A CATALYST BASED ON AN ORGANIC COMPOUND AND ITS USE IN A HYDROTREATING AND / OR HYDROCRACKING PROCES

专利摘要:
The subject of the invention is 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 an organic compound of formula (I) in which R 1, R 2, R 3, R 4 and R 5 is chosen from a hydrogen atom or a hydroxyl radical or a hydrocarbon radical comprising from 1 to 12 carbon atoms which may further comprise at least one oxygen atom and R 6 is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms may further comprise at least one oxygen atom, a methacryloyl radical, an acryloyl radical or an acetyl radical. The invention also relates to the process for preparing said catalyst and its use in a hydrotreatment and / or hydrocracking process.
公开号:FR3035008A1
申请号:FR1657308
申请日:2016-07-28
公开日:2016-10-21
发明作者:Pierre-Louis Carrette
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] The invention relates to a catalyst additive to an organic compound, its method of preparation and its use in the field of hydrotreatment and / or hydrocracking. Usually, a hydrotreating catalyst for hydrocarbon cuts is intended to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to bring a petroleum product to the required specifications (sulfur content, aromatic content, etc.) for a given application (motor fuel, gasoline or diesel, heating oil, jet fuel). It may also be pretreat this load in order to remove impurities or hydrogenate before subjecting it to various transformation processes to modify the physicochemical properties, such as for example reforming processes, d hydrocracking of vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or under vacuum. The composition and use of the hydrotreatment catalysts are particularly well described in the article by B. S Clausen, HT Topsee, and FE Massoth, from Catalysis Science and Technology, Volume 11 (1996), Springer- Verlag. The tightening of automobile pollution standards in the European Community (Official Journal of the European Union, L76, 22 March 2003, Directive 2003/70 / EC, pages L76 / 10-L76 / 19) has forced refiners to reduce very sharply sulfur content in diesel fuels and gasoline (up to 10 parts per million weight (ppm) of sulfur as of January 1, 2009, compared to 50 ppm as of January 1, 2005). In addition, refiners are forced to use loads that are more and more resistant to hydrotreatment processes because the crudes are heavier and therefore contain more and more impurities, on the other hand, because of the increase in conversion processes in refineries. Indeed, these generate cuts more difficult to hydrotreat than the cuts directly from the atmospheric distillation. More difficult to hydrotreat, usually means higher operating temperatures to achieve the same sulfur content in the effluent, and consequently cycle times that can be reduced. These fillers 3035008 2 require catalysts having hydrodesulphurizing and hydrogenating functions which are greatly improved over traditional catalysts. In addition, conversion processes such as catalytic cracking or hydrocracking use catalysts having an acid function, which makes them particularly sensitive to the presence of nitrogen impurities, and particularly basic nitrogen compounds. It is therefore necessary to use pretreatment catalysts of these fillers so as to remove these compounds. Conventional hydrotreatment catalysts generally comprise an oxide support and an active phase based on Group VIB and VIII metals in their oxide forms as well as phosphorus. The preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, followed by drying and calcination to obtain the active phase in their oxide forms. Prior to their use in a hydrotreatment and / or hydrocracking reaction, these catalysts are generally sulphurized 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, especially for catalysts which have been prepared by impregnation followed by drying without subsequent calcination. These catalysts are often called "dried catalyst additives".
[0002] Numerous documents describe the use of different ranges of organic compounds as additives, such as organic compounds containing nitrogen and / or organic compounds containing oxygen. A family of compounds now well known in the literature relates to chelating nitrogen compounds (EP0181035, EP1043069 and US6540908) with, for example, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, diethylenetriamine or nitrilotriacetic acid. (NTA). In the family of organic compounds containing oxygen, the use of optionally etherified mono-, di- or polyalcohols is described in the documents 3035008 3 WO96 / 41848, W001 / 76741, US4012340, US3954673, E P601722, and WO2005 / 035,691. There are also several patents that claim the use of carboxylic acids (EP1402948, EP0482817). In particular, in 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 conducted at a temperature below 200 ° C. The prior art more rarely refers to additives comprising ester functions (EP1046424, WO2006 / 077326).
[0003] US2013 / 267409 discloses the use of an organic compound of formula R1COCH2COR2 wherein R1 and R2 are the same or different and are selected from a group consisting of C1 to C12 alkyl, C6 to C12 allyl allyl, C1-C12 alkoxy and hydroxy. Whatever the compounds chosen, the induced modifications do not always make it possible to increase sufficiently the performance of the catalyst to meet the specifications relating to the sulfur and / or nitrogen contents of the fuels. In addition, it is often very difficult to proceed with their industrial deployment as the methods are complex to implement. Therefore, it is essential for catalyst manufacturers to find new hydrotreatment and / or hydrocracking catalysts with improved performance. SUMMARY The invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and an organic compound of formula (I) 3035008 Wherein R 1, R 2, R 3, R 4 and R 5 are chosen from a hydrogen atom, a hydroxyl radical or a hydrocarbon radical comprising from 1 to 12 carbon atoms, which may comprise from 1 to 5 carbon atoms. in addition to at least one oxygen atom and R6 is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms which may further comprise at least one oxygen atom, a methacryloyl radical, an acryloyl radical; or an acetyl radical. The applicant has indeed found that the use of the compound of formula (I) as an organic additive on a catalyst containing at least one element of group VIII and at least one element of group VIB, made it possible to obtain a catalyst. hydrotreating and / or hydrocracking process exhibiting improved catalytic performance. Indeed, the catalyst according to the invention shows an increased activity compared to the catalysts not additivés and dried catalysts additives known.
[0004] 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 fuel charge, in ULSD or Ultra Low Sulfur Diesel mode according to Anglo-Saxon terminology) can be lowered. In the same way, the stability is increased because the cycle time is prolonged thanks to the necessary temperature reduction.
[0005] The catalyst according to the present invention is in addition easier to prepare because of a high solubility of the compound of formula (I) in water or any other protic polar solvent. According to one variant, the organic compound of formula (I) is chosen from a derivative of 2-alkoxyethyl 3-oxobutanoates, in which R1 is a methyl group, R2, R3, R4 and R5 is a hydrogen atom and R6 is chosen from a hydrogen atom 3035008, a hydrocarbon radical comprising from 1 to 12 carbon atoms may further comprise at least one oxygen atom, a methacryloyl radical, an acryloyl radical or an acetyl radical. According to one variant, the organic compound of formula (I) is chosen from 2-methoxyethyl 2-methyl-3-oxopropanoate, 2-methoxyethyl 2-methyl-3-oxopropanoate, 2-hydroxyethyl 3-oxobutanoate, 3- 2-hydroxypropyl oxobutanoate, 2-methoxyethyl 3-oxobutanoate, 2ethoxyethyl 3-oxobutanoate, 2-propoxyethyl 3-oxobutanoate, 2-acetyloxyethyl 3-oxobutanoate, 2-acryloyloxyethyl 3-oxobutanoate, 210 methacryloyloxyethyl 3-oxobutanoate, 1- (2-hydroxyethyl) -3-methyl propanedioate, 1-ethyl-3- (2-hydroxyethyl) propanedioate, 1,3-bis (2-hydroxyethyl) propanedioate , 1- (2-methoxyethyl) -3-methyl propanedioate, 1-ethyl-3- (2-methoxyethyl) propanedioate, 1- (2-ethoxyethyl) -3-methyl propanedioate and mono (2-methoxyethyl) -propanedioate. hydroxyethyl) ester of propanedioic acid.
[0006] According to one variant, the content of group VIB element is between 5 and 40% by weight expressed as Group VIB metal oxide relative to the total weight of the catalyst, the content of Group VIII element is between 1 and 10% 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 additionally contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P2O5 relative to the total weight of the catalyst and the phosphorus ratio on the Group VIB element in the catalyst. is greater than or equal to 0.05.
[0007] According to one variant, the content of organic compound of formula (I) is between 1 and 45% by weight relative to the total weight of the catalyst. According to one variant, the catalyst additionally contains an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. According to this variant, this organic compound is preferably chosen from a compound comprising one or more chemical functional groups chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide. Preferably, it is chosen from triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, dimethylformamide and N-methylpyrrolidone. propylene carbonate, bicine, or tricine. According to a variant, the catalyst is at least partially sulphurized.
[0008] The invention also relates to the process for preparing said catalyst comprising the following steps: a) at least one component of a group VIB element, at least one component of a group VIII element, an organic compound is brought into contact with each other; of formula (I) and optionally phosphorus with a support based on alumina or silica or silica-alumina, or is brought into contact a regenerated catalyst containing a support based on alumina or silica or silica- alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus with an organic compound of formula (I), so as to obtain a catalyst precursor, b said catalyst precursor from step a) is dried at a temperature below 200 ° C., without subsequently calcining it. According to one variant, step a) is the following step: a ') a support is impregnated with base of alumina or silica or silica-alumina by at least one solution containing at least one group VIB element, at least one group VIII element, an organic compound of formula (I) and optionally phosphorus so as to obtain a catalyst precursor.
[0009] According to another variant, step a) comprises the following steps: a1) impregnating a support based on alumina or silica or silica-alumina with at least one solution containing at least one group VIB element, at least one group VIII element and optionally phosphorus to obtain an impregnated support, a2) the impregnated support obtained in step a1) is dried at a temperature below 200 ° C to obtain a dried impregnated support, and optionally calcine the dried impregnated support to obtain a calcined impregnated support, a3) the impregnated dried and optionally calcined support obtained in step a2) is impregnated with an impregnating solution comprising at least one organic compound of formula (I) to obtain a catalyst precursor, a4) optionally, the catalyst precursor obtained in step a3) is allowed to mature. According to another variant, step a) comprises the following steps: a ') is prepared a support comprising at least one organic compound of formula (I) and optionally at least a portion of the phosphorus, a2') is impregnated the support obtained in step a1 ') by an impregnating solution comprising at least one group VIB element, at least one group VIII element and optionally phosphorus so as to obtain a catalyst precursor, a3') optionally, is allowed to mature the catalyst precursor obtained in step a2 ').
[0010] According to another variant, step a) comprises the following steps: anon contacts by co-impregnation a solution containing at least one element of group VIB, at least one element of group VIII, at least one organic compound containing oxygen and / or nitrogen and / or sulfur, and optionally phosphorus with a support based on alumina or silica or silica-alumina so as to obtain an impregnated support, a2 "). Dry the impregnated support from step a1 ") at a temperature below 200 ° C, without subsequently calcining it to obtain a dried impregnated support, a3"). The dried impregnated support resulting from step a2 is brought into contact with each other. ") with a solution of at least one organic compound containing oxygen and / or nitrogen and / or sulfur identical to or different from that used in step a1" ") so as to obtain a catalyst precursor , 10 a4 ") optionally, the catalyst precursor is allowed to mature it is obtained in step a3 "), and at least one of the organic compounds of step a1" ") or of step a3" ") is an organic compound of formula (I). According to a variant, when it is desired to prepare the catalyst according to the invention from a regenerated catalyst, stage a) of the preparation process comprises the following steps: a) a regenerated catalyst containing a support is impregnated based on alumina or silica or silica-alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus with an impregnating solution comprising at least one the organic compound of the formula (I) is reduced to at least one organic compound of the formula (I) so that the catalyst precursor obtained in step (a) is allowed to mature.
[0011] According to one variant, the molar ratio of the organic compound of formula (I) per element (s) of group VIII is between 0.1 and 5.0 mol / mol.
[0012] The invention also relates to the use of the catalyst according to the invention or prepared according to the preparation process according to the invention in a hydrotreatment and / or hydrocracking process of hydrocarbon cuts. In the following, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC Press, editor in chief D. R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification. Hydrotreatment is understood to mean reactions including hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and aromatic hydrogenation (HDA). Detailed description of the invention Catalyst The catalyst according to the invention is a catalyst additive to an organic compound.
[0013] More particularly, the catalyst according to the invention comprises 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 an organic compound of formula (I ). The catalyst according to the invention may be a fresh catalyst, that is to say a catalyst which has not been used as catalyst previously in a catalytic unit and in particular in hydrotreatment and / or hydrocracking. The catalyst according to the invention may also be a rejuvenated catalyst. A rejuvenated catalyst is understood to mean a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreatment and / or hydrocracking and which has been subjected to at least one calcination step in order to burn the coke (regeneration). This regenerated catalyst is then additive with at least one organic compound of formula (I) to obtain the rejuvenated catalyst. This rejuvenated catalyst may contain one or more other organic additive (s) which may be added before, after or at the same time as the organic compound of formula (I).
[0014] The hydrogenating function of said catalyst, also called the active phase, is provided by at least one group VIB element and at least one group VIII element. 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 cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten elements. In the case where an important activity in hydrodesulfurization, or hydrodenitrogenation and hydrogenation of the aromatics is desired, the hydrogenating function is advantageously provided by the combination of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum may also be advantageous. In the case of vacuum or heavier distillate fillers, cobalt-nickel-molybdenum combinations may be advantageously used. The total content of Group VIB and Group VIII elements 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 Group VIB metal oxide with respect to the total weight. catalyst. The element content of group VIII 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 Group VIII metal oxide with respect to 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.
[0015] The catalyst according to the invention advantageously also comprises phosphorus as a dopant. The dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase. The phosphorus content in said catalyst is preferably between 0.1% and 20% by weight expressed as P2O5, preferably between 0.2 and 15% by weight expressed as P2O5, and very preferably between 0.3 and 11% by weight. weight expressed in P2O5. The phosphorus molar ratio on the element of the group VIB in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably of between 0.08 and 1, preferably of between 0.01 and 0.01. and 0.9 and most preferably between 0.15 and 0.8. The catalyst according to the invention may advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine. When the catalyst contains boron, the boron content is preferably between 0.1 and 10% by weight expressed as boron oxide, preferably between 0.2 and 7 weight, and very preferably between 0.2 and 5% by weight. When the catalyst contains fluorine, the fluorine content is preferably between 0.1 and 10% by weight expressed as fluorine, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight. % weight When the catalyst contains boron and fluorine, the total content of boron and fluorine is preferably between 0.1 and 10% by weight expressed as boron oxide and fluorine, 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.
[0016] When the support of said catalyst is based on alumina, it contains more than 50 of alumina and, in general, it contains only alumina or silica-alumina as defined below.
[0017] 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 cm3g-1, preferably between 0.4 and 1.1 cm3g-1. The total pore volume is measured by mercury porosimetry according to ASTM D4284 with a wetting angle of 140 °, as described in Rouquerol F; Rouquerol J .; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academic Press, 1999, for example by means of an Autopore III TM model apparatus of the Microméritics ™ 10 brand. The specific surface of the alumina support is advantageously between 5 and 400 m2.g-1, preferably between 10 and 350 m2.g-1, more preferably between 40 and 350 m2.e. The specific surface is determined in the present invention by the method B.E.T according to ASTM D3663, method described in the same work cited above.
[0018] In another preferred case, the support of said catalyst is a silica-alumina containing at least 50% by weight of alumina. The silica content in the support is at most 50% by weight, most often less than or equal to 45% by weight, preferably less than or equal to 40%. Silicon sources are well known to those skilled in the art. For example, silicic acid, silica in powder form or in colloidal form (silica sol), tetraethylorthosilicate Si (OEt) 4. When the support of said catalyst is based on silica, it contains more than 50% by weight of silica and, in general, it contains only silica. According to a particularly preferred variant, the support consists of alumina, silica or silica-alumina. The support may also advantageously contain from 0.1 to 50% by weight of zeolite. In this case, all the zeolite sources and all the associated preparation methods known to those skilled in the art can be incorporated.
[0019] Preferably, the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and, preferably, the zeolite is chosen from the group FAU and BEA, such as zeolite Y and / or beta. . In some particular cases, the support may also contain at least a portion of metal (s) VIB and VIII, and / or at least a portion of dopant (s) whose phosphorus and / or at least a part of organic compound (s) containing oxygen (the organic compound of formula (I) or other) and / or nitrogen and / or sulfur which have been introduced outside impregnations (introduced for example during the preparation of the support).
[0020] The support is advantageously in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates whose specific shape may result from a crushing step. The catalyst according to the invention also comprises an organic compound which corresponds to the following formula (I): ## STR1 ## Wherein R 1, R 2, R 3, R 4 and R 5 are chosen from a hydrogen atom, a hydroxyl radical or a hydrocarbon radical comprising from 1 to 12 carbon atoms which may also comprise at least one atom. oxygen and R6 is selected from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms which may further comprise at least one oxygen atom, a methacryloyl radical -C (O) C (CH2) CH3, an acryloyl radical -C (O) CHCH2 or an acetyl radical -C (O) CH3. Preferably, R 1, R 2, R 3, R 4 and R 5 are chosen from a hydrogen atom or a hydrocarbon radical comprising from 1 to 12 carbon atoms which may further comprise at least one oxygen atom and R 6 is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms may further comprise at least one oxygen atom, a methacryloyl radical - C (O) C (CH2) CH3, an acryloyl radical -C (0) CHCH2 or an acetyl radical -C (O) CH3.
[0021] Preferably, R1, R2, R3, R4 and R5 are chosen from a hydrogen atom or a hydrocarbon radical comprising from 1 to 4 carbon atoms and R6 is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to to 12 carbon atoms which may furthermore comprise at least one oxygen atom, a methacryloyl radical -C (O) C (CH2) CH3, an acryloyl radical -C (O) CHCH2 or an acetyl radical -C (O) CH3. Preferably, the organic compound is chosen from a derivative of 2-alkoxyethyl 3-oxobutanoates, in which R 1 is a methyl group, R 2, R 3, R 4 and R 5 is a hydrogen atom and R 6 is chosen from an atom of hydrogen, a hydrocarbon radical comprising from 1 to 12 carbon atoms which may also comprise at least one oxygen atom, a methacryloyl radical -C (O) C (CH 2) CH 3, an acryloyl radical -C (O) CHCH 2 or an acetyl radical -C (O) CH3. The compound of formula (I) may be chosen from 2-methoxy-2-methyl-3-oxopropanoate, 2-ethoxyethyl-2-methyl-3-oxopropanoate, 2-hydroxyethyl 3-oxobutanoate and 2-hydroxyethyl-3-oxobutanoate. hydroxypropyl, 2-methoxyethyl 3-oxobutanoate, 2-ethoxyethyl 3-oxobutanoate, 2-propoxyethyl 3-oxobutanoate, 2-acetyloxyethyl 3-oxobutanoate, 2-acryloyloxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, 1- (2-hydroxyethyl) -3-methyl propanedioate, 1-ethyl-3- (2-hydroxyethyl) propanedioate, 1,3-bis (2-hydroxyethyl) propanedioate ), 1- (2-methoxyethyl) -3-methylpropanedioate, 1-ethyl-3- (2-methoxyethyl) propanedioate, 1- (2-ethoxyethyl) -3-methylpropanedioate and mono (2-hydroxyethyl) ester of propanedioic acid. Preferably, the compound of formula (I) is chosen from 2-methoxyethyl 3-oxobutanoate and 2-methacryloyloxyethyl 3-oxobutanoate.
[0022] 2-Methoxyethyl-3-oxobutanoate and 2-methacryloyloxyethyl-3-oxobutanoate respectively correspond to the following formulas (a) and (b) described below: oooo cK'D (a) / / 0 (B) The presence of the organic compound of formula (I) on the catalyst makes it possible to observe an increased activity relative to the non-additive catalysts and to the known dried additivated catalysts. The content of organic compound of formula (I) on the catalyst according to the invention is between 1 and 45% by weight, preferably between 2 and 30% by weight, and more preferably between 3 and 25% by weight with respect to total weight of the catalyst. During the preparation of the catalyst, the drying step (s) consecutive to the introduction of the organic compound of formula (I) is (are) carried out at a temperature below 200 ° C. so as to preserve preferably at least 30%, preferably at least 50%, and most preferably at least 70% of the amount of the organic compound of formula (I) introduced calculated on the basis of the carbon remaining on the catalyst. The catalyst according to the invention may comprise, in addition to the organic compound of formula (I), another organic compound or a group of organic compounds known for their role as additives. The function of the additives is to increase the catalytic activity compared to the non-additive catalysts. More particularly, the catalyst according to the invention may further comprise one or more oxygen-containing organic compounds other than the organic compound of formula (I) and / or one or more organic compounds containing nitrogen and / or one or more organic compounds containing sulfur. Preferably, the catalyst according to the invention may further comprise one or more oxygen-containing organic compounds other than the organic compound of formula (I) and / or one or more nitrogen-containing organic compounds. Preferably, the organic compound contains at least 2 carbon atoms and at least one oxygen and / or nitrogen atom.
[0023] In general, the organic compound is chosen from a compound comprising one or more chemical functional groups chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide. Preferably, the organic compound is selected from a compound having two alcohol functions and / or two carboxylic functions and / or two ester functions and / or at least one amide function. The oxygen-containing organic compound may be one or more selected from compounds having one or more chemical functions selected from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function.
[0024] By way of example, the oxygen-containing organic compound may be one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (with a molecular weight between 200 and 1500). g / mol), propylene glycol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, triethylene glycol dimethyl ether, glycerol, acetophenone, 2,4-pentanedione, pentanone, acetic acid, maleic acid, malic acid, malonic acid, malic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, succinate C1-C4 dialkyl, methyl acetoacetate, ethyl acetoacetate, dibenzofuran, crown ether, orthophthalic acid, glucose and propylene carbonate.
[0025] The nitrogen-containing organic compound may be one or more of the compounds having one or more chemical functions selected from an amine or nitrile function. By way of example, the nitrogen-containing organic compound may be one or more selected from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. acetonitrile, octylamine, guanidine or carbazole. The organic compound containing oxygen and nitrogen may be one or more selected from compounds having one or more chemical functional groups selected from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate function. amine, nitrile, imide, amide, urea or oxime. For example, the organic compound containing oxygen and nitrogen may be one or more selected from the group consisting of 1,2-cyclohexane diamine tetraacetic acid, monoethanolamine (MEA), N-methylpyrrolidone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), tetramethylurea, glutamic acid, dimethylglyoxime, bicine or tricine, or a lactam. The sulfur-containing organic compound may be one or more selected from compounds having one or more chemical functions selected from thiol, thioether, sulfone or sulfoxide function. For example, the sulfur-containing organic compound may be one or more selected from the group consisting of thioglycolic acid, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxidized derivative of a benzothiophene.
[0026] Preferably, the organic compound contains oxygen, most preferably it is selected from triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, and the like. citric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, bicine, or tricine.
[0027] When (s) is / are present, the content of the organic compound (s) containing oxygen-containing additive function (s) (other than the organic compound of formula (I)) and / or of the 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 weight total catalyst.
[0028] Preparation Process The catalyst according to the invention may be prepared according to any method of preparation of a supported catalyst additive with an organic compound known to those skilled in the art.
[0029] The catalyst according to the invention may be prepared according to a preparation process comprising the following steps: a) at least one component of a group VIB element is brought into contact with at least one component of a group VIII element , an organic compound of formula (I) and optionally phosphorus with a support based on alumina or silica or silica-alumina, or a regenerated catalyst containing a support based on alumina or silica is brought into contact or silica-alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus with an organic compound of formula (I), so as to obtain a precursor catalyst, b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without subsequently calcining it will be described firstly the process for preparing a fresh catalyst, then thereafter the 15th trial de preparation of a rejuvenated catalyst. Process for the Preparation of a Fresh Catalyst Step a) of bringing into contact comprises several modes of implementation which are distinguished in particular by the moment of introduction of the organic compound of formula (I) which can be carried out either at the same time the impregnation of the metals (co-impregnation), either after the impregnation of the metals (post-impregnation), or finally before the impregnation of the metals (pre-impregnation). In addition, the contacting step can combine at least two modes of implementation, for example co-impregnation and post-impregnation. These different modes of implementation will be described later. Each mode, taken alone or in combination, may take place in one or more steps. 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 organic compound of formula (I) or any other organic compound containing oxygen and / or nitrogen and / or sulfur to preserve at least a part of the organic compound of formula (I) or any other organic compound in the catalyst. The term "calcination" here means a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200 ° C. However, the catalyst precursor may undergo a calcination step before the introduction of the organic compound of formula (I) or any other organic compound containing oxygen and / or nitrogen and / or sulfur, in particular after the impregnation of the elements of group VIB and VIII (post-impregnation) optionally in the presence of phosphorus and / or another dopant or during a regeneration of a catalyst already used. The hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called the 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 the active phase, is then not in an oxide form. Whatever the embodiment, the contacting step a) generally comprises at least one impregnation step, preferably a dry impregnation step, in which the support is impregnated with a solution of water. impregnation comprising at least one group VIB element, at least one group VIII element, and optionally phosphorus. In the case of the co-impregnation described below in detail, this impregnation solution further comprises at least one organic compound of formula (I). The Group VIB and Group VIII elements are generally introduced by impregnation, preferably by dry impregnation or impregnation in excess of solution. Preferably, all the elements of group VIB and group VIII are introduced by impregnation, preferably by dry impregnation and this regardless of the embodiment.
[0030] 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 a matrix, the rest of the hydrogenating elements then being introduced later. by impregnation. Preferably, when the Group VIB and Group VIII elements are introduced in part at the time of mixing, the proportion of Group VIB element introduced in this step is less than 5% by weight of the total amount of Group VIB element introduced on the final catalyst. Preferably, the group VIB element is introduced at the same time as the group VIII element, regardless of the mode of introduction. The molybdenum precursors that 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 and phosphomolybdic acid. (H3PMo12040) and their salts, and optionally silicomolybdic acid (H4SiMo12040) and its salts. The sources of molybdenum may also be heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example. Molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, Keggin, Lacunaire or substituted Keggin type are preferably used. The tungsten precursors that can be used are also well known to those skilled in the art. For example, among the sources of tungsten, there may be used 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 (H4SiW12O40) and its salts. The sources of tungsten may also be heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, for example. Oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of the Keggin, Keggin, Lacunaire or substituted Keggin type are preferably used.
[0031] The precursors of the group VIII elements which may be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of the group VIII elements, for example nickel hydroxycarbonate, carbonate or calcium carbonate. cobalt hydroxide are used in a preferred manner. Phosphorus, when present, may be introduced in whole or in part by impregnation. Preferably, it is introduced by an impregnation, preferably dry, using a solution containing the precursors of Group VIB elements and Group VIII.
[0032] Said phosphorus may be advantageously introduced alone or in admixture with at least one of the group VIB and group VIII elements, and this during any of the steps of impregnation of the hydrogenating function if this is introduced in several times. Said phosphorus may also be introduced, all or part, during the impregnation of the organic compound of formula (I) if it is introduced separately from the hydrogenating function (case of the post-pre-impregnation described later) and this in the presence or absence of an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. It can also be introduced as soon as the synthesis of the support, at any stage of the synthesis thereof. It may 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 PO 4, but its salts and esters such as ammonium phosphates are also suitable. Phosphorus can also be introduced together with Group VIB element (s) in the form of Keggin, Keggin lacunary, Keggin substituted or Strandberg heteropolyanions. The organic compound of formula (I) is advantageously introduced into an impregnating solution which, according to the method of preparation, may be the same solution 3035008 22 or a solution different from that containing the elements of group VIB and VIII, in an amount corresponding total: - at a molar ratio of the organic compound of formula (I) to element (s) of group VIB of the catalyst precursor of between 0.01 and 5 mol / mol, preferably between 0.05 and 3 mol mol, preferably between 0.1 and 1.5 mol / mol and very preferably between 0.2 and 1 mol / mol, calculated on the basis of the components introduced into the solution (s) impregnation, and at a molar ratio of the organic compound of formula (I) per element (s) of group VIII of the catalyst precursor of between 0.02 and 17 mol / mol, preferably between 0.1 and 10 mol / mol, preferably between 0.2 and 5 mol / mol and re very preferably between 0.4 and 3.5 mol / mol, calculated on the basis of the components introduced in the solution (s) impregnation.
[0033] Any impregnating solution described in the present invention may comprise any polar solvent known to those skilled in the art. Said polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol and cyclohexanol, taken alone or as a mixture. Said polar solvent may 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 conventional polar solvents as well as 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. Most preferably, the solvent used is water or ethanol, and most preferably the solvent is water. In one possible embodiment, the solvent may be absent in the impregnating solution, in particular during a pre- or post-impregnation preparation. When the catalyst further comprises a dopant selected from boron, fluorine or a mixture of boron and fluorine, the introduction of this dopant (s) can be done in the same way as the introduction. phosphorus at various stages of preparation and in various ways. Said dopant may advantageously be introduced alone or in admixture with at least one of the group VIB and group VIII elements, and during any of the steps of impregnation of the hydrogenating function if this is introduced in several times. Said dopant may also be introduced, in whole or in part, during the impregnation of the organic compound of formula (I) if it is introduced separately from the hydrogenating function (case of the post- and pre-impregnation described later) and this in the presence or absence of an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. It can also be introduced as soon as 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 the aluminum oxyhydroxide (boehmite) precursor of alumina.
[0034] Said dopant, when there is one, is advantageously introduced in admixture with the precursor (s) of the elements of group VIB and of group VIII, in whole or in part on the support formed by an impregnation dry of said support with a solution, preferably aqueous, containing the metal precursors, the phosphorus precursor and the precursor (s) of the dopant (s), (and also containing the organic compound of formula (I) in the mode of coimprégnation). Boron precursors may be boric acid, orthoboric acid H3B03, biborate or ammonium pentaborate, boron oxide, boric esters. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture or in a water / ethanolamine mixture. Preferably the boron precursor, if boron is introduced, is orthoboric acid. The fluorine precursors that 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 the hydrofluoric acid. The fluorine may be introduced for example by impregnation with an aqueous solution of hydrofluoric acid, or ammonium fluoride or ammonium bifluoride.
[0035] When the catalyst further comprises an additional additive (in addition to the organic compound of formula (I)) or a further group of additives selected from an organic compound other than the organic compound of formula (I) containing oxygen and and / or nitrogen and / or sulfur, it may be introduced into the impregnation solution of step a).
[0036] The molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur by group VIB element (s) on the catalyst is between 0.05 and 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 impregnating solution (s).
[0037] The molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur by organic compound of formula (I) is between 0.05 and 5 mol / mol, preferably between 0.1 and 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s).
[0038] Advantageously, after each impregnation stage, the impregnated support is allowed to mature. The maturation allows the impregnating 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 of between 17 ° C. and 50 ° C., and preferably at room temperature. Generally a ripening time 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 improve.
[0039] According to 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 calcination step. higher. Any drying step subsequent to the introduction of the organic compound of formula (I) described in the present invention is carried out at a temperature below 200 ° C, preferably between 50 and 180 ° C, preferably between 70 and 200 ° C. 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 under reduced pressure. This step is preferably carried out at atmospheric pressure. It is advantageously carried out in crossed bed using air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is either air or an inert gas such as argon or nitrogen. Very preferably, the drying is carried out in a traversed 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 retain at least 30% of the organic compound of formula (I) introduced during an impregnation step, preferably this amount is greater than 50% and even more preferably greater than at 70%, calculated on the basis of the carbon remaining on the catalyst. When an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur is present, the drying step is carried out so as preferably to preserve at least one 30%, preferably at least 50%, and most preferably at least 70% of the amount added 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.
[0040] Co-impregnation According to a first embodiment of step a) of the catalyst preparation process (fresh), the said components of the elements of group VIB, of group VIII, of the organic compound of formula (I) and optionally phosphorus on said support, by one or more co-impregnation steps, that is to say that said components of group VIB elements, of group VIII, the organic compound of formula (I) and optionally phosphorus are introduced simultaneously into said support ("co-impregnation"). According to one variant, step a) is the following step: a) a support based on alumina or silica or silica-alumina is impregnated with at least one solution containing at least one group VIB element, at least one group VIII element, the organic compound of formula (I) and optionally phosphorus so as to obtain a catalyst precursor.
[0041] The co-impregnation step (s) is (are) preferably carried out by dry impregnation or impregnation in excess of solution. When this first mode comprises the implementation of several co-impregnation steps, each co-impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C., advantageously between 50 and 180 ° C. ° C, preferably between 70 and 150 ° C, very preferably between 75 and 130 ° C and optionally a dematuration period was observed between the impregnation and drying. Very preferably, during the preparation via co-impregnation, the elements of group VIB and of group VIII, the organic compound of formula (I), optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur are introduced in step a) in full after the shaping of said support by dry impregnation of said support with an aqueous impregnating solution containing the precursors of group VIB and group VIII elements, the organic compound of formula (I), optionally the phosphorus precursor. , optionally the dopant precursor chosen from boron and / or fluorine and optionally the organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur.
[0042] Post-impregnation According to a second embodiment of step a) of the process for preparing the (fresh) catalyst according to the invention, at least one organic compound of formula (I) is brought into contact with an impregnated support dried and optionally calcined comprising at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus, said support being based on alumina or silica or silica-alumina to obtain a catalyst precursor. This second embodiment is a "post-impregnation" preparation of the organic compound of formula (I). This is carried out for example by dry impregnation. According to this second embodiment, the contacting according to step a) comprises the following successive steps which will be detailed below: a1) impregnating a support based on alumina or silica or silica; alumina by at least one solution containing at least one group VIB element, at least one group VIII element and optionally phosphorus to obtain an impregnated support, a2) drying the impregnated support obtained in step a1) at a temperature less than 200 ° C to obtain a dried impregnated support, and optionally the dried impregnated support is calcined to obtain a calcined impregnated support, a3) the dried and optionally calcined impregnated support obtained in step a2) is impregnated with an aqueous solution. impregnation comprising at least the organic compound of formula (I) so as to obtain a catalyst precursor, optionally, the catalyst precursor is allowed to mature; in step a3). In step a1) of the implementation by post-impregnation, the introduction of the elements of group VIB and group VIII and optionally phosphorus on the support can be advantageously carried out by one or more impregnations in excess of solution on the support, or preferably by one or more dry impregnation, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s) containing the or metal precursors and preferably the phosphorus precursor.
[0043] When carrying out several impregnation steps, each impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C., advantageously between 50 and 180 ° C., preferably between 70 and 150 ° C, very preferably between and 130 ° C and optionally a period of maturation was observed between the impregnation and drying.
[0044] Each intermediate drying step prior to the introduction of the organic compound of formula (I) may be followed by a calcination step under the conditions described below for step a2). Very preferably, during the post-impregnation preparation, the elements of group VIB and group VIII and optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur are introduced in step a1) in full after the shaping of said support, by dry impregnation of said support to using an aqueous impregnation solution containing the precursors of group VIB and Group VIII elements, the phosphorus precursor, and optionally the dopant precursor chosen from boron and / or fluorine and optionally the organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur.
[0045] According to another variant, the elements of group VIB and group VIII and optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur can be introduced in step a1) successively by several impregnating solutions containing one or more of the components. Advantageously, the impregnated support obtained in step a1) is allowed to mature under the conditions described for the above ripening. According to step a2), the impregnated support obtained in step a1) is dried at a temperature below 200 ° C to obtain a dried impregnated support under the conditions described for drying above. Optionally, the dried impregnated support can then be calcined. The calcination is generally carried out at a temperature of between 200 ° C. and 900 ° C., preferably between 250 ° C. and 75 ° C. The calcination time is generally between 0.5 hours and 16 hours, preferably between 1 hour and 5 hours. It is usually done under air. Calcination makes it possible to convert the precursors of Group VIB and VIII metals into oxides. According to step a3), the dried impregnated support obtained in step a2) is impregnated with an impregnating solution comprising at least the organic compound of formula (I) so as to obtain a catalyst precursor. The organic compound of formula (I) can advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art. Preferably, the organic compound of formula (I) is introduced in dry impregnation, in the presence or absence of a solvent as described above. Preferably, the solvent in the impregnating solution used in step a3) is water, which facilitates the implementation on an industrial scale.
[0046] The organic compound of formula (I) is advantageously introduced into the impregnation solution of step a3) with the molar ratios per element of group VIB or group VIII described above. When it is desired to further introduce an additional additive (in addition to the organic compound of formula (I)) or a further group of additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur, it can be introduced into the impregnating solution of step a1) and / or into the impregnation solution of step a3) or by an additional impregnation step to any the time of the preparation process 10 before the final drying of step b), it being understood that no calcination step is carried out after it has been introduced. This compound is introduced in the proportions described above. According to step a4), the catalyst precursor obtained in step a3) is optionally allowed to mature, and this under the conditions of maturation described above.
[0047] According to step b) of the preparation process according to the invention, the catalyst precursor which has been optionally matured in step a4) is subjected to a drying step at a temperature below 200 ° C without a step subsequent calcination, as described above. Pre-impregnation According to a third embodiment of step a) of the process for preparing the (fresh) catalyst according to the invention, at least one component of a group VIB element is brought into contact with at least one a component of a group VIII element, optionally phosphorus with the support based on alumina or silica or silica-alumina which contains an organic compound of formula (I) so as to obtain a catalyst precursor. This third embodiment is a preparation by "pre-impregnation" of the organic compound of formula (I). This is carried out for example by dry impregnation.
[0048] According to this third embodiment, the contacting according to step a) comprises the following successive steps which will be detailed below: a ') a support is prepared comprising at least one organic compound of formula ( I) and optionally at least a portion of the phosphorus, 5 a2 ') the support obtained in step a1') is impregnated with an impregnating solution comprising at least one group VIB element, at least one group VIII element and optionally, phosphorus so as to obtain a catalyst precursor, a3 ') optionally, the catalyst precursor obtained in step a2') is allowed to mature. In step a1 ') of the implementation by pre-impregnation, a support is prepared comprising at least one organic compound of formula (I) and optionally at least a portion of the phosphorus. The organic compound of formula (I) can be introduced at any time during the preparation of the support, and preferably during the shaping or by impregnation on a support already formed. If the introduction of the organic compound of formula (I) onto the previously shaped support is chosen, then this can be carried out as indicated for step a3) of the post-impregnation. It will then be followed by an optional ripening step and drying at a temperature below 200 ° C under the ripening and drying conditions as described above. If we choose the introduction during the shaping, preferably, said shaping is carried out by extrusion kneading, by pelletizing, by the method of drop coagulation (oil-drop according to the English terminology), by rotating plate granulation or any other method well known to those skilled in the art. Very preferably, said shaping is carried out by extrusion kneading, the organic compound of formula (I) being able to be introduced at any time of the kneading extrusion. The formed material obtained at the end of the forming step is then advantageously subjected to a heat treatment step at a temperature such that at least a part of the organic compound of formula (I) remains present. It is the same for the phosphorus possibly present in said support of step al '). The phosphorus may be introduced at any time during the preparation of the support, and preferably during the shaping or by impregnation on a support already formed as described above. If the phosphorus is introduced alone to the shaping, that is to say without the organic compound of formula (I) itself then introduced by impregnation, the calcination temperature subsequent to its introduction can then advantageously be carried out at a temperature below 1000 ° C. In step a2 ') of the implementation by pre-impregnation, the introduction of Group VIB and Group VIII elements and optionally phosphorus can be advantageously 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, with solution (s), preferably aqueous (s), containing the precursor (s) metals and possibly the phosphorus precursor. Advantageously, the catalyst precursor obtained in step a2 ') is allowed to mature under the conditions of maturation described above.
[0049] When it is desired to further introduce an additional additive (in addition to the organic compound of formula (I)) or a further group of additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur, it can be introduced into the support of step a1 ') during shaping or impregnation, and / or in the impregnating solution of step a2') or again by a additional impregnation stage at any time of the preparation process before the final drying of step b), it being understood that no calcination step is carried out after its introduction.
[0050] The three modes described above can be implemented alone as described or mixed to give rise to other hybrid preparation modes depending on the technical and practical constraints. According to another alternative embodiment, the contacting according to step a) combines at least two contacting modes, for example the co-impregnation of an organic compound and the post-impregnation of an organic compound. which may be identical or different from that used for the co-impregnation, since at least one of the organic compounds is an organic compound of formula (I). According to this alternative embodiment, the contacting according to step a) comprises the following successive steps: anon contacts by co-impregnation a solution containing at least one element of group VIB, at least one element of the group VIII, at least one organic compound containing oxygen and / or nitrogen and / or sulfur, and optionally phosphorus with a support based on alumina or silica or silica-alumina so as to obtain an impregnated support, a2 ") the impregnated support from step a1" ") is dried at a temperature below 200 ° C., without subsequently calcining it to obtain a dried impregnated support, a3") the support is brought into contact with dried impregnated material from step a2 ") with a solution of at least one organic compound containing oxygen and / or nitrogen and / or sulfur identical to or different from that used in step a1" ) so as to obtain a catalyst precursor, a4 ") optionally The catalyst precursor obtained in step a3 ") is allowed to mature. And at least one of the organic compounds of step a1 "- or step a3") is an organic compound of formula (I). The operating conditions described above are of course applicable in the context of this latter embodiment.
[0051] Process for the Preparation of a Rejected Catalyst The catalyst according to the invention may be a rejuvenated catalyst. This catalyst may be prepared according to the preparation method comprising the following steps: a) a regenerated catalyst containing a support based on alumina or silica or silica-alumina is contacted with at least one component of an element group VIB, at least one component of a group VIII element and optionally phosphorus, with an organic compound of formula (I) so as to obtain a catalyst precursor, b) drying said catalyst precursor from the step a) at a temperature below 200 ° C, without further calcining According to step a) a regenerated catalyst is contacted with an organic compound of formula (I), so as to obtain a catalyst precursor. The regenerated catalyst is a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreatment and / or hydrocracking and which has been subjected to at least one calcination step in order to burn the coke (regeneration). The regeneration allows the combustion of the carbon deposited on the catalyst during its industrial use. It can be performed by any means known to those skilled in the art. The regeneration is generally carried out at temperatures between 350 and 550 ° C, and the pbs often between 400 and 520 ° C, 20 or between 420 and 520 ° C, or between 450 and 520 ° C temperatures below 500 ° C are often advantageous. The regenerated catalyst contains a support based on alumina or silica or silica-alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally with phosphorus in the group. respective proportions indicated above. Following the regeneration (calcination step) the hydrogenating function comprising the elements of group VIB and group VIII of the regenerated catalyst is in an oxide form. It may also contain other dopants than phosphorus, as described above.
[0052] According to this embodiment, the contacting according to step a) comprises the following successive steps: a) is impregnated a regenerated catalyst containing a support based on alumina or silica or silica-alumina , at least one component of a Group VIB element, at least one component of a group VIII element and optionally phosphorus with an impregnating solution comprising at least one organic compound of formula (I) so as to obtain a catalyst precursor, a2 "') optionally, is allowed to mature the catalyst precursor obtained in step al -). Preferably, the contacting of step a) is carried out by impregnating the regenerated catalyst with an impregnating solution comprising at least one organic compound of formula (I) so as to obtain a catalyst precursor. The organic compound of formula (I) may 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 organic compound of formula (I) is introduced in dry impregnation, in the presence or absence of a solvent as described above. Preferably, the solvent in the impregnating solution used is water, which makes it easier to use on an industrial scale. The organic compound of formula (I) is advantageously introduced into the impregnation solution with the molar ratios per element of group VIB or group VIII described above. When it is desired to further introduce an additional additive (in addition to the organic compound of formula (I)) or a further group of additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur, this can be introduced into the impregnation solution of step a1 "") or by a further impregnation step at any time of the preparation process before the final drying of the step b) it being understood that a calcination step is not carried out after it has been introduced This compound is introduced in the proportions described above According to step a 2 "), the catalyst precursor is optionally allowed to mature Obtained in step a1 "'), and this under the conditions of maturation described above In accordance with step b) of the preparation process according to the invention, the catalyst precursor which has been optionally matured during step a2 ") is subject to a drying step at a temperature below 200 ° C without subsequent calcination step, as described above.
[0053] Sulfurization Prior to its use for the hydrotreatment and / or hydrocracking reaction, it is advantageous to convert the dried catalyst obtained according to any of the methods of introduction described in the present invention into a sulphurized catalyst in order to form it. active species. This activation or sulphurization 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 modes of preparation of the process according to the invention, said catalyst obtained is thus advantageously subjected to a sulphurization step, without intermediate calcination step.
[0054] Said dried catalyst is advantageously sulphurized ex situ or in situ. The sulfurizing agents are H25 gas or any other sulfur-containing compound used to activate hydrocarbon feeds to sulphurize the catalyst. Said sulfur-containing compounds are advantageously chosen from alkyl disulphides such as, for example, dimethyl disulphide (DMDS), alkyl sulphides, such as, for example, dimethyl sulphide, thiols such as for example butyl mercaptan (or 1-butanethiol), polysulfide compounds tertiononylpolysulfide type, or any other compound known to those skilled in the art for obtaining a good sulfuration of the catalyst. Preferably the catalyst is sulfided in situ in the presence of a sulfurizing agent and a hydrocarbon feedstock. Very preferably, the catalyst is sulphurized in situ in the presence of a hydrocarbon feed additive of dimethyl disulfide. Finally, another object of the invention is the use of the catalyst according to the invention or prepared according to the preparation method according to the invention in hydrotreatment and / or hydrotreatment processes. hydrocracking of hydrocarbon cuts. The catalyst according to the invention, preferably having previously undergone a sulphurisation step, is advantageously used for the hydrotreatment and / or hydrocracking reactions of hydrocarbonaceous feedstocks such as petroleum cuts, cuts from coal or hydrocarbons produced. from natural gas, optionally in mixtures or from a hydrocarbon fraction derived from biomass and more particularly for the hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulphurization, hydrodeoxygenation, hydrogenation reactions. hydrodemetallization or hydroconversion of hydrocarbon feedstocks. In these uses, the catalyst according to the invention and having preferably previously undergone a sulphurization step has an improved activity compared to the catalysts of the prior art. This catalyst may also advantageously be used during the pretreatment of the catalytic cracking or hydrocracking feeds, or the hydrodesulfurization of the residues or the deep hydrodesulphurization of gas oils (ULSD Ultra Low Sulfur Diesel according to the English terminology). The feedstocks employed 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, waste oils, residues or deasphalted crudes, fillers derived from thermal or catalytic conversion processes, lignocellulosic fillers or more generally biomass feedstocks, alone or as a mixture. The feedstocks which are treated, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy feedstocks, they most often also contain metals. The operating conditions used in the processes employing the hydrotreating reactions of hydrocarbon feedstocks described above are generally as follows: the temperature is advantageously between 180 and 450 ° C., and preferably between 250 and 440 ° C., the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume velocity is advantageously between 0.1 and 20 h -1 and preferably between 0.2 and 5 h -1; 1, and the hydrogen / charge ratio expressed as a volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge is advantageously between 50 1/1 to 5000 1/1 and preferably 80 to 20001 / 1. According to a first mode of use, said hydrotreatment process according to the invention is a hydrotreatment process, and in particular hydrodesulphurization (HDS) of a gas oil fraction carried out in the presence of at least one catalyst according to the invention. invention. Said hydrotreatment process according to the invention aims at eliminating the sulfur compounds present in said diesel fuel cup so as to reach the environmental standards in force, namely a permissible sulfur content of up to 20 ppm. It also makes it possible to reduce the aromatics and nitrogen contents of the diesel fraction to be hydrotreated. Said gasoil fraction to be hydrotreated according to the process of the invention contains from 0.02 to 5.0% by weight of sulfur. It is advantageously derived from the straight distillation (or straight run diesel according to the English terminology), a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology). -saxonne), a steam cracking unit (steam cracking according to the English terminology), a hydrotreating unit and / or hydrocracking heavier charges and / or a catalytic cracking unit (Fluid Catalytic Cracking according to Anglo-Saxon terminology). Said gasoil fraction preferably has at least 90% of the compounds whose boiling point is between 250 ° C. and 400 ° C. at atmospheric pressure. The process for hydrotreating said diesel fuel cutter according to the invention is carried out under the following operating conditions: a temperature of between 200 and 400 ° C., preferably between 300 and 380 ° C., a total pressure of 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 as 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 space velocity of between 1 and 10 h -1, preferably between 2 and 8 1-1-1. The VVH corresponds to the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock to the volume of catalyst charged to the reaction unit implementing the hydrotreatment process according to the invention. invention. The reaction unit implementing the hydrotreating process of said gasoil fraction according to the invention is preferably carried out 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 hydrotreating process (in particular hydrodesulfurization, hydrodeaazoation, hydrogenation of aromatics) and / or hydrocracking of a section. vacuum distillate produced in the presence of at least one catalyst according to the invention. Said hydrotreatment and / or hydrocracking process, otherwise known as the hydrocracking or hydrocracking pretreatment method according to the invention, is intended, depending on the case, to eliminate the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to perform pre-treatment before conversion to catalytic cracking or hydroconversion processes, or to hydrocrack the distillate cut that may have been previously pretreated if necessary. A wide variety of feeds can be processed by the hydrotreatment and / or vacuum distillate hydrocracking processes described above. Generally 3035008 contain at least 20% volume and often at least 80% volume of compounds boiling above 340 ° C at atmospheric pressure. The feedstock may be, for example, vacuum distillates as well as feedstocks from aromatic extraction units of lubricating oil bases or from solvent dewaxing of lubricating oil bases, and / or oils. deasphalted, or the filler may be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the aforementioned fillers. In general, the feeds have a boiling point T5 greater than 340 ° C at atmospheric pressure, and more preferably greater than 370 ° C at atmospheric pressure, ie 95% of the compounds present in the feed have a boiling point above 340 ° C, and more preferably above 370 ° C. The nitrogen content of the feeds Laity 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 fillers treated in the processes according to the invention is usually between 0.01 and 5.0% by weight. The filler may optionally contain metals (eg nickel and vanadium). The asphaltene content is generally less than 3000 ppm by weight. The hydrotreatment and / or hydrocracking catalyst is generally brought into contact, in the presence of hydrogen, with the previously described feeds, at a temperature above 200 ° C., often between 250 ° C. and 480 ° C. advantageously between 320 ° C and 450 ° C, deference between 330 ° C and 435 ° C, under a pressure greater than 1 MPa, solder between 2 and 25 MPa, preferably between 3 and 20 MPa, the speed volume ranging from 0.1 to 20.0 h -1 and preferably 0.1 to 6.0 h -1, preferably 0.2 to 3.0 h -1, and the amount of hydrogen introduced is such that the volume ratio of hydrogen per liter of hydrocarbon, expressed as volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge, is between 80 and 5,000 1/1 and most often between 100 and 2000 1/1. These operating conditions used in the processes according to the invention generally make it possible to achieve pass conversions, products having boiling points below 340 ° C. at atmospheric pressure, and better still below 370 ° C. at 3035008 pressure. atmospheric, greater than 15% and even more preferably between 20 and 95%. The processes for hydrotreatment and / or hydrocracking of vacuum distillates using the catalysts according to the invention cover the pressure and conversion ranges 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 fixed bed catalytic beds, in one or more reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the unconverted fraction. or in a two-stage hydrocracking scheme, optionally in combination with a hydrorefining catalyst located upstream of the catalyst of the present invention.
[0055] According to a third mode of use, said hydrotreatment and / or hydrocracking process according to the invention is advantageously used as pretreatment in a fluidized-bed catalytic cracking process (or FCC method for Fluid Catalytic Cracking according to US Pat. Anglo-Saxon terminology). The pretreatment operating conditions in terms of temperature range, pressure, hydrogen recycle rate, hourly space velocity are generally the same as those described above for 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 the appropriate cracking conditions to produce lower molecular weight hydrocarbon products. For example, a brief 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 method of hydrotreating and / or hydrocracking according to US Pat. The invention is a process for hydrotreatment (especially hydrodesulfurization) of a gasoline cut in the presence of at least one catalyst according to the invention. In contrast to other hydrotreatment processes, the hydrotreatment (in particular the hydrodesulfurization) of the species must make it possible to respond to a double antagonistic constraint: to ensure a deep hydrodesulphurization of the species and to limit the hydrogenation of the unsaturated compounds present in order to limit the loss of octane number. The feed is generally a hydrocarbon cut having a distillation range of between 30 and 260 ° C. Preferably, this hydrocarbon cut is a gasoline cut. In a very preferred manner, the gasoline cut is an olefinic gasoline cut resulting for example from a catalytic cracking unit (Fluid Catalytic Cracking according to the English terminology). The hydrotreatment process comprises contacting the hydrocarbon fraction with the catalyst according to the invention and with hydrogen under the following conditions: at a temperature of between 200 and 400.degree. C., preferably between 230 and 330 ° C, at a total pressure of between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa, at a Time Volumetric Velocity (VVH), defined as the volume flow rate of charge relative to the volume of catalyst , between 1 and 10 h -1, preferably between 2 and 6 h -1 and at a volume ratio hydrogen / gasoline charge between 100 and 600 NI / 1, preferably between 200 and 400 N1 / 1. The process for hydrotreatment of gasolines 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 carried out using at least two reactors in series, it is possible to provide a device for removing the H2S from the effluent coming from the first hydrodesulfurization reactor before treating said effluent in the second hydrodesulfurization reactor.
[0056] The following examples demonstrate the significant increase in activity on the catalysts prepared according to the process according to the invention with respect to the catalysts of the prior art and specify the invention without however limiting its scope. EXAMPLES Example 1 Preparation of CoMoP catalysts on alumina without organic compounds C1 and C2 (not in accordance with the invention). On an alumina support having a BET surface area of 230 m 2 / g, a pore volume obtained by mercury porosimetry of 0.78 ml / g and an average pore diameter of 11.5 nm defined as the median diameter by volume. Mercury porosimetry, which is in the "extruded" form, is added cobalt, molybdenum and phosphorus. The impregnation solution is prepared by dissolving 90 ° C. of molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) in 11.8 g of an aqueous solution of acid. 85% phosphoric acid and water. After dry impregnation, the extrudates are allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 90 ° C for 16 hours. The dried catalyst precursor thus obtained is denoted C1. Calcination of the catalytic precursor C1 at 450 ° C. for 2 hours leads to the calcined catalyst C2. The final composition of the catalysts C1 and C2 expressed in the form of oxides and relative to the mass of dry catalyst is then as follows: MoO3 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% weight and P2O5 = 6.7 ± 0.1% by weight. EXAMPLE 2 Preparation of CoMoP catalysts on alumina C3 (not in accordance with the invention), C4 (in accordance with the invention) by co-impregnation On the alumina support described above in Example 1 and which is in the "extruded" form, cobalt, molybdenum and phosphorus are added. The impregnating solution was prepared by dissolving molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in 90 ° C. in 15.85 g of an aqueous solution. 85% phosphoric acid and water. After homogenization of the above mixture, 38 g of citric acid was added before adjusting the volume of the solution to the pore volume of the support by addition of 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 allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 120 ° C for 16 hours. The dried catalyst precursor thus obtained is denoted C3. The final composition of catalyst C3, expressed in the form of oxides and based on the dry catalyst mass, is then as follows: MoO 3 = 19.6 ± 0.2% by weight, CoO = 3.7 ± 0.1% by weight and P2O5 = 6.7 ± 0.1% by weight. Catalysts C4 according to the invention is prepared as follows. On the alumina support 10 described in Example 1 and which is in the "extruded" form, cobalt, molybdenum and phosphorus are added. An impregnating solution was prepared by dissolving molybdenum oxide (39 g) and cobalt hydroxide (9.3 g) at 90 ° C. in 21.9 g of an aqueous phosphoric acid solution. 85% and water. After homogenization of the above mixture, 2-methoxyethyl 3-oxobutanoate was added to the 0.5 mole solution per mole of molybdenum, ie 1.4 moles per mole of cobalt to yield catalyst C4. The volume of the solution was adjusted to the pore volume of the support by adding water before each impregnation. After dry impregnation, the extrudates of both catalysts were allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 120 ° C for 16 hours. The final composition of the catalyst C4, expressed in oxide form and relative to the mass of dry catalyst, is then as follows: MoO 3 = 19.5 ± 0.2% by weight, CoO = 3.5 ± 0.1% by weight and P2O 5 '± = 6 8 + 0' 1% wt. Example 3 Preparation of the CoMoP catalyst on C5 alumina (according to the invention) by pre-impregnation. On the alumina support described above in Example 1 and which is in the "extruded" form, 15.2 g of 2-methoxyethyl 3-oxobutanoate diluted in water are added in order to obtain a solution of total volume equal to the pore volume of the support. The solution thus formed is then impregnated dry on the support before observing a maturation time of 3 hours in a saturated atmosphere with water and at ambient temperature, followed by drying at 120 ° C. for 2 hours. The modified support is then impregnated with a new impregnating solution prepared by hot dissolving molybdenum oxide (27.3 g) and cobalt hydroxide (6.5 g) in 15.3 g. an 85% aqueous solution of phosphoric acid and water, taking care to adjust the volume of the latter solution by the addition of water to the pore volume of the previously modified support. After dry impregnation, the extrudates were allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 120 ° C for 16 hours to yield catalyst C5. The final composition of the catalyst C5, expressed in oxide form and relative to the dry catalyst mass, is then as follows: Mo03 = 19.7 ± 0.2% by weight, CoO = 3.5 ± 0.1% by weight and P2O5 = 6.8 ± 0.1% by weight. The amounts involved are such that the amount of 2-methoxyethyl 3-oxobutanoate is 0.5 moles per mole of molybdenum or 1.4 moles per mole of cobalt. EXAMPLE 4 Evaluation in HDS of Diesel of Catalysts C1, C2 and C3 (not in Accordance with the Invention) and C4 and C5 (in Accordance with the Invention) Catalysts C1, C2 and C3 (not in Accordance with the Invention) and C4 and C5_ (in accordance with the invention) were tested in diesel HDS.
[0057] Characteristics of the diesel fuel used: density at 15 ° C: 0.8522 g / cm3, sulfur: 1.44% by weight. - Simulated Distillation: - PI: 155 ° C - 10% 247 ° C 25 - 50% 315 ° C - 90% 392 ° C - mp: 444 ° C 3035008 46 The test is conducted in an isothermal pilot reactor with fixed bed crossed , fluids flowing from bottom to top. After sulphurisation in situ at 350 ° C. in the unit under pressure using the test gas oil to which 2% by weight of dimethyl disulphide is added, the hydrodesulfurization test was carried out under the following operating conditions: a total pressure of 7 MPa, a catalyst volume of 30 cm3, a temperature of 330 to 360 ° C, a hydrogen flow rate of 24 1 / h and a load rate of 60 cm3 / h. The catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius from a comparative catalyst chosen as reference (C2): they correspond to the temperature difference to be applied to reach 50 ppm of sulfur. in the effluent. A negative value means that the target of sulfur content is reached for a lower temperature and that there is a gain in activity. A positive value means that the target of sulfur content is reached for a higher temperature and that there is therefore a loss of activity. The results obtained are reported in Table 1.
[0058] Table 1 clearly shows the gain on the catalytic effect provided by 2-methoxyethyl-3-oxobutanoate. Indeed, the catalysts C4 and C5 (according to the invention) have higher activities than those obtained for all the other catalysts evaluated. 2-Methoxyethyl 3-oxobutanoate thus provides a gain in catalytic activity irrespective of its mode of introduction.
[0059] The advantage of the catalyst according to the invention is significant while it has a lower proportion of organic compound than the C3 catalyst, and thus an intrinsic efficiency of 2-methoxyethyl I3-oxobutanoate greater than that of the other compounds for which it is necessary to introduce a greater proportion of compound to observe a significant catalytic effect.
[0060] Table 1: Activity relative to iso-volume in hydrodesulfurization of gas oil of catalysts C1, C2 and C3 (not in accordance with the invention) and C4 and C5 (in accordance with the invention) with respect to catalyst C2 (non-compliant ) Catalyst Compound Method of introduction of the organic compound Heat treatment HDS activity (comparative or organic used and (post- / co- / pre-impregnation according to molar ratio / Mo the invention) Cl (comp) none Dried 120 ° C Base + 1.0 ° C C2 (comp) n / a Not applicable Calcium Base C3 (comp) Citric acid - 1.0 CO Dry 120 ° C Base - 2.9 ° C C4 (inv) 3-methoxyethyl-2-oxobutanoate, 5 CO Dry 120 ° C Base - 5.6 ° C C5 (inv) 3-Methoxyethyl 2-oxobutanoate - 0.5 PRE Dried 120 ° C Base - 5.9 ° C

权利要求:
Claims (19)
[0001]
REVENDICATIONS1. Catalyst comprising a support based on alumina or silica or silica-alumina, at least one group VIII element, at least one group VIB element, and an organic compound of formula (I) ## STR5 ## R 5 (I) in which R 1, R 2, R 3, R 4 and R 5 are chosen from a hydrogen atom, a hydroxyl radical or a hydrocarbon radical comprising from 1 to 12 carbon atoms which may also comprise at least one oxygen atom; and R 6 is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms which may further comprise at least one oxygen atom, a methacryloyl radical, an acryloyl radical or an acetyl radical.
[0002]
The catalyst of claim 1, wherein the organic compound of formula (I) is selected from a derivative of
[0003]
2-alkoxyethyl 3-oxobutanoates, wherein R1 is a methyl group, R2, R3, R4 and R5 is a hydrogen atom and R6 is selected from a hydrogen atom, a hydrocarbon radical having 1 to 12 carbon atoms, carbon may also comprise at least one oxygen atom, a methacryloyl radical, an acryloyl radical or an acetyl radical. 3. Catalyst according to claim 2, wherein the organic compound of formula (I) is chosen from 2-methoxyethyl 2-methyl-3-oxopropanoate, 2-ethoxyethyl 2-methyl-3-oxopropanoate, 3- 2-hydroxyethyl oxobutanoate, 2-hydroxypropyl 3-oxobutanoate, 2-methoxyethyl 3-oxobutanoate, 2-ethoxyethyl 3-oxobutanoate, 2-propoxyethyl 3-oxobutanoate, 2-acetyloxyethyl 3-oxobutanoate , 2-acryloyloxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, 1- (2-hydroxyethyl) -3-methyl propanedioate, 1-ethyl-3- (2-hydroxyethyl) propanedioate , 1,3-bis (2-hydroxyethyl) propanedioate, 1- (2-methoxyethyl) -3-methyl propanedioate, 1-ethyl-3- (2-methoxyethyl) propanedioate, propanedioate of (2-ethoxyethyl) -3-methyl and the mono (2-hydroxyethyl) ester of propanedioic acid.
[0004]
4. Catalyst according to one of claims 1 to 3, wherein the element content of group VIB is between 5 and 40% by weight expressed as Group VIB metal oxide relative to the total weight of the catalyst and the content of element Group VIII is between 1 and 10% weight expressed as Group VIII metal oxide relative to the total weight of the catalyst.
[0005]
5. Catalyst according to one of claims 1 to 4, wherein the molar ratio of Group VIII element to Group VIB element in the catalyst is between 0.1 and 0.8.
[0006]
6. Catalyst according to one of claims 1 to 5, which further contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P2O5 relative to the total weight of the catalyst and the phosphorus to the group VIB element in the catalyst is greater than or equal to 0.05.
[0007]
7. Catalyst according to one of claims 1 to 6, wherein the content of organic compound of formula (I) is between 1 and 45% by weight relative to the total weight of the catalyst.
[0008]
8. Catalyst according to one of claims 1 to 7, which further contains an organic compound other than the organic compound of formula (I) containing oxygen and / or nitrogen and / or sulfur
[0009]
The catalyst according to claim 8, wherein the organic compound is selected from a compound having one or more chemical functions selected from carboxylic, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate function. amine, nitrile, imide, oxime, urea and amide. 3035008 50
[0010]
10. Catalyst according to claim 9, wherein the organic compound other than the organic compound of formula (I) is chosen from triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, bicine, or tricine.
[0011]
11. Catalyst according to one of claims 1 to 10, characterized in that it is at least partially sulphurized.
[0012]
12. Process for the preparation of a catalyst according to one of claims 1 to 11 comprising the following steps: a) at least one component of a group VIB element is brought into contact with at least one component of an element group VIII, an organic compound of formula (I) and optionally phosphorus with a support based on alumina or silica or silica-alumina, or is brought into contact a regenerated catalyst containing an alumina-based support or silica or silica-alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus with an organic compound of formula (I), so as to obtain a catalyst precursor, b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without subsequently calcining it
[0013]
13. The method of claim 12, wherein step a) is the following step: a ') impregnates a support based on alumina or silica or silica-alumina with at least one solution containing at least one group VIB element, at least one group VIII element, the organic compound of formula (I) and optionally phosphorus so as to obtain a catalyst precursor.
[0014]
14. The method of claim 12, wherein step a) comprises the following steps: 3035008 51 a1) impregnating a support based on alumina or silica or silica-alumina by at least one solution containing at least one group VIB element, at least one group VIII element and optionally phosphorus to obtain an impregnated support, a2) drying the impregnated support obtained in step a1) at a temperature below 200 ° C to obtain an impregnated support dried, and optionally drying the dried impregnated support to obtain a calcined impregnated support, a3) impregnating the dried and optionally calcined impregnated support obtained in step a2) with an impregnating solution comprising at least the organic compound of formula (I) so as to obtain a catalyst precursor, a4) optionally, the catalyst precursor obtained in step a3) is allowed to mature.
[0015]
15. The process according to claim 12, wherein step a) comprises the following steps: a) a support is prepared comprising at least one organic compound of formula (I) and optionally at least a portion of the phosphorus, a2 ' ) the support obtained in step a1 ') is impregnated with an impregnating solution comprising at least one element of group VIB, at least one element of group VIII and optionally with phosphorus so as to obtain a catalyst precursor, a3 optionally, the catalyst precursor obtained in step a2 ') is allowed to mature.
[0016]
16. The process according to claim 12, wherein step a) comprises the following steps: a) a solution containing at least one group VIB element, at least one group VIII element is contacted by co-impregnation; at least one organic compound containing oxygen and / or nitrogen and / or sulfur, and optionally phosphorus with a support based on alumina or silica or silica-alumina so as to obtain an impregnated support, a2 "), the impregnated support from step a1" ") is dried at a temperature below 200 ° C., without subsequently calcining it to obtain a dried impregnated support, a3") the support is brought into contact with dried impregnated material from step a2 ") with a solution of at least one organic compound containing oxygen and / or nitrogen and / or sulfur identical to or different from that used in step a1" in order to obtain a catalyst precursor, a 4 ") optionally, it is allowed to maturing the catalyst precursor obtained in step a3 "), and at least one of the organic compounds of step a1" - or step a3 ") is an organic compound of formula (I).
[0017]
17. The process according to claim 12, wherein step a) comprises the following steps: a) regenerating a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one component of a group VIB element, at least one component of a group VIII element and optionally phosphorus by an impregnating solution comprising at least one organic compound of formula (I) so as to obtain a catalyst precursor , a2 "') optionally, the catalyst precursor obtained in step a"') is allowed to mature.
[0018]
18. The process as claimed in one of claims 12 to 17, in which the molar ratio of the organic compound of formula (I) per element (s) of group VIII is between 0.1 and 5.0 mol / mol.
[0019]
19. Use of the catalyst according to one of claims 1 to 11 or prepared according to one of claims 12 to 18 in a process for hydrotreating and / or hydrocracking of hydrocarbon cuts.

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公开号 | 公开日

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EP3490707B1|2021-04-14|

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FR3035008B1|2021-08-27|

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US20190151834A1|2019-05-23|

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EP3490707A1|2019-06-05|

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DK3490707T3|2021-07-05|

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US11097258B2|2021-08-24|

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WO2018019492A1|2018-02-01|

引用文献:

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WO2018114398A1|2016-12-22|2018-06-28|IFP Energies Nouvelles|Selective hydrogenation method using a nickel-based catalyst produced using an additive comprising an alcohol function|

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WO2018114396A1|2016-12-22|2018-06-28|IFP Energies Nouvelles|Selective hydrogenation method using a nickel-based catalyst produced using an additive comprising a carboxylic acid function|

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FR3061195A1|2016-12-22|2018-06-29|IFP Energies Nouvelles|SELECTIVE HYDROGENATION PROCESS USING A PREPARED NICKEL CATALYST USING AN ADDITIVE COMPRISING AMINO ACID, AMIDE FUNCTION OR AN AMINO ACID|

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WO2018202467A1|2017-05-04|2018-11-08|IFP Energies Nouvelles|Method for adding an organic compound to a porous solid in the gaseous phase|

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WO2020002138A1|2018-06-27|2020-01-02|IFP Energies Nouvelles|C5 or c6 acid ester-based catalyst and use thereof in a hydroprocessing and/or hydrocracking process|

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WO2020002137A1|2018-06-27|2020-01-02|IFP Energies Nouvelles|Catalyst based on a beta-oxygen ester and use thereof in a hydrotreating and/or hydrocracking process|JPS526711B1|1971-02-01|1977-02-24|

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KR101816318B1|2010-12-09|2018-01-12|에스케이이노베이션 주식회사|Hydroprocessing catalyst and Method for preparing the same|

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KR101918775B1|2012-08-23|2018-11-15|에스케이이노베이션 주식회사|Oxidative desulfurization process for hydrocarbon|BR112020008273A2|2017-10-27|2020-10-20|Xyleco, Inc.|biomass processing|

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RU2757365C1|2020-09-18|2021-10-14|Публичное акционерное общество "Нефтяная компания "Роснефть" |Method for reactivation of a deactivated hydrotreatment catalyst|

法律状态:
2017-05-26| PLSC| Search report ready|Effective date: 20170526 |

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2017-07-31| PLFP| Fee payment|Year of fee payment: 2 |

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2018-07-25| PLFP| Fee payment|Year of fee payment: 3 |

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2019-07-25| PLFP| Fee payment|Year of fee payment: 4 |

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2020-07-28| PLFP| Fee payment|Year of fee payment: 5 |

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2021-07-26| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1657308A|FR3035008B1|2016-07-28|2016-07-28|CATALYST BASED ON AN ORGANIC COMPOUND AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|FR1657308A| FR3035008B1|2016-07-28|2016-07-28|CATALYST BASED ON AN ORGANIC COMPOUND AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|

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PCT/EP2017/065386| WO2018019492A1|2016-07-28|2017-06-22|Catalyst made from an organic compound and use thereof in a hydroprocessing and/or hydrocracking method|

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DK17731170.1T| DK3490707T3|2016-07-28|2017-06-22|CATALYST ON THE BASIS OF AN ORGANIC COMPOUND AND ITS USE IN A HYDROGEN TREATMENT AND / OR HYDROGEN CRACKING PROCEDURE|

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US16/321,098| US11097258B2|2016-07-28|2017-06-22|Catalyst made from an organic compound and use thereof in a hydroprocessing and/or hydrocracking method|

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EP17731170.1A| EP3490707B1|2016-07-28|2017-06-22|Catalyst based on an organic compound and the use thereof in a process of hydrotreating and/or hydrocracking|