WO2020002138A1

WO2020002138A1 - C5 or c6 acid ester-based catalyst and use thereof in a hydroprocessing and/or hydrocracking process

Info

Publication number: WO2020002138A1
Application number: PCT/EP2019/066435
Authority: WO
Inventors: Bertrand Guichard
Original assignee: IFP Energies Nouvelles
Priority date: 2018-06-27
Filing date: 2019-06-21
Publication date: 2020-01-02
Also published as: FR3083140A1; FR3083140B1

Abstract

The invention relates to a catalyst comprising a substrate based on alumina or silica or silica-alumina, at least one element from group VIII, at least one element from group VIB and at least one C5 or C6 acid ester compound, additionally having a ketone chemical function, the two functions being 1 or 3 carbon atoms apart from one another. The invention also relates to the process for producing said catalyst and to the use thereof in a hydroprocessing and/or hydrocracking process.

Description

CATALYST BASED ON A C5 OR C6 ACID ESTER AND ITS USE IN A HYDROTREATMENT PROCESS AND / OR

HYDROCRACKING

The invention relates to a catalyst additivated using a compound of the ester type of a C5 or C6 acid and additionally containing a chemical function of the ketone type, its method of preparation and its use in the field of hydrotreating and / or hydrocracking.

Usually, the purpose of a hydrotreating 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, optionally, phosphorus. The preparation of these catalysts generally comprises a step of impregnating the metals and optionally phosphorus on the support, followed by drying and calcination allowing the active phase to be obtained in their oxide forms. Before their use in a hydrotreating 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. Several patents are thus found 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). In particular, patent EP1046424 describes compounds of the phthalate ester type and which therefore also have a benzoic cycle making the electronic behavior of the ester function different from that of a so-called linear ester. Application WO2006 / 077326 describes it symmetrical linear diesters between C3 and C20, such as dimethyl succinate.

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

Patent applications WO2016 / 064938, EP2650049 and JP2004313946A cover monoesters with a focus on C4 esters such as acetoacetates.

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

It is also noted that, to our knowledge, there is no catalyst which is prepared with a C5 or C6 acid ester which also contains a ketone function. On the contrary, the literature could even suggest that this type of molecule is of no interest for the catalytic performance of hydrotreatment catalysts.

Consequently, it emerges as essential, for catalyst manufacturers, to find new hydrotreating and / or hydrocracking catalysts with improved performance and which are, if possible, easily industrializable. 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 ester type of an acid. in C5 or C6 and further containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another.

In the remainder of the text, the expression “an ester type compound” or “an ester type compound of a C5 or C6 acid and also containing a chemical ketone type functional group” means a compound of ester type of a C5 or C6 acid and additionally containing a chemical ketone function in which the two functions are 1 or 3 carbon atoms apart.

The Applicant has in fact found that the use of a compound of the ester type of a C5 or C6 acid and also containing a chemical function of the ketone type as an organic additive on a catalyst containing at least one element of the group VIII and at least one element of group VIB, made 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 as the cycle time is extended by the necessary temperature reduction. According to a preferred variant, the ester-type compound is of formula (I), (II), (III) or (IV).

in which R1 is a linear or branched or cyclic hydrocarbon radical containing from 1 to 20 carbon atoms.

According to a preferred variant, the radical R1 is chosen from the methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) and butyl (-C ₄ H ₉ ) radical. According to a variant, the compound of ester type of a C5 or C6 acid and further containing a chemical function of ketone type is chosen from the methyl ester of 4 oxo-pentanoic acid, the ethyl ester of 4 oxo-acid pentanoic, propyl ester of 4 oxo-pentanoic acid, butyl ester of 4 oxo-pentanoic acid, methyl ester of 3-methyl-2-oxo-butanoic acid, ethyl ester of 3-methyl-2 -oxo-butanoic acid, propyl ester of 3-methyl-2-oxo-butanoic acid, butyl ester of 3-methyl-2-oxo-butanoic acid, methyl-2-oxo-valerate, ethyl -2-oxo-valerate, propyl-2-oxo-valerate, butyl-2- oxo-valerate, 3-oxo-cyclopentane acid methyl ester, 3-oxo acid ethyl ester -cyclopentane, propyl ester of 3-oxo-cyclopentane acid, butyl ester of 3-oxo-cyclopentane acid

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 one variant, the catalyst also contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P ₂ 0 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 ester type 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 ester type compound containing oxygen and / or nitrogen and / or sulfur. 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 g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3- oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl ) -2-furaldehyde or 5-HMF), 2-acetylfuran and 5-methyl-2-furaldehyde.

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

The catalyst according to the invention is a catalyst additive to at least one compound of ester type of a C5 or C6 acid and also containing a chemical function of ketone type. More particularly, the catalyst according to the invention comprises a support based on alumina or on silica or on silica-alumina, at least one element from group VIII, at least one element from group VIB and at least one compound of ester type d 'a C5 or C6 acid and containing in addition a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from each other.

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 step of partial or total elimination of coke for example by calcination (regeneration). This regenerated catalyst is then additivated at least with a compound of the ester type of a C5 or C6 acid and additionally containing a chemical function of the ketone type in order 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 ester compound.

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, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten.

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.

When it contains it, the phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed as P ₂ 0 ₅ relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight expressed in P ₂ 0 ₅ , and very preferably between 0.3 and 11% by weight expressed in P ₂ 0 ₅ .

In this case, 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 comprised between 0.08 and 1, preferably comprised between 0.1 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", Academie 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), tetraethylorthosil icate Si (OEt) 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 70% 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 ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type or the like) and / or nitrogen and / or sulfur which have been introduced outside of the impregnations (introduced for example during the preparation of the support).

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 ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type, the two functions being separated by 1 or 3 carbon atoms, one of the other.

According to a variant, the compound of ester type is a compound of ester type of a C5 or C6 monocarboxylic acid additionally containing, as the only additional chemical function, a function of ketone type. According to a preferred variant, the ester-type compound is of formula (I), (II), (III) or (IV).

According to a preferred variant, the radical R1 is a linear or branched hydrocarbon radical containing from 1 to 4 carbon atoms. Preferably, the radical R1 is chosen from the methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) and butyl (- C ₄ H ₉ ) radical.

According to a variant, the compound of the ester type of a C5 or C6 acid and also containing a chemical function of the ketone type is chosen from the methyl ester of 4 oxo-pentanoic acid, the ethyl ester of 4 oxo-acid pentanoic, butyl ester of 4 oxo-pentanoic acid, methyl ester of 3-methyl-2-oxo-butanoic acid, ethyl ester of 3-methyl-2-oxo-butanoic acid, butyl ester of 3-methyl-2-oxo-butanoic acid, methyl-2-oxo-valerate, ethyl-2-oxo-valerate, butyl-2-oxo-valerate, methyl ester of 3-oxo acid -cyclopentane, the ethyl ester of 3-oxo-cyclopentane acid and the butyl ester of 3-oxo-cyclopentane acid.

In a particularly preferred manner, the ester type compound is chosen from the esters of 4-oxo-pentanoic acid, in particular, the methyl ester, the ethyl ester or the butyl ester. The presence of the compound of ester type 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 ester type compounds, in particular two ester type compounds. The content of compound (s) 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 subsequent to the introduction of said compound 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 said compound introduced calculated on the basis of the carbon remaining on the catalyst.

The catalyst according to the invention may comprise, in addition to the ester compound, 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 ester type compound and / or one or more organic compounds containing nitrogen and / or one or more compounds organic containing sulfur. Preferably, the catalyst according to the invention may also comprise one or more organic compounds containing oxygen other than the ester type compound 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 the compounds including a furan cycle or sugars. The organic compound containing oxygen can be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function or alternatively compounds including a furanic cycle or sugars. By way of 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, acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, g-ketovaleric acid, a succinate of dialkyl C1 - C4, and more particularly dimethyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, dibenzofuran, a crown ether , orthophthalic acid, glucose, fructose, saccha rose, sorbitol, xylitol, y-valerolactone, 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-2-furaldehyde, methyl 2-furoate, furfuryl alcohol (also known as furfuranol) and furfuryl acetate .

The organic compound containing nitrogen can 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 can be one or more chosen from the group consisting of 1,2-cyclohexanediaminetetraacetic acid, monoethanolamine (MEA), 1- methyl-2-pyrrolidinone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) ethylenediamine-N, N ', N '-triacetic (HEDTA), diethylene triaminepentaacetic acid (DTPA), tetramethylurea, glutamic acid, dimethylglyoxime, bicine and tricine.

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

Preferably, the organic compound contains oxygen, preferably it is chosen from g-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, g-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3- oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl ) -2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde. When it (s) is / are present, the content of organic compound (s) with additive function (s) containing oxygen (other than the ester type compound) 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 method of preparation of a supported catalyst additive with an organic compound known to those skilled in the art.

According to a first variant, the catalyst according to the invention can be prepared by implementing a step of impregnating said compound of ester type, advantageously using a solution containing a solvent in which said compound is diluted. According to this variant, the process for the preparation of said catalyst implements a step of adding said compound by the liquid phase. After impregnation, a drying step is then necessary to remove the solvent and / or the excess of said compound 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 ester-type compound by the gas phase. These variants will be described later.

Introduction of the compound of ester type of a C5 or C6 acid and also containing a chemical function of ketone type 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 ester type of a C5 or C6 acid and further containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart, and possibly phosphorus with a support based on alumina or silica or silica-alumina, or a regenerated catalyst is placed in contact containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least an element of group VIII and optionally phosphorus, with at least one compound of ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms l ' one from the other, 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 be described first, and then the process for the preparation of a rejuvenated catalyst.

I) Process for preparing a fresh catalyst

Step a) of contacting comprises several methods of implementation which are distinguished in particular by the time of introduction of the compound of ester type which can be carried out either at the same time as the impregnation of the metals (co-impregnation ), either after the metal impregnation (post-impregnation), or finally before the metal impregnation (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 ester type compound (s) or any other organic compound containing oxygen and / or nitrogen and / or sulfur in order to at least partially preserve said compound 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 ester-type compound or any other organic compound containing oxygen and / or nitrogen and / or sulfur, in particular after impregnation elements from group VIB and VIII (post-impregnation) possibly in the presence of phosphorus and / or another dopant or during the regeneration of an already used catalyst. 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 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 ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type. 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 of the elements from group VIB and from group VIII are introduced by impregnation, preferably by dry impregnation, regardless of 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 group VIII are partly introduced at the time of kneading, the proportion of element of group VIB introduced during this stage is less than 5% by weight of the total amount of element of group VIB introduced into the final catalyst.

Preferably, the element of group VIB is introduced at the same time as the element of group VIII, 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 ( H ₃ PMoi20 ₄ o) and their salts, and optionally silicomolybdic acid (H ₄ SiMoi ₂ 0 ₄ o) 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 optionally silicotungstic acid (H ₄ SiWi ₂ 0 ₄ o) and its salts. The sources of tungsten can also be heteropoly compounds of the Keggin, Kungin Gap, Substituted Keggin, Dawson type, for example. Preferably used oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of Keggin, Keggin lacunar or substituted Keggin type.

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

Said phosphorus can advantageously be introduced alone or as a mixture 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 ester type compound if the latter is introduced separately from the hydrogenating function (case of the post- and pre-impregnation described later) and this in the presence or absence of an organic compound other than the ester type compound 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 H ₃ P0 ₄ , 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 the ester type of a C5 or C6 acid and also containing a chemical function of the ketone type is advantageously introduced into an impregnation solution which, depending on the method of preparation, may be the same solution or a solution different from that containing the elements of group VIB and VIII, in a corresponding quantity: at a molar ratio of the ester type compound per element (s) of the VIB group of the catalyst precursor of between 0.01 to 5 mol / mol, preferably between 0.05 to 3 mol / mol, preferably included 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

at a molar ratio of the ester type compound 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, preferably included 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 be advantageously 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 (s) dopant (s) can be carried out same as the introduction of phosphorus described above at various stages of the 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 ester type compound) or a group of additional additives chosen from an organic compound other than the ester type compound 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 ester type compound is between 0.05 and 5 mol / mol, preferably between 0.1 and 4 mol / mol, preferably included 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 subsequent calcination step.

Any drying step subsequent to the introduction of the compound of ester type of a C5 or C6 acid and further containing a chemical function of ketone type described in the present invention is carried out at a temperature below 200 ° C., preferably included 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 like 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 preferentially preserve at least 30% of the compound of the ester type of a C5 or C6 acid and also containing a chemical function of the ketone type introduced during an impregnation step, preferably this quantity 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 said compound according to the invention and 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 ester type of an acid C5 or C6 and further containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another, and optionally from phosphorus on said support, by one or more stages of co- impregnation, that is to say that said compounds comprising the elements of group VIB, of group VIII, the compound of ester type and optionally phosphorus are introduced simultaneously into said support (“co-impregnation”).

Post-impregnation

According to a second mode of implementation of step a) of the process for preparing the catalyst (fresh) according to the invention, at least one compound of the ester type of a C5 or C6 acid is brought into contact and containing besides a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart, 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 ester type compound.

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 ester-type compound, 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 ester type of a C5 or C6 acid and further containing a chemical function of ketone type 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 ester type compound 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 the preparation of 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 ester type of a C5 or C6 acid and further containing a chemical function of ketone type , the two functions being distant from 1 or 3 carbon atoms from one another, so as to obtain a catalyst precursor.

This third mode of implementation is a preparation by "prepreg" of the ester type compound.

The ester type compound 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 ester type compound is chosen on the previously shaped support, then this can be carried out as indicated for the post-impregnation.

If the introduction is chosen during the shaping, preferably, said shaping is carried out by kneading extrusion, by tableting, by the method of drop coagulation (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 ester type compound being able to be introduced at any time during kneading. extrusion. 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 ester-type compound remains present, preferably at a temperature below 200 ° C.

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

The three modes described above can be implemented alone as described or combined to give rise to other hybrid preparation modes 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 ester type of a C5 or C6 acid and also containing a chemical function of ketone type.

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 stages:

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 ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another, so as to obtain a precursor of catalyst, b) said catalyst precursor from step a) is dried at a temperature below 200 ° C., without calcining it subsequently.

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 from group VIB, at least one element from group VIII and optionally phosphorus in the respective proportions indicated above. Following regeneration, the hydrogenating function comprising the elements of group VIB and 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 impregnation of the regenerated catalyst with an impregnation solution comprising at least one compound of ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type so as to obtain a catalyst precursor.

The ester-type compound 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 per 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 ester type of a C5 or C6 acid and also containing a chemical function of ketone type 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 ester type of a C5 or C6 acid and also containing a chemical function of ketone type by the gas phase. as described in the French applications filed under the 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 ester type. Consequently, it is not necessary to carry out a drying step after introduction of the ester type compound.

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 ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart, on a support based on alumina or on silica or on silica-alumina by implementing a step in which said support and the compound of ester type of a C5 or C6 acid are simultaneously present and further containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from each other, in the liquid state and without physical contact between the support and said organic compound according to the invention in the state liquid, at a temperature below the boiling point of said compound and under conditions of pressure and duration such that a fraction of said compound is transferred in the gaseous state to the support,

ii) at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII, and optionally phosphorus are brought into contact 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 by the fact that the addition of the type compound to the support is carried out without physical contact with said organic compound in the liquid state, that is to say without impregnation of the support by the liquid. The process is based on the principle of the existence of a vapor pressure of the organic compound which is generated by its liquid phase at a given temperature and pressure. Thus, part of the molecules of compound of ester type 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 organic compound according to the invention 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 ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart , on a support based on alumina or silica or silica-alumina by implementing a step in which the support is placed in a closed or open enclosure with a porous solid containing at least one compound of the type ester of a C5 or C6 acid and also containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another, this step being carried out under temperature conditions, of pressure and duration such that a fraction of said ester type compound is transferred by gas from the porous solid 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 possibly t of 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 ester type compound consists in bringing into contact, in an open or closed enclosure, a first batch of porous solid rich in an ester type compound which has been previously deposited on said solid with liquid state, with a support (second batch of porous solid poor in said organic compound). The objective of this bringing together of porous solids is to allow a gaseous transfer of a part of the ester type compound contained in the first batch of porous solid in the second batch of porous solid. According to the invention, the term “poor in organic compound” covers in particular the case where the second batch of porous solid is free from said compound of ester type.

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

The porous solid rich in organic compound according to the invention 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 ester type of a C5 or C6 acid and also containing a chemical function of ketone type) / (support or second batch of solid poor in this same organic compound) is a function the porous distribution of the solids and the objective in terms of the quantity of ester-type compound targeted on the solids from step i ') 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 batches 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 ester type compound to be transferred by 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 into presence in an open or closed enclosure, with possibly 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 ester-type compound 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 "bringing together" 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 ester type compound of a C5 or C6 acid and additionally containing a chemical ketone type function" translates the fact that the solid contains more than 50% of the total amount of said ester type compound used. work in step i '), preferably at least 60%, 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 ester-type compound contains 100% of the total amount involved in step i') and the support (second batch of solid poor in this same compound) therefore contains 0% of the total amount of the said compound.

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 drying (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 ester type of a C5 or C6 acid and additionally containing a chemical function of ketone type in the liquid state or a porous solid containing at least one compound according to the invention so as to provide a catalyst additive with said compound. 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 ester type of a C5 or C6 acid and also containing a chemical function of ketone type so as to provide a support for catalyst additive of the organic compound (step i) or i ')), which after an optional maturation phase, is sent to the step of impregnating 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 ester type compound. 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 additional variants, the step of adding said ester-type compound 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 ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart , 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 ester-type compound of an acid are simultaneously brought into contact C5 or C6 and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from each other, in the liquid state and without physical contact between the regenerated catalyst and the compound organic according to the invention in the liquid state, at a temperature below the boiling temperature of the said compound and under pressure and duration conditions such that a fraction of the said compound is transferred in the gaseous state to the regenerated catalyst, or

i '”) at least one ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from the other, 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 brings together, in a closed or open enclosure, the regenerated catalyst with a porous solid containing at least one compound according to the invention, this step being carried out under conditions of temperature, pressure and duration such that a fraction of said compound is transferred gaseously from the porous solid to the regenerated catalyst.

The fresh or rejuvenated additive catalyst obtained by the introduction of the type compound 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 that 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 the gas phase addition processes 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 hydrotreating and / or hydrocracking reaction, it is advantageous to transform the catalyst obtained according to one of any 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 sulpho-reducing atmosphere in the presence of hydrogen and hydrogen sulphide. 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 sulfurization 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 cuts with a 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. 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.

Process of hvdrotraitement and / or hvdrocraquaqe

Finally, another subject 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 sulphurization 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, possibly in mixtures or from a hydrocarbon cut from biomass and more particularly for the hydrogenation, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallization or hydroconversion of hydrocarbon feedstock reactions.

In these uses, the catalyst according to the invention and having preferably previously undergone a sulfurization step exhibits 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 hydrodesulfurization of residues or 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 feedstocks 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 space velocity is advantageously between 0.1 and 20 h ¹ and preferably between 0.2 and 5 h ¹ , and the hydrogen / charge ratio expressed in 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 produced 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 English terminology), from a coking unit (coking according to English terminology), from a visbreaking unit (visbreaking according to English 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 volume ratio 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 in 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 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 feedstocks 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 charges treated in the processes according to the invention is usually between 0.01 and 5.0% by weight. The feed can optionally contain metals (for example nickel and vanadium). The asphaltenes content is generally less than 3000 ppm by weight.

The hydrotreating and / or hydrocracking catalyst is generally brought into contact, in the presence of hydrogen, with the feeds 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 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 5000 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 of 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 in a hydrocracking scheme called in two stages, optionally in combination with a hydrorefining catalyst located 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, the 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 being 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 N l / l, preferably between 200 and 400 N l / l.

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.

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

On an alumina support having a BET surface area 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 volume median diameter 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 (21.2 g) and cobalt hydroxide (5.09 g) in 7.51 g of an aqueous acid solution at 90 ° C. phosphoric at 85% by weight. 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 90 ° C. for 16 hours. The dried catalyst precursor thus obtained is noted A. The calcination of the catalyst precursor C1 at 450 ° C for 2 hours leads to the calcined catalyst B. The final metal composition of the catalyst precursor A and of the catalyst B expressed in the form of oxides and relative to the weight of the dry catalyst is then the following: M0O3 = 19.8 ± 0.2% by weight, CoO = 3.9 ± 0.1% by weight and P ₂ 0 ₅ = 4.2 ± 0.1% weight.

Example 2: Preparation of catalysts C0M0P on alumina C (not in accordance with the invention) and D (in accordance with 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 (28.34 g) and cobalt hydroxide (6.51 g) in 10.05 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 C. The final composition of catalyst C, expressed in the form of oxides and relative to the weight of the dry catalyst is then as follows: M0O3 = 20.3 ± 0.2% weight, CoO = 3.9 ± 0.1% by weight and P ₂ 0 ₅ = 4.3 ± 0.1% by weight.

Catalyst D according to the invention is prepared as follows. Cobalt, molybdenum and phosphorus are added to the alumina support described in Example 1 and which is in the "extruded" form. An impregnation solution was prepared by dissolving molybdenum oxide (39.2 g) and cobalt hydroxide (9.32 g) in 13.75 g of an aqueous solution of phosphoric acid at 90 ° C. 85% and water. After homogenization of the above mixture, a solution of ethyl 4-oxopentanoate was added to the solution at 0.8 mole per mole of molybdenum, ie 2.2 moles per mole of cobalt, to give the catalyst precursor D. The volume of the solution was adjusted to the pore volume of the support by adding water before impregnation and after homogenization of the mixture (the latter tending to demix slightly over time). After dry impregnation, the extrudates of catalyst precursor were left to mature in an atmosphere saturated with water for 24 hours at room temperature, then dried at 120 ° C. for 16 hours. The final composition of catalyst D expressed in the form of oxides and relative to the weight of the dry catalyst is then as follows: M0O3 = 19.8 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P ₂ 0 ₅ = 4.1 ± 0.1% by weight.

C0M0P on alumina E (conforms to

10 g of catalyst precursor A described above in example 1 are impregnated, which is in the "extruded" form with an aqueous solution containing 1.42 g of ethyl 4-oxo-pentanoate and whose volume is equal to pore volume of catalyst precursor C1. The amounts used are such that the amount of ethyl 4-oxo-pentanoate 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 8 h at room temperature. The catalyst precursor E is then dried at 110 ° C. for 2 hours to give the catalyst E. The final metal composition of catalyst E relative to the weight of the dry catalyst is: M0O3 = 19.7 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P ₂ 0 ₅ = 4.3 ± 0.1% by weight.

Example 4 Preparation of the catalyst C0M0P on alumina F (according to the invention) by introduction of an organic compound in the vapor phase after the impregnation of the metals.

In a closed enclosure are placed 3.0 g of ethyl 3-methyl-2-oxobutanoate contained in a crystallizer. 10 g of catalyst precursor A are introduced into the same closed enclosure and placed on a stainless steel grid so that the liquid ethyl 3-methyl-2-oxobutanoate is not in physical contact with the catalyst precursor A The closed enclosure is placed in an oven at 140 ° C for 3 hours 30 minutes. 11.9 g of catalyst F are thus obtained after bringing the catalyst precursor A into contact with the ethyl compound 3-methyl-2-oxobutanoate in the liquid state. The amount of ethyl 3- methyl-2-oxobutanoate thus transferred to the catalyst is such that the ethyl 3-methyl-2-oxobutanoate / Mo molar ratio is 1.0 mol per mol of molybdenum (corresponding to 2, 5 moles per mole of cobalt). The final metal composition of catalyst F relative to the weight of the dry catalyst is: Mo0 ₃ = 19.8 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P ₂ 0 ₅ = 4.2 ± 0.1% by weight.

Example 5 Evaluation in Hydrodesulfurization (HDS) of Azole Catalysts

A, B and C (not in accordance with the invention) and D, E, F (in accordance with the invention)

Catalysts A, B and C (not in accordance with the invention) and D, E, F (in accordance with the invention) were tested in diesel HDS.

The characteristics of the diesel feedstock used are as follows: density at 15 ° C = 0.8672 g / cm ³ , sulfur content = 1.04% by weight.

• Simulated distillation:

- PI: 158 ° C

- 10%: 242 ° C

- 50%: 331 ° C

- 90%: 390 ° C

- MP: 436 ° C

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

The catalyst precursors are previously sulfurized in situ at 350 ° C. in the reactor under pressure using diesel fuel from the test to which 2% by weight of dimethyldisulphide is added.

The hydrodesulfurization tests were carried out under the following operating conditions: a total pressure of 5 MPa, a volume of catalyst of 30 cm ³ , a temperature of 330 to 350 ° C, with a hydrogen flow rate of 20 l / h and with a charge rate 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 catalyst B (comparative) chosen as reference: they correspond to the temperature difference at apply to reach 50 ppm sulfur in the effluent. A negative value 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 for a higher temperature and therefore there is a loss of activity.

Table 1 clearly shows the gain on the catalytic effect provided by the organic compounds according to the invention. Indeed, the catalysts D, E, F (according to the invention) exhibit activities higher than those obtained for all the other catalysts evaluated. The compounds of ester type of a C5 or C6 acid and also containing a chemical function of ketone type therefore provide a gain in catalytic activity whatever their mode of introduction: co-impregnation with metals, introduction after impregnation of metals (post-impregnation) in solution and introduction into the gas phase after impregnation of the metals.

The advantage of the catalysts according to the invention is significant when they have a lower proportion of organic compound than catalyst C, 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 A and C (not in accordance with the invention) and D, E, F (in accordance with the invention) relative to catalyst B (not in conformity).

Claims

1. Catalyst comprising a support based on alumina or on silica or on silica-alumina, at least one element of group VIII, at least one element of group VIB, and at least one compound of ester type of a C5 acid or C6 and further containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another.

2. Catalyst according to claim 1, in which the ester-type compound is of formula (I), (II), (III) or (IV).

3. Catalyst according to the preceding claim, in which the radical R1 is chosen from the methyl, ethyl, propyl and butyl radical.

4. Catalyst according to one of the preceding claims, in which the ester-type compound is chosen from the methyl ester of 4 oxo-pentanoic acid, the ethyl ester of 4 oxo-pentanoic acid, the butyl ester of 4 oxo - pentanoic acid, the methyl ester of 3-methyl-2-oxo-butanoic acid, the ethyl ester of 3-methyl-2-oxo-butanoic acid, the butyl ester of 3-methyl-2-oxo-acid butanoic, methyl-2-oxo-valerate, ethyl-2-oxo-valerate, butyl-2-oxo-valerate, methyl ester of 3-oxo-cyclopentane acid, ethyl ester of l 3-oxo-cyclopentane acid and the butyl ester of 3-oxo-cyclopentane acid.

5. Catalyst according to one of the preceding claims, 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 between 1 and 10% by weight expressed as metal oxide of group VIII relative to the total weight of the catalyst.

6. Catalyst according to one of the preceding claims, in which the molar ratio of group VIII element to group VIB element in the catalyst is between 0.1 and 0.8.

7. Catalyst according to one of the preceding claims, which also contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P ₂ 0 ₅ relative to the total weight of the catalyst and the phosphorus molar ratio on the element of group VIB in the catalyst is greater than or equal to 0.05.

8. Catalyst according to one of the preceding claims, in which the content of compound of ester type is between 1 and 45% by weight relative to the total weight of the catalyst.

9. Catalyst according to claim 1, which also contains an organic compound other than the ester type compound containing oxygen and / or nitrogen and / or sulfur.

10. Catalyst according to the preceding claim, in which 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, amide or the compounds including a furan cycle or sugars.

11. Catalyst according to claims 9 or 10, in which the organic compound other than the ester type compound is chosen from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra- acid acetic, maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, dimethylformamide, 1 - methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde, 5-hydroxymethylfurfural, 2-acetylfuran and 5-methyl-2-furaldehyde.

12. Catalyst according to one of the preceding claims, being at least partially sulfurized.

13. Process for the preparation of a catalyst according to one of claims 1 to 12 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 the ester type of a C5 or C6 acid and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart, and optionally phosphorus with a support based on alumina or silica or silica-alumina, or contact is made a regenerated catalyst containing a support based on alumina or on silica or on 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 ester type a C5 or C6 acid and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from each other, 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.

14. Method for preparing a catalyst according to one of claims 1 to 12 comprising the following steps: i) at least one ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart, on a support based on alumina or on silica or on silica-alumina by implementing a step in which said support and the ester type compound are simultaneously present in the liquid state and without physical contact between the support and the compound of ester type in the liquid state, at a temperature below the boiling temperature of the compound of ester type and under conditions of pressure and duration such that a fraction of said compound of ester type of an acid in C5 or C6 and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from each other, is transferred in the gaseous state to the support,

ii) at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII, and optionally phosphorus are brought into contact 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).

15. Process for the preparation of the catalyst according to one of claims 1 to 12 comprising the following steps:

i ') at least one ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart , on a support based on alumina or silica or silica-alumina by implementing a step in which the support is placed in a closed or open enclosure with a porous solid containing at least one compound of the type ester of a C5 or C6 acid and also containing a chemical function of ketone type, the two functions being distant from 1 or 3 carbon atoms from one another, this step being carried out under temperature conditions, of pressure and duration such that a fraction of said ester-type compound is transferred by gas from the porous solid to the support, ii) at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII, and optionally phosphorus are brought into contact 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).

16. Process for the preparation of the catalyst according to one of claims 1 to 12 comprising the following steps:

i ”) at least one ester-type compound of a C5 or C6 acid is deposited and further containing a chemical function of ketone type, the two functions being 1 to 3 carbon atoms apart , 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 ester-type compound of a C5 or C6 acid and simultaneously containing a chemical function of ketone type are placed in the presence simultaneously, the two functions being 1 or 3 carbon atoms apart on the other, in the liquid state and without physical contact between the regenerated catalyst and said compound of ester type in the liquid state, at a temperature below the boiling temperature of the compound of ester type and under conditions pressure and duration such that a fraction of said ester type compound is transferred in the gaseous state to the regenerated catalyst, or

i '”) at least one ester-type compound of a C5 or C6 acid is deposited and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from the other, 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 is placed in the presence, in a closed or open enclosure, of the catalyst regenerated with a porous solid containing at least one compound of ester type of a C5 or C6 acid and also containing a chemical function of ketone type, the two functions being 1 or 3 carbon atoms apart from each other, this step being carried out under temperature, pressure and duration conditions such that a fraction of said ester type compound is gaseous transfer from the porous solid to the regenerated catalyst.

17. Use of the catalyst according to one of claims 1 to 12 in a hydrotreatment and / or hydrocracking process of hydrocarbon fractions.