containing nitrogen and / or one or several organic compounds containing sulfur. Preferably, the catalyst according to the invention can also comprise one or more organic compounds containing oxygen other than the compound of formula (I) and / or one or more organic compounds containing nitrogen. Preferably, the organic compound contains at least 2 carbon atoms and at least one oxygen and / or nitrogen atom.

Generally, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or compounds including a furan cycle or sugars.

The organic compound containing oxygen can be one or more chosen from the compounds comprising one or more chemical functions chosen from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function or alternatively the compounds including a furanic cycle or sugars. For example, the organic compound containing oxygen can be one or more chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, a polyethylene glycol (with a molecular weight of between 200 and 1500 g / mol), propylene glycol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2 (2-methoxyethoxy) ethanol, triethylene glycoldimethyl ether, glycerol, acetophenone, 2,4-pentanedione, pentanone, l acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, γ-ketovaleric acid, a dialkyl succinate C1C4, and more particularly dimethyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, dibenzofuran, a crown ether, the orthophthalic acid, the glucose, fructose, sucrose, sorbitol, xylitol, yvalerolactone, 2-acetylbutyrolactone, propylene carbonate, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2furaldehyde, methyl 2-furoate, furfuryl alcohol (also known as furfuranol), acetate furfuryl, ascorbic acid, butyl lactate, butyl butyryllactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, methyl 3-methoxypropanoate, 2-ethoxyethyl acetate, l 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 3- ethyl-1,5pentanediol, 2,4-diethyl-1,5-pentanediol and 5-methyl-2 (3H) -furanone.

The nitrogen-containing organic compound may be one or more chosen from compounds comprising one or more chemical functions chosen from an amine or nitrile function. By way of example, the organic compound containing nitrogen can be one or more chosen from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexane, acetonitrile , octylamine, guanidine or a carbazole.

The organic compound containing oxygen and nitrogen may be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate, amine function , nitrile, imide, amide, urea or oxime. By way of example, the organic compound containing oxygen and nitrogen may be one or more chosen from the group consisting of acid

1,2 cyclohexanediaminetetraacetic, monoethanolamine (MEA), 1-methyl-2pyrrolidinone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- ( 2hydroxyethyl) ethylenediamine-N, N ', N'-triacetic (HEDTA), diethylenetriaminepentaacetic acid (DTPA), tetramethylurea, glutamic acid, dimethylglyoxime, bicine, tricine, 2-methoxyethyl cyanoacetate, 1,3dimethyl-2-imidazolidinone, 1- (2-hydroxyethyl) -2-pyrrolidinone, 1- (2hydroxyethyl) -2,5-pyrrolidinedione, 1-methyl-2-piperidinone, 1-acetyl-2azepanone, 1-vinyl-2-azepanone and 4-aminobutanoic acid.

The organic sulfur-containing compound may be one or more chosen from compounds comprising one or more chemical functions chosen from a thiol, thioether, sulfone or sulfoxide function. For example, the organic sulfur-containing compound may be one or more chosen from the group consisting of thioglycolic acid, 2,2'-thiodiethanol, 2-hydroxy-4methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxide derivative of a benzothiophene, methyl 3- (methylthio) propanoate and ethyl 3 (methylthio) propanoate.

Preferably, the organic compound contains oxygen, preferably it is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5 (hydroxymethyl) -2 -furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2furaldehyde, ascorbic acid, butyl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, acetate 2-ethoxyethyl, 2butoxyethyl acetate, 2-h acrylate ydroxyethyl, 1,3-dimethyl-2-imidazolidinone, 1,5pentanediol, 1- (2-hydroxyethyl) -2-pyrrolidinone, 1- (2-hydroxyethyl) -2,5 pyrrolidinedione, 5-methyl- 2 (3H) -furanone, 1-methyl-2-piperidinone and 4 aminobutanoic acid.

When it (s) is / are present, the content of organic compound (s) with additive function (s) containing oxygen (other than the compound of formula (I)) and / or nitrogen and / or sulfur on the catalyst according to the invention is between 1 and 30% by weight, preferably between 1.5 and 25% by weight, and more preferably between 2 and 20% by weight relative to the total weight of the catalyst.

Preparation process

The catalyst according to the invention can be prepared according to any mode of preparation of a supported catalyst additivated by an organic compound known to humans.

According to a first variant, the catalyst according to the invention can be prepared by implementing a step of impregnating said compound of formula (I), advantageously using a solution containing a solvent in which the compound of formula (I). According to this variant, the process for preparing said catalyst implements a step of adding said compound of formula (I) by the liquid phase. After impregnation, a drying step is then necessary to remove the solvent and / or the excess of the compound of formula (I) and thus release the porosity necessary for the use of the catalyst.

According to a second and third variant, the catalyst according to the invention can be prepared by implementing a step of adding said compound of formula (I) by the gas phase. These variants will be described later.

Introduction of the compound of formula (I) by liquid phase

According to the first variant, the catalyst according to the invention can be prepared according to a preparation process comprising the following steps:

a) contacting at least one compound comprising an element of group VIB, at least one compound comprising an element of group VIII, at least one compound of formula (I) and optionally phosphorus with a support based on alumina or of silica or of silica-alumina, or a regenerated catalyst containing a support based on alumina or of silica or of silica-alumina is brought into contact, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, with at least one compound of formula (I), so as to obtain a catalyst precursor,

b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without calcining it later.

According to this variant, the process for the preparation of a fresh catalyst will first be described, and then the process for the preparation of a rejuvenated catalyst.

I) Process for preparing a fresh catalyst

Step a) of contacting comprises several modes of implementation which are distinguished in particular by the time of introduction of the compound of formula (I) which can be carried out either at the same time as the impregnation of metals (co-impregnation ), either after the impregnation of metals (post-impregnation), or finally before the impregnation of metals (pre-impregnation). In addition, the contacting step can combine at least two modes of implementation, for example co-impregnation and post-impregnation. These different modes of implementation will be described later. Each mode, taken alone or in combination, can take place in one or more stages.

It is important to emphasize that the catalyst according to the invention during its preparation process does not undergo calcination after the introduction of the compound of formula (I) or any other organic compound containing oxygen and / or l nitrogen and / or sulfur in order to preserve at least in part the compound of formula (I) or any other organic compound in the catalyst. By calcination is meant here a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200 ° C.

However, the catalyst precursor can undergo a calcination step before the introduction of the compound of formula (I) or of any other organic compound containing oxygen and / or nitrogen and / or sulfur, in particular after l 'impregnation of elements of group VIB and VIII (post-impregnation) possibly in the presence of phosphorus and / or another dopant or during the regeneration of a catalyst already used. The hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called active phase, is then found in an oxide form.

According to another variant, the catalyst precursor does not undergo a calcination step after the impregnation of the elements of group VIB and VIII (post-impregnation), it is simply dried. The hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called active phase, is therefore not in an oxide form.

Whatever the mode of implementation, step a) of contacting generally comprises at least one impregnation step, preferably a dry impregnation step, in which the support is impregnated with a solution of impregnation comprising at least one element from group VIB, at least one element from group VIII, and optionally phosphorus. In the case of the co-impregnation described below in detail, this impregnation solution also comprises at least one compound of formula (I). The elements of group VIB and of group VIII are generally introduced by impregnation, preferably by dry impregnation or by impregnation in excess of solution. Preferably, all the elements of group VIB and of group VIII are introduced by impregnation, preferably by dry impregnation and this whatever the mode of implementation.

The elements of group VIB and of group VIII can also be introduced in part during the shaping of said support at the time of mixing with at least one alumina gel chosen as matrix, the rest of the hydrogenating elements then being introduced subsequently by impregnation . Preferably, when the elements of group VIB and of group VIII are introduced partially at the time of mixing, the proportion of element of group VIB introduced during this stage is less than 5% by weight of the total quantity of element of group VIB introduced on the final catalyst.

Preferably, the group VIB element is introduced at the same time as the group VIII element, whatever the mode of introduction.

The molybdenum precursors which can be used are well known to those skilled in the art. For example, among the sources of molybdenum, it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( H3PM012O40) and their salts, and optionally silicomolybdic acid (HUSiMo- ^ CUo) and its salts. The sources of molybdenum can also be heteropoly compounds of the Keggin, Lacunary Keggin, Substituted Keggin, Dawson, Anderson, Strandberg type, for example. Preferably, molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, lacunary Keggin or substituted Keggin type are used.

The tungsten precursors which can be used are also well known to those skilled in the art. For example, among the sources of tungsten, it is possible to use oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts, and possibly silicotungstic acid (H4S1W-12O40) and its salts. The sources of tungsten can also be heteropoly compounds of the Keggin, Keggin lacunar, substituted Keggin, Dawson type, for example. Ammonium oxides and salts such as ammonium metatungstate or heteropolyanions of the Keggin, Lacunary Keggin or substituted Keggin type are preferably used.

The precursors of group VIII elements which can be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of group VIII elements, for example, nickel hydroxycarbonate, carbonate or hydroxide cobalt are preferably used.

Phosphorus, when present, can be introduced in whole or in part by impregnation. Preferably, it is introduced by impregnation, preferably dry, using a solution containing the precursors of elements of group VIB and of group VIII.

Said phosphorus can advantageously be introduced alone or in admixture with at least one of the elements of group VIB and of group VIII, and this during any of the steps for impregnating the hydrogenating function if the latter is introduced several times. Said phosphorus can also be introduced, in whole or in part, during the impregnation of the compound of formula (I) if it is introduced separately from the hydrogenating function (case of the post- and pre-impregnation described later) and this in presence or absence of an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. It can also be introduced from the synthesis of the support, at any stage of the synthesis thereof. It can thus be introduced before, during or after the kneading of the chosen alumina gel matrix, such as for example and preferably aluminum oxyhydroxide (boehmite) precursor of alumina.

The preferred phosphorus precursor is orthophosphoric acid H3PO4, but its salts and esters such as ammonium phosphates are also suitable. The phosphorus can also be introduced at the same time as the element (s) of group VIB in the form of heteropolyanions of Keggin, Keggin lacunar, substituted Keggin or of Strandberg type.

The compound of formula (I) is advantageously introduced into an impregnating solution which, depending on the method of preparation, can be the same solution or a solution different from that containing the elements of group VIB and VIII, in a corresponding amount:

- a molar ratio of the compound of formula (I) per element (s) of group VIB of the catalyst precursor of between 0.01 to 5 mol / mol, preferably between 0.05 to 3 mol / mol, so preferred between 0.05 and 1.5 mol / mol and very preferably, between 0.1 and 1 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s), and

- a molar ratio of the compound of formula (I) per element (s) of group VIII of the catalyst precursor of between 0.02 to 17 mol / mol, preferably between 0.1 to 10 mol / mol, so preferred between 0.15 and 5 mol / mol and very preferably, between 0.2 and 3.5 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).

When several compounds of formula (I) are present, the different molar ratios apply for each of the compounds of formula (I) present.

Any impregnation solution described in the present invention can comprise any polar solvent known to a person skilled in the art. Said polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol, cyclohexanol, taken alone or as a mixture. Said polar solvent can also advantageously be chosen from the group formed by propylene carbonate, DMSO (dimethylsulfoxide), N-methylpyrrolidone (NMP) or sulfolane, taken alone or as a mixture. Preferably, a polar protic solvent is used. A list of common polar solvents and their dielectric constant can be found in the book "Solvents and Solvent Effects in Organic Chemistry", C. Reichardt, Wiley-VCH, 3rd edition, 2003, pages 472-474. Very preferably, the solvent used is water or ethanol, and particularly preferably, the solvent is water. In one possible embodiment, the solvent can be absent in the impregnation solution, in particular during a preparation in pre- or post-impregnation.

When the catalyst also comprises a dopant chosen from boron, fluorine or a mixture of boron and fluorine, the introduction of this (these) dopant (s) can be carried out in the same way as the introduction of the phosphorus described above at various stages of preparation and in various ways.

The boron precursors can be boric acid, orthoboric acid H3BO3, ammonium biborate or pentaborate, boron oxide, boric esters.

Boron can be introduced for example by a solution of boric acid in a water / alcohol mixture or also in a water / ethanolamine mixture. Preferably the boron precursor, if boron is introduced, is orthoboric acid.

The fluorine precursors which can be used are well known to those skilled in the art. For example, the fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. Fluorine can be introduced, for example, by impregnating an aqueous solution of hydrofluoric acid, or ammonium fluoride or alternatively ammonium bifluoride.

When the catalyst also comprises an additional additive (in addition to the compound of formula (I)) or a group of additional additives chosen from an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur, this can be introduced into the impregnation solution of step a).

The molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur per element (s) of group VIB on the catalyst is between 0.05 to 5 mol / mol, preferably between 0.1 to 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).

The molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur per compound of formula (I) is between 0.05 and 5 mol / mol, preferably between 0.1 and 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).

When several organic compounds containing oxygen and / or nitrogen and / or sulfur are present, the different molar ratios apply for each of the organic compounds present.

Advantageously, after each impregnation step, the impregnated support is left to mature. The maturation allows the impregnation solution to disperse homogeneously within the support.

Any maturation step described in the present invention is advantageously carried out at atmospheric pressure, in an atmosphere saturated with water and at a temperature between 17 ° C and 50 ° C, and preferably at room temperature. Generally a ripening period of between ten minutes and forty-eight hours and preferably between thirty minutes and five hours is sufficient. Longer durations are not excluded, but do not necessarily bring improvement.

In accordance with step b) of the preparation process according to the invention, the catalyst precursor obtained in step a) optionally matured is subjected to a drying step at a temperature below 200 ° C. without a subsequent calcination step.

Any drying step subsequent to the introduction of the compound of formula (I) described in the present invention is carried out at a temperature below 200 ° C, preferably between 50 and 180 ° C, preferably between 70 and 150 ° C and very preferably between 75 and 130 ° C.

The drying step is advantageously carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure, and preferably at atmospheric pressure. It is advantageously carried out in a crossed bed using air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is either air, or an inert gas such as argon or nitrogen. Very preferably, the drying is carried out in a crossed bed in the presence of nitrogen and / or air. Preferably, the drying step has a short duration of between 5 minutes and 4 hours, preferably between 30 minutes and 4 hours and very preferably between 1 hour and 3 hours. The drying is then carried out so as to preferably retain at least 30% of the compound of formula (I) introduced during an impregnation step, preferably this amount is greater than 50% and even more preferably, greater than 70 %, calculated on the basis of the carbon remaining on the catalyst. When an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur is present, the drying step is carried out so as to preferably preserve at least 30 %, preferably at least 50%, and very preferably at least 70% of the amount introduced calculated on the basis of the carbon remaining on the catalyst.

At the end of the drying step b), a dried catalyst is obtained, which is not subjected to any subsequent calcination step.

Co-impregnation

According to a first embodiment of step a) of the process for preparing the catalyst (fresh), the said compounds are deposited comprising the elements of group VIB, of group VIII, of the compound of formula (I) and optionally phosphorus on said support, by one or more co-impregnation steps, that is to say that said compounds comprising the elements of group VIB, of group VIII, the compound of formula (I) and optionally phosphorus are introduced simultaneously into said support (“co-impregnation”).

Post-impregnation

According to a second embodiment of step a) of the process for the preparation of the catalyst (fresh) according to the invention, at least one compound of formula (I) is brought into contact with a dried and optionally calcined impregnated support comprising at least one element from group VIB, at least one element from group VIII and optionally phosphorus, said support being based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor.

This second mode of implementation is a preparation by "post-impregnation" of the compound of formula (I).

The introduction of elements from group VIB and group VIII and optionally phosphorus onto the support can advantageously be carried out by one or more impregnations in excess of solution on the support, or preferably by one or more dry impregnations, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s), containing the metal precursor (s) and preferably the phosphorus precursor.

When several impregnation steps are carried out, each impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C. Each intermediate drying step, prior to the introduction of the compound of formula (I) can be followed by a calcination step. The calcination is generally carried out at a temperature between 200 ° C and 900 ° C, preferably between 250 ° C and 750 ° C. The calcination time is generally between 0.5 hour and 16 hours, preferably between 1 hour and 5 hours. It is generally carried out in air. Calcination makes it possible to transform the precursors of the metals of group VIB and VIII into oxides.

The compound of formula (I) can then advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art. Preferably, the compound of formula (I) is introduced in dry impregnation, in the presence or absence of a solvent as described above.

Preferably, the solvent in the impregnation solution is water, which facilitates implementation on an industrial scale.

The catalyst precursor which has been optionally matured is then subjected to a drying step at a temperature below 200 ° C. without a subsequent calcination step, as described above.

Prepregs

According to a third mode of implementation of step a) of the process for preparing the catalyst (fresh) according to the invention, at least one compound comprising an element from group VIB is brought into contact, at least one compound comprising an element of group VIII, optionally phosphorus with the support based on alumina or silica or silica-alumina which contains at least one compound of formula (I) so as to obtain a catalyst precursor.

This third embodiment is a preparation by "prepreg" of the compound of formula (I).

The compound of formula (I) can be introduced at any time during the preparation of the support, and preferably during the shaping or by impregnation on an already formed support.

If the introduction of the compound of formula (I) is chosen on the previously shaped support, then this can be carried out as indicated for the post-impregnation.

If one chooses the introduction during the shaping, preferably, said shaping is carried out by kneading extrusion, by tableting, by the method of coagulation in drop (oil-drop according to English terminology), by granulation on the turntable or by any other method well known to those skilled in the art. Very preferably, said shaping is carried out by extrusion kneading, the compound of formula (I) can be introduced at any time during extrusion kneading. The formed material obtained at the end of the shaping step then advantageously undergoes a heat treatment step at a temperature such that at least part of the compound of formula (I) remains present, preferably at a lower temperature. at 200 ° C.

The introduction of the elements of group VIB and of group VIII and optionally phosphorus can then advantageously be carried out by one or more impregnations.

The three methods described above can be used alone as described or combined to give rise to other hybrid preparation methods according to technical and practical constraints.

According to another alternative embodiment, the contacting according to step a) combines at least two contacting methods, for example the co-impregnation of the elements of group VIB and of group VIII and optionally phosphorus with a compound organic, followed by drying at a temperature below 200 ° C, then by post-impregnation of an organic compound which may be the same or different from that used for co-impregnation, given that at least one organic compound is a compound of formula (I).

II) Process for the preparation of a rejuvenated catalyst

The catalyst according to the invention can be a rejuvenated catalyst. Its preparation process includes the following steps:

a) contacting a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, with at least one compound of formula (I) so as to obtain a catalyst precursor,

b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without calcining it later.

The regenerated catalyst is a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and / or hydrocracking and which has been subjected to at least one step of partial or total elimination of coke for example by calcination (regeneration ). Regeneration can be carried out by any means known to those skilled in the art. Regeneration is generally carried out by calcination at temperatures between 350 and 550 ° C, and most often between 400 and 520 ° C, or between 420 and 520 ° C, or even between 450 and 520 ° C, lower temperatures at 500 ° C being often advantageous.

The regenerated catalyst contains a support based on alumina or silica or silica alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus in the respective proportions indicated above. Following the regeneration, the hydrogenating function comprising the elements of group VIB and of group VIII of the regenerated catalyst is in an oxide form. It can also contain dopants other than phosphorus, as described above.

Preferably, the contacting of step a) is carried out by impregnating the regenerated catalyst with an impregnating solution comprising at least one compound of formula (I) so as to obtain a catalyst precursor.

The compound of formula (I) can advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to a person skilled in the art in the same way as described above and with the molar ratios by element of group VIB or group VIII described above.

The operating conditions described above concerning the maturation and drying are of course applicable in the context of this latter embodiment.

Introduction of the compound of formula (I) by gas phase

According to two variants, the fresh catalyst according to the invention can be prepared by implementing a step of adding said compound of formula (I) by the gas phase as described in the French applications filed under national numbers 17 / 53.921 and 17 / 53,922. According to these variants, the process for the preparation of said catalyst does not involve a conventional step of impregnating said compound of formula (I). Consequently, it is not necessary to carry out a drying step after introduction of the compound of formula (I).

According to the first of the two variants, the process for preparing the catalyst according to the invention comprises the following steps:

i) at least one compound of formula (I) is deposited on a support based on alumina or silica or silica-alumina by implementing a step in which said support and the compound of formula ( I) in the liquid state and without physical contact between the support and the compound of formula (I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under conditions of pressure and duration such that a fraction of said compound of formula (I) is transferred in the gaseous state to the support, ii) at least one compound comprising an element of group VIB is brought into contact, at least one compound comprising an element of group VIII, and optionally phosphorus with the support based on alumina or silica or silica-alumina, iii) the solid obtained at the end of step ii) is dried, step i) being carried out before or after steps ii) and iii) or during step iii).

This variant is characterized in that the addition of the compound of formula (I) to the support is carried out without physical contact with the compound of formula (I) in the liquid state, that is to say without impregnation of the liquid support. The process is based on the principle of the existence of a vapor pressure of the compound of formula (I) which is generated by its liquid phase at a given temperature and pressure. Thus a part of the molecules of compound of formula (I) in the liquid state passes to the gaseous state (vaporization) and is then transferred (by gaseous route) to the support. This step i) of bringing together is carried out for a sufficient time to reach the targeted content of compound of formula (I) in the support.

Generally, step i) is carried out at an absolute pressure of between 0 and 1 MPa.

Preferably, the processing temperature of step i) is less than 200 ° C, preferably between 10 ° C and 150 ° C, more preferably between 25 ° C and 120 ° C.

According to the second of the two variants, the process for preparing the catalyst according to the invention comprises the following steps:

i ′) at least one compound of formula (I) is deposited on a support based on alumina or on silica or on silica-alumina by implementing a step in which is placed in a closed or open enclosure, the support with a porous solid containing at least one compound of formula (I), this step being carried out under temperature, pressure and duration conditions such that a fraction of said compound of formula (I) is transferred by gas from the solid porous to the support, ii) contacting at least one compound comprising an element of group VIB, at least one compound comprising an element of group VIII, and optionally phosphorus with the support based on alumina or silica or silica-alumina, iii) the solid obtained at the end of step ii) is dried, step i ') being carried out separately before or after steps ii) and iii).

According to this second variant, the addition of the compound of formula (I) consists in bringing into contact, in an open or closed enclosure, a first batch of porous solid rich in a compound of formula (I) which has been previously deposited on said solid in the liquid state, with a support (second batch of porous solid poor in said compound of formula (I)). The objective of this bringing together of porous solids is to allow a gaseous transfer of a part of the compound of formula (I) contained in the first batch of porous solid in the second batch of porous solid. According to the invention, the term poor in compound of formula (I) covers in particular the case where the second batch of porous solid is free of said compound of formula (I).

This second variant is also based on the principle of the existence of a vapor pressure of the compound of formula (I) at a given temperature and pressure. Thus, part of the molecules of compound of formula (I) of the batch of porous solid rich in compound of formula (I) passes in gaseous form (vaporization) and is then transferred (by gaseous route) to the support (solid poor in compound of formula (I)). According to the invention, the porous solid rich in compound of formula (I) plays the role of source in compound of formula (I) to enrich in compound of formula (I) the support (porous solid poor in compound of formula (I) ).

The porous solid rich in compound of formula (I) is advantageously a porous support, preferably a support based on alumina or silica or silica-alumina which can contain at least one element of group VIB, at least one element of group VIII, and possibly phosphorus.

The mass ratio (first batch of solid rich in compound of formula (I)) / (support or second batch of solid poor in compound of formula (I)) is a function of the porous distribution of the solids and of the objective in terms of target quantity of compound of formula (I) on the solids from step a) of contacting.

This mass ratio is generally less than or equal to 10, preferably less than 2 and even more preferably between 0.05 and 1, limits included. The step of bringing lots of porous solids together is preferably carried out under controlled temperature and pressure conditions and so that the temperature is lower than the boiling temperature of said compound of formula (I) to be transferred by way of gas. Preferably, the processing temperature is less than 150 ° C and the absolute pressure is generally between 0 and 1 MPa, preferably between 0 and 0.5 MPa and more preferably between 0 and 0.2 MPa . It will thus be possible to operate the step of bringing together in an open or closed enclosure, possibly with a control of the composition of the gas present in the enclosure.

When the step of bringing porous solids together takes place in an open enclosure, it will be ensured that the entrainment of the compound of formula (I) outside the enclosure is limited as much as possible. Alternatively, the step of bringing porous solids into contact can be carried out in a closed enclosure, for example in a container for storing or transporting the solid which is impermeable to gas exchange with the external environment.

The term “presence” designates the fact that the solids are present at the same time in the enclosure without there necessarily being physical contact of the two batches of solids.

The term rich in compound of formula (I) translates the fact that the solid contains more than 50% of the total amount of said compound of formula (I) used in step i), preferably at least 60%, of preferably at least 80%, preferably at least 90% and preferably 100%. According to one embodiment, at the start of step i '), the porous solid rich in compound of formula (I) contains 100% of the total amount involved in step i') and the support (second batch solid poor in compound of formula (I)) therefore contains 0% of the total amount of said compound of formula (I).

The two variants of catalyst preparation (fresh) by gas phase can be carried out according to two embodiments.

According to a first embodiment, the active phase is first introduced comprising at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII and optionally phosphorus on a porous support (step ii), then dried (step iii), then the dried support containing the active metallic phase and optionally phosphorus is treated according to step i) or i ') of bringing into contact with at least one compound of formula (I) in the liquid state or a porous solid containing at least one compound of formula (I) so as to provide a catalyst additive to said compound of formula (I). According to a variant of this first embodiment, step i) is carried out at the same time as step iii).

According to another embodiment, the support is first subjected to a step of adding the compound of formula (I) so as to provide a catalyst support additivated with the organic compound (step i) or i ')), which after an optional maturation phase, is sent to the impregnation step of the active phase (step ii) and then to drying (step iii).

In both embodiments, the porous support may in particular already contain an additional organic compound different from the compound of formula (I). Likewise, this additional organic compound can be introduced with the solution containing the active phase of the metals and optionally the phosphorus.

According to two other variants, the step of adding said compound of formula (I) by the gas phase can also be carried out on a regenerated catalyst.

According to these two variants, the process for preparing the catalyst according to the invention comprises the following steps:

i ”) at least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, by implementing a step in which said regenerated catalyst and at least one compound of formula (I) are brought into contact simultaneously in the liquid state and without physical contact between the regenerated catalyst and the compound of formula ( I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under pressure and duration conditions such that a fraction of said compound of formula (I) is transferred to l 'gaseous state with regenerated catalyst, or i' ”) at least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of the group VI B, at least one element from group VIII and optionally phosphorus, by implementing a step in which the regenerated catalyst is brought into contact, in a closed or open enclosure, with a porous solid containing at least one compound of formula (I ), this step being carried out under conditions of temperature, pressure and duration such that a fraction of said compound of formula (I) is transferred by gas from the porous solid to the regenerated catalyst.

The fresh or rejuvenated additive catalyst obtained by the introduction of the compound of formula (I) by gas phase as described above can also be treated by one or more subsequent stages in order to incorporate one or more other additional organic compounds different from the one used in step i) i '), i ”) or i'”). The incorporation of one or more other different additional organic compounds can be carried out by means of gas phase addition methods or by any other method known to those skilled in the art, for example by impregnating a solution containing the compound. additional organic.

sulphidation

Before its use for the hydrotreatment and / or hydrocracking reaction, it is advantageous to convert the catalyst obtained according to any of the modes of introduction described in the present invention into a sulfur catalyst in order to form its active species. This activation or sulfurization step is carried out by methods well known to those skilled in the art, and advantageously under a sulfo-reducing atmosphere in the presence of hydrogen and hydrogen sulfide.

At the end of step b) according to the different methods of preparing the process according to the invention, said catalyst obtained is therefore advantageously subjected to a sulphurization step, without an intermediate calcination step.

Said dried catalyst is advantageously sulfurized ex situ or in situ. Sulfurizing agents are H ₂ S gas, elemental sulfur, CS ₂ , mercaptans, sulfides and / or polysulfides, hydrocarbon fractions with boiling point below 400 ° C containing sulfur compounds or any other compound containing sulfur used for the activation of the hydrocarbon charges in order to sulfurize the catalyst. Said sulfur-containing compounds are advantageously chosen from alkyl disulfides such as for example dimethyl disulfide (DMDS), alkyl sulfides, such as for example dimethyl sulfide, thiols such as for example n- butylmercaptan (or 1-butanethiol) and tertiononylpolysulfide-type polysulfide compounds. The catalyst can also be sulfurized by the sulfur contained in the feed to be desulphurized. Preferably, the catalyst is sulfurized in situ in the presence of a sulfurizing agent and a hydrocarbon feed. Very preferably, the catalyst is sulfurized in situ in the presence of a hydrocarbon feed additive with dimethyl disulfide.

Hydrotreating and / or hydrocracking process

Finally, another object of the invention is the use of the catalyst according to the invention or prepared according to the preparation process according to the invention in hydrotreatment and / or hydrocracking processes of hydrocarbon fractions.

The catalyst according to the invention and having preferably undergone a sulfurization step beforehand is advantageously used for hydrotreatment and / or hydrocracking reactions of hydrocarbon feedstocks such as petroleum cuts, cuts derived from coal or hydrocarbons produced at from natural gas, optionally in mixtures or from a hydrocarbon fraction obtained from biomass and more particularly for hydrogenation, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation and hydrodemetallization reactions or hydroconversion of hydrocarbon feedstocks.

In these uses, the catalyst according to the invention and preferably having previously undergone a sulfurization step has an improved activity compared to the catalysts of the prior art. This catalyst can also advantageously be used during the pretreatment of catalytic cracking or hydrocracking charges, or the hydrodesulfurization of residues or the advanced hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel according to English terminology).

The fillers used in the hydrotreatment process are for example gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or more generally fillers from biomass, taken alone or as a mixture. The charges which are treated, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy charges, they most often also contain metals.

The operating conditions used in the processes implementing the hydrotreatment reactions of hydrocarbon feeds described above are generally the following: the temperature is advantageously between 180 and 450 ° C, and preferably between 250 and 440 ° C, the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume speed is advantageously between 0.1 and 20 h ' ¹ and preferably between 0.2 and 5 h' ¹ , and the hydrogen / charge ratio expressed by volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid charge is advantageously between 50 l / l to 5000 l / l and preferably 80 to 2000 l / l .

According to a first mode of use, said hydrotreatment process according to the invention is a hydrotreatment process, and in particular hydrodesulfurization (HDS) of a diesel cut carried out in the presence of at least one catalyst according to the invention . Said hydrotreatment process according to the invention aims to eliminate the sulfur compounds present in said diesel cut so as to achieve the environmental standards in force, namely an authorized sulfur content up to 10 ppm. It also makes it possible to reduce the aromatic and nitrogen contents of the diesel cut to be hydrotreated.

Said diesel cut to be hydrotreated according to the process of the invention contains from 0.02 to 5.0% by weight of sulfur. It is advantageously obtained from direct distillation (or straight run diesel according to Anglo-Saxon terminology), from a coking unit (coking according to Anglo-Saxon terminology), from a visbreaking unit (visbreaking according to Anglo-Saxon terminology) Saxon), a steam cracking unit (steam cracking according to English terminology), a hydrotreating and / or hydrocracking unit for heavier charges and / or a catalytic cracking unit (Fluid Catalytic Cracking according to Anglo-Saxon terminology). Said diesel cut preferably has at least 90% of the compounds whose boiling temperature is between 250 ° C and 400 ° C at atmospheric pressure.

The hydrotreatment process of said diesel cut according to the invention is implemented under the following operating conditions: a temperature between 200 and 400 ° C, preferably between 300 and 380 ° C, a total pressure between 2 MPa and 10 MPa and more preferably between 3 MPa and 8 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid feedstock, between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and an hourly volume speed (WH) of between 1 and 10 h ' ¹ , preferably between 2 and 8 h' ¹ . The WH corresponds to the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock to the volume of catalyst loaded into the reaction unit implementing the hydrotreatment process according to the invention . The reaction unit implementing the hydrotreatment process of said diesel cut according to the invention is preferably operated in a fixed bed, in a moving bed or in a bubbling bed, preferably in a fixed bed.

According to a second mode of use, said hydrotreatment and / or hydrocracking process according to the invention is a hydrotreatment process (in particular hydrodesulfurization, hydrodeazoation, hydrogenation of aromatics) and / or hydrocracking of a cut of vacuum distillate produced in the presence of at least one catalyst according to the invention. Said hydrotreatment and / or hydrocracking process, otherwise called hydrocracking or hydrocracking pretreatment process according to the invention aims, depending on the case, to remove the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to effect a pretreatment before conversion in catalytic cracking or hydroconversion processes, or in hydrocracking the distillate cut which would possibly have been pretreated before if necessary.

A wide variety of fillers can be treated by the hydrotreatment and / or hydrocracking processes of vacuum distillates described above. Generally they contain at least 20% volume and often at least 80% volume of compounds boiling above 340 ° C at atmospheric pressure. The feed can be, for example, vacuum distillates as well as feeds from aromatic extraction units from the lubricating oil bases or from solvent dewaxing with lubricating oil bases, and / or deasphalted oils , or the filler can be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the aforementioned fillers. In general, the charges have a boiling point T5 greater than 340 ° C at atmospheric pressure, and better still greater than 370 ° C at atmospheric pressure, that is to say that 95% of the compounds present in the charge have a point boiling above 340 ° C, and better still above 370 ° C. The nitrogen content of the feeds treated in the processes according to the invention is usually greater than 200 ppm by weight, preferably between 500 and 10 000 ppm by weight. The sulfur content of the feeds treated in the processes according to the invention is usually between 0.01 and 5.0% by weight. The charge may optionally contain metals (for example nickel and vanadium). The asphaltenes content is generally less than 3000 ppm by weight.

The hydrotreatment and / or hydrocracking catalyst is generally brought into contact, in the presence of hydrogen, with the fillers described above, at a temperature above 200 ° C, often between 250 ° C and 480 ° C, advantageously between 320 ° C and 450 ° C, preferably between 330 ° C and 435 ° C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the volume speed being included between 0.1 and 20.0 h ' ¹ and preferably 0.1-6.0 h' ¹ , preferably 0.2-3.0 h ' ¹ , and the amount of hydrogen introduced is such that the volume ratio liter of hydrogen / liter of hydrocarbon, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge, ie between 80 and 5,000 l / l and most often between 100 and 2,000 l / l. These operating conditions used in the processes according to the invention generally make it possible to achieve conversions by pass, into products having boiling points below 340 ° C at atmospheric pressure, and better still below 370 ° C at atmospheric pressure, higher at 15% and even more preferably between 20 and 95%.

The hydrotreatment and / or hydrocracking processes for vacuum distillates using the catalysts according to the invention cover the pressure and conversion domains ranging from mild hydrocracking to high pressure hydrocracking. Mild hydrocracking is understood to mean hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.

The catalyst according to the invention can be used alone, in one or more catalytic beds in a fixed bed, in one or more reactors, in a hydrocracking scheme known as one step, with or without liquid recycling of the unconverted fraction, or also in a hydrocracking scheme known as in two stages, optionally in combination with a hydrorefining catalyst situated upstream of the catalyst of the present invention.

According to a third mode of use, said hydrotreatment and / or hydrocracking process according to the invention is advantageously implemented as pretreatment in a catalytic cracking process in a fluidized bed (or FCC process for Fluid Catalytic Cracking according to the terminology Anglo-Saxon). The operating conditions of the pretreatment in terms of temperature range, pressure, hydrogen recycling rate, hourly volume speed are generally identical to those described above for the hydrotreatment and / or hydrocracking processes of vacuum distillates. The FCC process can be carried out in a conventional manner known to those skilled in the art under adequate cracking conditions in order to produce lower molecular weight hydrocarbon products. For example, a summary description of catalytic cracking can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pages 61 to 64.

According to a fourth mode of use, said hydrotreatment and / or hydrocracking process according to the invention is a hydrotreatment process (in particular hydrodesulfurization) of a gasoline fraction in the presence of at least one catalyst according to the invention. 'invention.

Unlike other hydrotreatment processes, hydrotreatment (in particular hydrodesulfurization) of gasolines must make it possible to respond to a double antagonistic constraint: ensuring deep hydrodesulfurization of gasolines and limiting the hydrogenation of the unsaturated compounds present in order to limit loss of octane number.

The feed is generally a cut of hydrocarbons having a distillation range between 30 and 260 ° C. Preferably, this cut of hydrocarbons is a cut of the gasoline type. Very preferably, the gasoline cut is an olefinic gasoline cut, for example from a catalytic cracking unit (Fluid Catalytic Cracking according to English terminology).

The hydrotreatment process consists in bringing the fraction of hydrocarbons into contact with the catalyst according to the invention and hydrogen under the following conditions: at a temperature between 200 and 400 ° C, preferably between 230 and 330 ° C, at a total pressure between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa, at an Hourly Volume Velocity (WH), defined as the volume flow rate of feed relative to the volume of catalyst, between 1 and 10 h ' ¹ , preferably between 2 and 6 h' ¹ and at a hydrogen / gasoline volume ratio between 100 and 600 Nl / I, preferably between 200 and 400 Nl / I.

The gasoline hydrotreatment process can be carried out in one or more reactors in series of the fixed bed type or of the bubbling bed type. If the process is implemented by means of at least two reactors in series, it is possible to provide a device for removing H ₂ S from the effluent from the first hydrodesulfurization reactor before treating said effluent in the second hydrodesulfurization reactor.

The examples which follow demonstrate the significant gain in activity on the catalysts prepared according to the process according to the invention compared to the catalysts of the prior art and specify the invention without however limiting its scope.

EXAMPLES

Example 1: Preparation of CoMoP catalysts on alumina without organic compound C1 and C2 (not in accordance with the invention).

On an alumina support having a BET surface of 230 m ² / g, a pore volume measured by mercury porosimetry of 0.78 ml / g and an average pore diameter of 11.5 nm defined as the median diameter by volume by mercury porosimetry and which is in the “extruded” form, cobalt, molybdenum and phosphorus are added. The impregnation solution is prepared by dissolving molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) in 11.8 g of an aqueous acid solution at 90 ° C phosphoric at 85% by weight. After dry impregnation, the extrudates are left to mature in an atmosphere saturated with water for 24 h at room temperature, then they are dried at 90 ° C. for hours. The dried catalyst precursor thus obtained is denoted C1. The calcination of the catalyst precursor C1 at 450 ° C for 2 hours leads to the calcined catalyst C2. The final metal composition of the catalyst precursor C1 and of the catalyst C2 expressed in the form of oxides and relative to the weight of the dry catalyst is then the following: Mo0 ₃ = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P ₂ O ₅ = 6.7 ± 0.1% by weight.

Example 2: Preparation of CoMoP catalysts on alumina C3 (not according to the invention) and C4 and C5 (according to the invention) by co-impregnation.

Cobalt, molybdenum and phosphorus are added to the alumina support described above in example 1 and which is in the "extruded" form. The impregnation solution is prepared by dissolving molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in 15.85 g of an aqueous acid solution at 90 ° C. 85% phosphoric and water. After homogenization of the above mixture, 38 g of citric acid were added before adjusting the volume of solution to the pore volume of the support by adding water. The molar ratio (citric acid) / Mo is equal to 1 mol / mol and that (citric acid) / Co is equal to 2.7 mol / mol. After dry impregnation, the extrudates are left to mature in a water-saturated atmosphere for 24 h at room temperature, then they are dried at 120 ° C for 16 hours. The dried catalyst with citric acid additive thus obtained is denoted C3. The final composition of the catalyst C3, expressed in the form of oxides and related to the weight of the dry catalyst is then the following: Mo0 ₃ = 19.6 ± 0.2% by weight, CoO = 3.7 ± 0.1% by weight and P ₂ O ₅ = 6.7 ± 0.1% by weight.

Catalyst C4 is prepared in a similar way to catalyst C3, but after homogenization of the metal solution containing cobalt, molybdenum and phosphorus, 1-vinyl-2-pyrrolidinone is added, again in a proportion of 1 mole per mol of molybdenum or 2.8 moles per mole of cobalt. Catalyst C4 was left to mature in a water saturated atmosphere for 12 hours at room temperature, then dried at 120 ° C for 16 hours. The final composition of catalyst C4, expressed in the form of oxides and related to the mass of dry catalyst is then as follows: Mo0 ₃ = 19.5 ± 0.2% by weight, CoO = 3.5 ± 0.1% by weight and P ₂ O ₅ = 6.6 ± 0.1% by weight.

Catalyst C5 is prepared analogously to catalyst C3, but after homogenization of the metal solution containing cobalt, molybdenum and phosphorus, 1-ethyl-2-pyrrolidinone is added, again in a proportion of 1 mole per mol of molybdenum or 2.8 moles per mole of cobalt. Catalyst C5 was left to mature in a water saturated atmosphere for 12 hours at room temperature, then dried at 120 ° C for 16 hours. The final composition of catalyst C5, expressed in the form of oxides and related to the mass of dry catalyst is then as follows: M0O3 = 19.5 ± 0.2% by weight, CoO = 3.7 ± 0.1% by weight and P2O5 = 6.6 ± 0.1% by weight.

Example 3: Preparation of the CoMoP catalyst on C6 alumina (according to the invention) by post-additivation.

18 g of catalyst precursor C1, described above in Example 1, which is in the “extruded” form, are impregnated with an aqueous solution containing 2.2 g of 1-vinyl-2-pyrrolidinone and whose volume is equal to pore volume of catalyst precursor C1. The amounts used are such that the amount of 1-vinyl-2-pyrrolidinone is 0.8 moles per mole of molybdenum (corresponding to 2.2 moles per mole of cobalt). The extrudates are left to mature in an atmosphere saturated with water for 16 h at room temperature. The catalyst precursor C6 is then dried at 120 ° C for 2 hours to give the catalyst C6. The final metal composition of catalyst C6 relative to the weight of the dry catalyst is: M0O3 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P ₂ O ₅ = 6.7 ± 0 , 1% by weight.

Example 4: Preparation of the CoMoP catalyst on C7 alumina (according to the invention) by post-additivation.

18 g of catalyst precursor C1, described above in Example 1, which is in the "extruded" form, are impregnated with an aqueous solution containing 2.2 g of 1-ethyl-2-pyrrolidinone and whose volume is equal to pore volume of catalyst precursor C1. The amounts used are such that the amount of 1-ethyl-2-pyrrolidinone is 0.8 moles per mole of molybdenum (corresponding to 2.2 moles per mole of cobalt). The extrudates are left to mature in an atmosphere saturated with water for 16 h at room temperature. The catalyst precursor 5 C7 is then dried at 120 ° C for 2 hours to give the catalyst

C7. The final metal composition of catalyst C7 relative to the weight of the dry catalyst is: M0O3 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P2O5 = 6.7 ± 0.1% weight.

EXAMPLE 5 Evaluation in Hydrodesulfurization (HDS) of Diesel Fuel of Catalysts 10 C1, C2 and C3 (not in accordance with the invention) and C4, C5, C6 and C7 (in accordance with the invention).

Catalysts C1, C2 and C3 (not in accordance with the invention) and C4, C5, C6 and C7 (in accordance with the invention) were tested in diesel HDS.

The characteristics of the diesel feedstock used are as follows: density 15 to 15 ° C = 0.8522 g / cm ³ , sulfur content = 1.44% by weight.

• Simulated distillation:

-PI: 155 ° C

- 10%: 247 ° C

- 50%: 315 ° C

- 90%: 392 ° C _ PF: 444 ° C

The test is carried out in an isothermal pilot reactor with a fixed bed traversed, the fluids flowing from bottom to top.

The catalyst precursors are previously sulfurized in situ at 350 ° C. in the pressure reactor by means of test gas oil to which 2% by weight of dimethyldisulphide is added.

The hydrodesulfurization tests were carried out under the following operating conditions: a total pressure of 7 MPa, a volume of catalyst of 30 cm ³ , a temperature of 330 to 360 ° C, with a hydrogen flow rate of 24 l / h and with a flow rate of 30 charges of 60 cm ³ / h.

The catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius relative to the catalyst C2 (comparative) chosen as reference: they correspond to the temperature difference to be applied to reach 50 ppm of sulfur in the effluent. A negative value 5 means that the sulfur content target is reached for a lower temperature and that there is therefore a gain in activity. A positive value means that the sulfur content target is reached at a higher temperature and therefore there is a loss of activity.

Table 1 clearly shows the gain on the catalytic effect provided by the 10 organic compounds according to the invention. In fact, the catalysts C4, C5, C6 and C7 (according to the invention) have a higher activity than those obtained for all the other catalysts evaluated.

The advantage of the catalysts according to the invention is therefore significant whatever their mode of introduction whereas they have a lower proportion of organic compound than the catalyst C3, with thus an intrinsic efficiency higher than that of the other compounds for which it is necessary to introduce a greater proportion of compound to observe a significant catalytic effect.

Table 1: Activities relating to iso-volume in hydrodesulfurization of diesel fuel of catalysts C1 and C3 (not in accordance with the invention) and C4, C5, C6 and C7 (in accordance with the invention) compared to catalyst C2 (not in conformity ).

Catalyst (comparative or according to the invention) Organic compound used and compound / Mo molar ratio Method of introducing the organic compound Activity H DS C1 (comp) nothingness Not applicable Base + 1.0 ° C C2 (comp) nothingness Not applicable Based C3 (comp) Citric acid - 1.0 mol / mol Mo Co-impregnation Base-2.9 ° C C4 (inv) 1-vinyl-2-pyrrolidinone 0.8 mol / mol Mo Co-impregnation Base -6.6 ° C C5 (inv) 1-ethyl-2-pyrrolidinone 0.8 mol / mol Mo Co-impregnation Base -5.9 ° C C6 (inv) 1-vinyl-2-pyrrolidinone 0.8 mol / mol Mo Post-additive Base -5.0 ° C C7 (inv) 1-ethyl-2-pyrrolidinone 0.8 mol / mol Mo Post-additive Base -4.5 ° C

Claims (14)

1. Catalyst comprising a support based on alumina or silica or silica alumina, at least one element of group VIII, at least one element of group VIB, and at least one compound of formula (I)

in which R1 is chosen from a vinyl group and an ethyl group. 2. Catalyst according to claim 1, in which the content of element of group VIB is between 5 and 40% by weight expressed as metal oxide of group VIB relative to the total weight of the catalyst and the content of element of group VIII is included between 1 and 10% by weight expressed as metal oxide of group VIII relative to the total weight of the catalyst. 3. Catalyst according to one of claims 1 to 2, wherein the molar ratio element of group VIII to element of group VIB in the catalyst is between 0.1 and 0.8. 4. Catalyst according to one of claims 1 to 3, which also contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P2O5 relative to the total weight of the catalyst and the phosphorus to molar ratio the element of group VIB in the catalyst is greater than or equal to 0.05. 5. Catalyst according to one of claims 1 to 4, in which the content of compound of formula (I) is between 1 and 45% by weight relative to the total weight of the catalyst. 6. Catalyst according to one of claims 1 to 5, which further contains an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. 7. Catalyst according to claim 6, in which the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate function, amine, nitrile, imide, oxime, urea, amide or the compounds including a furan cycle or sugars. 8. Catalyst according to claim 7, in which the organic compound other than the compound of formula (I) is chosen from γ-valerolactone, 2acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid, maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl- 2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde, 5-hydroxymethylfurfural, 2-acetylfuran, 5methyl-2-furaldehyde, ascorbic acid , butyl lactate, ethyl 3hydroxybutanoate, ethyl 3-ethoxypropanoate, 2ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1,3dimethyl-2-imidazolidinone , 1,5-pentanediol, 1- (2-hydroxyethyl) -2pyrrolidinone, 1- (2-hydroxyethyl) -2,5-pyrrolidinedione, 5-methyl-2 (3H) furanone, 1-methyl-2-piperidinone and 4-aminobutanoic acid. 9. Catalyst according to one of claims 1 to 8, being at least partially sulfurized. 10. Process for the preparation of a catalyst according to one of claims 1 to 9 comprising the following steps: a) contacting at least one compound comprising an element of group VIB, at least one compound comprising an element of group VIII, at least one compound of formula (I) and optionally phosphorus with a support based on alumina or of silica or of silica-alumina, or a regenerated catalyst containing a support based on alumina or of silica or of silica-alumina is brought into contact, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, with at least one compound of formula (I), so as to obtain a catalyst precursor, b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without calcining it later. 11. Process for the preparation of a catalyst according to one of claims 1 to 9 comprising the following steps: i) at least one compound of formula (I) is deposited on a support based on alumina or silica or silica-alumina by implementing a step in which said support and the compound of formula ( I) in the liquid state and without physical contact between the support and the compound of formula (I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under conditions of pressure and duration such that a fraction of said compound of formula (I) is transferred in the gaseous state to the support, ii) at least one compound comprising an element of the group is brought into contact VIB, at least one compound comprising an element from group VIII, and optionally phosphorus with the support based on alumina or silica or silica-alumina, iii) the solid obtained at the end of stage ii is dried ), step i) being carried out before or after steps ii) and iii) or during step iii). 12. Process for the preparation of the catalyst according to one of claims 1 to 9 comprising the following steps: i ′) at least one compound of formula (I) is deposited on a support based on alumina or on silica or on silica-alumina by implementing a step in which is placed in a closed or open enclosure, the support with a porous solid containing at least one compound of formula (I), this step being carried out under temperature, pressure and duration conditions such that a fraction of said compound of formula (I) is transferred by gas from the solid porous to the support, ii) contacting at least one compound comprising an element of group VIB, at least one compound comprising an element of group VIII, and optionally phosphorus with the support based on alumina or silica or silica-alumina, iii) the solid obtained at the end of step ii) is dried, step i ') being carried out separately before or after steps ii) and iii). 13. Method for preparing the catalyst according to one of claims 1 to 9 comprising the following steps: i ”) at least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, by implementing a step in which said regenerated catalyst and at least one compound of formula (I) are placed in the liquid state without physical contact between the regenerated catalyst and the compound of formula ( I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under pressure and duration conditions such that a fraction of said compound of formula (I) is transferred to l 'gaseous state with regenerated catalyst, or i' ”) at least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of the group VI B, at least one element from group VIII and optionally phosphorus, by implementing a step in which the regenerated catalyst is brought into contact, in a closed or open enclosure, with a porous solid containing at least one compound of formula (I ), this step being carried out under conditions of temperature, pressure and duration such that a fraction of said compound of formula (I) is transferred by gas from the porous solid to the regenerated catalyst. 14. Use of the catalyst according to one of claims 1 to 9 in a hydrotreatment and / or hydrocracking process of hydrocarbon fractions.