Title of Invention	"HYDROPROCESSING CATALYST, METHOD FOR THE PREPARATION THEREOF AND USE OF THE SAME"
Abstract	The invention relates to a hydrocarbon hydroconversion catalyst comprising a car- rier based on refractory oxide, a metal of the group VIII, and a metal of the group VIB. Said catalyst is characterised in that it also comprises at least one organic compound selected from the alkenediols of formula (I) wherein R1 represents a C2-10 alkenylene group, preferably C2-4 alkenylene, a C6-18 arylene group, or a C7-18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-18alkyl group, a C1-18alkeny! group, a C1-18 aryl group, a C3-8 cycloalkyl group, or a C7-2o alkylaryl or arylalkyl group, or the two groups R2 together form a divalent C3-8 group, the carbonated chain of the R2 groups containing or carrying at least one heteroatom selected from S, N and O. The invention also relates to a method for preparing one such catalyst, and to the use of said catalyst for hydrotreatment or hydroconversion.

Title of Invention

"HYDROPROCESSING CATALYST, METHOD FOR THE PREPARATION THEREOF AND USE OF THE SAME"

Abstract

The invention relates to a hydrocarbon hydroconversion catalyst comprising a car- rier based on refractory oxide, a metal of the group VIII, and a metal of the group VIB. Said catalyst is characterised in that it also comprises at least one organic compound selected from the alkenediols of formula (I) wherein R1 represents a C2-10 alkenylene group, preferably C2-4 alkenylene, a C6-18 arylene group, or a C7-18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-18alkyl group, a C1-18alkeny! group, a C1-18 aryl group, a C3-8 cycloalkyl group, or a C7-2o alkylaryl or arylalkyl group, or the two groups R2 together form a divalent C3-8 group, the carbonated chain of the R2 groups containing or carrying at least one heteroatom selected from S, N and O. The invention also relates to a method for preparing one such catalyst, and to the use of said catalyst for hydrotreatment or hydroconversion.

Full Text	HYDROPROCESSING CATALYST, METHOD FOR THE PREPARATION THEREOF AND USE OF THE SAME The present invention relates to a hydroprocessing catalyst, to the method for the preparation thereof and to the use of this catalyst in a method of hydroprocessing and/or hydrocracking hydrocarbons, in particular hydrocarbons derived from petroleum fractions with a boiling point range of between 40 and 560°C. Currently, the demand for desulfurized, denitrogenated and dearomatized hydrocarbon compounds is increasing and manufacturers are developing catalysts which are increasingly effective with respect to the purification of hydrocarbons. However, these new catalysts are much more expensive and are accessible only from a limited number of producers. In addition, from their first regeneration, these catalysts exhibit an activity that is often much lower than their initial activity in the fresh state under the same operating conditions. An additional specific rejuvenation treatment sometimes makes it possible to recover an activity similar to the initial activity and thus makes it possible to reuse the catalyst for a further cycle of deep hydrodesulfurization and the production of distillates having sulfur contents of less than 10 ppm. Several rejuvenation treatments are proposed on the market. They generally combine regeneration steps under specific conditions, and chemical and thermal treatments, and can be associated with ex situ sulfurizations of the catalyst. Numerous "conventional" catalysts, based on carriers formed of refractory oxide(s) and containing a combination of group VIB and VIII metals are today used in refineries, in the fresh or regenerated state, either in hydroprocessing or in hydrocracking. If it proves to be impossible to significantly increase their activity in desulfurization and/or denitrogenation, these catalysts will have to be recovered, stored or destroyed when the specifications imposed with regard to fuels become so restrictive that it will no longer be possible to use them. This storage or elimination of solids could also be subject to environmental and safety restrictions and could generate significant additional costs for refiners. The Applicant has therefore sought, firstly, to render known catalysts based on refractory oxide(s) and on group VIB and VIII metals more effective, and to confer on them desulfurization and denitrogenation activities that are at least equivalent to those of the best catalysts on the market, and, secondly, to improve the activity of regenerated hydroprocessing catalysts in order to increase the number of recycling cycles and to delay the point at which they are discarded and destroyed. All hydroprocessing or hydrocracking catalysts containing metals in the oxide state, in order to be active, must necessarily be sulfurized before use. This sulfurization can be carried out either in situ in the hydroprocessing reactor of the refinery, or ex situ. The sulfurization can be carried out by means of hydrogen sulfide, mercaptans, organic sulfides, polysulfides and/or elemental sulfur, these compounds being introduced alone, as a mixture with a solvent, or at the same time as the feedstock. Before this sulfurization step, some of these catalysts are premodified by a treatment with chelating or complexing organic compounds. The sulfurization and the premodification can be carried out in situ, i.e. in the hydroprocessing/hydro- conversion reactor, or else ex situ, i.e. in a dedicated reactor. A premodification ex situ combined with a sulf urization in situ in the hydroprocessing/hydroconversion reactor can also be envisioned. The range of chelating or complexing organic compounds that can be used is quite broad. It is thus known practice to modify these catalysts by means of acids of thioglycolic type, or else thioalcohols, thioacetone compounds and thiodiazoles, or thiocyanates as proposed, in particular, by the following applications: EP 289211, EP 300629, EP 338788, EP 357295, EP 456592, EP 478365 and EP 506206. Other catalysts have been modified by treatment with alcohol-acid organic compounds (EP 482817), optionally etherified mono-, di-or polyalcohols (EP 601722, US 3954673, US 4012340, WO 01/76741), compounds of urea type, polyamines, EDTA, hydrazine and other nitrogenous compounds (EP 181035, EP 335754, EP 1043069, WO 01/76741, US 3954673 and US 4012340). Catalysts modified with C2-Ci4 monoesters are described in patent applications EP 466 568 and EP 1046424. All these compounds are aimed at improving the effectiveness of the catalysts in hydroprocessing, more particularly in hydrodesulfurization. However, these modifications do not always make it possible to sufficiently increase the performance levels of the catalyst in order to face up to the specifications regarding sulfur contents in fuels which are continually becoming more and more restrictive for refiners. Thus, for example, according to the guidelines of the European Parliament and of the European Council, European Community countries must produce diesel fuel containing less than 50 ppm of sulfur from 2005 and less than 10 ppm by 2008-2011, while the 2004 standard is 350 ppm. Similarly, for all the countries of North America, the sulfur content of diesel must go from 500 ppm to 15 ppm from 2006. Certain countries such as Germany are ahead of the European legislation and already make it obligatory to sell diesel at less than 10 ppm. Similar restrictions already apply to petrol and the other fuels. This change in specifications imposes restrictions on the production by refineries, and refiners must bow to these restrictions at the cost of often ruinously expensive investments in hydroprocessing or hydrocracking units and/or, much more economically, through improving the desulfurization performance levels of the current catalysts and the possibility of recycling them several times at their highest performance level. With this aim, the Applicant has designed a new type of hydroprocessing catalyst, based on refractory oxides and on metals of groups VIB and VIII of the Periodic Table of Elements, which exhibit, after sulfurization, a greatly improved activity in desulfurization and in denitrogenation. The subject of the present invention is thus a hydrocarbon hydroprocessing catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB of the Periodic Table of Elements, characterized in that it also comprises at least one organic compound selected from the alkenediols of formula (I) (Formula Removed) RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C20 alkylaryl or C7-C20 arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and O. In fact, the Applicant has established that the presence on the catalysts of at least one organic compound of formula (I) considerably increases the effectiveness of the catalysts in desulfurization and in denitrogenation, after activation by sulfurization under known conditions. By using these new catalysts for hydrocarbon hydroprocessing, it is possible, in comparison with equivalent catalysts that have not undergone any premodification, to reduce the desulfurization reaction temperature by approximately 5 to 25°C, for a given residual sulfur content and all operating conditions being otherwise identical (pressure, amount of hydrogen and volume velocity per hour (VVH) ) . Such a gain in activity makes it possible to envision obtaining residual sulfur contents that are much less than 50 ppm, or even less than 10 ppm, in processed hydrocarbons, by varying the operating conditions. If the unit is already able to produce a low-sulfur petroleum fraction, this gain in activity will make it possible to reduce the temperature of the reactor for producing the desired sulfur content, and thus to keep the unit operational for an additional period that may be as long as several months. By way of examples of preferred compounds of formula (I), mention may be made of 2,3-dihydroxy-2-butenedioic acid, 4-cyclopentene-l,3-diol, 3-hexene-2,5-diol, pyrocatechol, 1,2-benzenedimethanol, 2,3-dihydroxy- napthoquinone, 2,3-butene-l, 4-diol, tetrahydroxy-quinone, 3,4-dihydroxybenzonitrile and 2,3-dihydroxy-benzaldehyde. In a preferred embodiment of the present invention, the compound of formula (I) is 2,3-butene-l,4-diol. Preferably, the basic catalyst is a catalyst consisting of a refractory oxide carrier of alumina, silica or silica-alumina type containing from 0.1% to 10% by weight of at least one metal of group VIII, preferably nickel and/or cobalt, and from 1% to 20% by weight of at least one metal of group VIB, preferably molybdenum. The catalyst may be a fresh, i.e. nonregenerated, catalyst originating directly from a manufacturer, but the pretreatment according to the invention with one or more compounds of formula (I) is also advantageous when it involves a catalyst regenerated by means of an appropriate chemical or thermal treatment, for example by means of calcination. It is nevertheless known that, due to a specific method of preparation, certain fresh catalysts can be more or less refractory to the recommended treatments. Similarly, for the same reasons or subsequent to specific operating conditions experienced in the unit, regenerated catalysts can prove to be more or less refractory to these treatments. The catalyst according to the invention preferably contains at least 0.001 mol of organic compound(s) of formula (I), in particular from 0.001 mol to 10 mol, preferably from 0.01 to 6 mol, and even more preferably from 0.1 to 3 mol of compound (s) of formula (I) per mole of metals of groups VIB and VIII. A subject of the invention is also a method for preparing the modified hydroprocessing catalyst described above. This method of modification comprises bringing a catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII in the oxide state and at least one metal of group VIB in the oxide state into contact with at least one organic compound selected from the alkenediols of formula (I): (Formula Removed) in which RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C20 alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0. According to the invention, the bringing into contact is generally and preferably an impregnation. When the compound(s) of formula (I) is (are) liquid(s) at the impregnation temperature, the bringing into contact with the catalyst can be carried out in the absence of solvent. The bringing of the nonmodified catalyst into contact with the organic compound of formula (I) is preferably carried out by bringing the catalyst into contact with a solution containing the organic agent. The volume of solution may be less than, equal to or greater than the pore volume of the catalyst. The method using a volume of solution less than or equal to the pore volume of the catalyst is sometimes called "dry impregnation". When the volume of solution is greater than the pore volume of the catalyst, the excess solution will be eliminated after the adsorption of the organic compound of formula (I) onto the catalyst. The catalyst can be brought into contact with the compound (s) of formula (I) or (II) in the presence of at least one solvent. When the bringing into contact is carried out in the presence of solvent, the organic compound(s) of formula (I) is (are) preferably at least partially soluble in the solvent used. The choice of the solvent is of particular importance in the implementation of the method. The selection of the solvent is based on various criteria, such as its solvent capacity for the compound(s) of formula (I), its dispersing effect on the compound(s) of formula (I), its wetting effect on the surface of the catalyst and its availability on the market under economically acceptable conditions. Among the solvents that will advantageously be used in the invention, mention may be made of water, supercritical fluids such as carbon dioxide, aromatic, aliphatic or alicyclic solvents, petroleum fractions, mono- and polyhydroxylated solvents such as ethanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propyiene glycol, polyethylene glycol (PEG), glycerol, alkyl esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, N-methylpyrrolidone, solvents containing an amide function such as dimethylacetamide, solvents containing a nitrile function such as acetonitrile, alkyl carbonates such as ethyl carbonate, ethers such as tetrahydrofuran, sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, acids such as acetic acid, and halogenated solvents, or a mixture of several of these solvents. Among these solvents, preference is in particular given to water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert-butanol, polyethylene glycol (PEG), most commonly of molecular weight from 118 (triethylene glycol) to 1000, white spirit and petroleum ether. The organic compound(s) of formula (I) can optionally be introduced in the presence of at least one acid, generally selected from carboxylic acids, hydrocarboxylic acids and polyacids (such as formic acid, acetic acid, glycolic acid, lactic acid, tartaric acid, maleic acid, citric acid, glyceric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, L-(+)-ascorbic acid, salicylic acid, oxalic acid, orthophthalic acid, succinic acid, glyoxylic acid, etc.), thiocarboxylic acids (such as thiobenzoic acid, mercaptoacetic acid, 1- and 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thioglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, etc.), aminocarboxylic acids (nitrilotriacetic acid, EDTA - for "ethylenediaminetetraacetic acid", etc.). It has already been possible to mention some of these acids previously as solvents. Among these acids, the acids particularly preferred are lactic acid, maleic acid, tartaric acid, citric acid, succinic acid, oxalic acid, thioacetic acid, thioglycolic acid, nitriloacetic acid and EDTA. The acid(s) can be introduced with the compound(s) of formula (I) or separately, if, for example, the mixture obtained is not homogeneous. In this case, it may be advantageous to use a solvent which allows the simultaneous introduction of the acid(s) with the compound(s) of formula (I), the solvent then ensuring dissolution of all the organic compounds present. Finally, it is also possible, when the acid(s) is (are) introduced separately (before or after, preferably before) from the compound of formula (I), to use a solvent different than that used to introduce the compound of formula (I). The bringing into contact of the catalyst, optionally predried at between 10 and 600°C, preferably between 15 and 300°C, more preferably from 20 to 180°C, with a solution of one or more compounds of formula (I) during the impregnation step can last from 1 minute to 7 days, preferably from 10 minutes to 8 hours, at a temperature of between 0°C and 200°C, preferably at ambient temperature, at a low pressure of between atmospheric pressure and 5 bar, preferably at atmospheric pressure. When a solution of acid(s) is introduced before the solution of organic compound(s) of formula (I), the operating conditions for the impregnation with the acid(s) are similar to those for the impregnation with the organic compound(s) of formula (I). In the optional case where the catalyst is dried, it is possible to advantageously take advantage of the residual heat of the catalyst to carry out a hot impregnation. At the end of the impregnation step, the catalyst can be subjected, optionally after elimination of an excess of impregnation solution, to an optional maturation step at a temperature generally of from 0 to 100°C, preferably ambient temperature (approximately 20°C) to 80°C, generally at atmospheric pressure or up to pressures that are generally used in hydroprocessing or hydroconversion methods, the duration of which may be between a few minutes and a few years, when the catalyst would remain stored in vats. Preferably, the maturation step can last from a few minutes to 2 days. An optional thermal treatment, consecutive to the maturation step, can be carried out at temperatures of from 50°C to 250°C, preferably from 60 to 180°C, lasting from a few minutes to several days, preferably from 30 minutes to 3 hours, under an inert or noninert atmosphere, with or without gas flow, generally at atmospheric pressure or up to pressures that are generally used in hydroprocessing or hydroconversion methods. The optional maturation and thermal treatment steps can be omitted when the catalyst is loaded directly into the hydroprocessing or hydroconversion unit. The catalyst modified by impregnation with the compound(s) of formula (I) is completely stable at ambient temperature and when exposed to the air. The modification of the catalyst can consequently be carried out ex situ, i.e. outside a hydroprocessing, generally hydroconversion, reactor, and this is a preferred embodiment of the method according to the invention. The ex situ implementation of the method according to the invention can optionally be combined with an ex situ sulfurization of the modified catalyst according to the invention. This allows the refiner to purchase a product immediately ready for use and to reduce as much as possible the time lost when initiating the unit. It is also advantageous to carry out the step of modification of the catalyst with the compound(s) of formula (I) ex situ, and to sulfurize the modified catalyst in situ in the hydroprocessing reactor. In this case, the catalyst can be placed in the processing unit more easily since, unlike the sulfurized catalyst, there is no risk of the nonsulf urized catalyst self-igniting . Yet another variant consists in carrying out both the modification of the catalyst and the subsequent sulfurization in situ. In this case, the method of preparation according to the invention is characterized in that the catalyst is brought into contact with the compound(s) of formula (I) or (II) in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds, generally in a hydroprocessing reactor. It should be noted that, even when the modification of the catalyst with the compound (s) of formula (I) is carried out in situ in the hydroprocessing reactor, these two operations generally constitute two separate steps carried out one after the other, the bringing into contact with the compound(s) of formula (I) always preceding the sulfurization step. However, these two steps can also be carried out simultaneously. In addition to the impregnation of the organic compounds into the pores of a fresh or regenerated catalyst, it is also possible to introduce said organic compounds during the manufacturing/forming of the catalyst. It is, for example, possible to incorporate the organic compound(s) of formula (I) into the carrier, even before the deposition of the compounds of metals of groups VIB and VIII. This can be done by mixing one or more organic compounds with the constituents of the carrier before the forming of the latter, or else by impregnating the carrier formed with the organic compounds. Another possibility consists in introducing the organic compound(s) and the compounds of metals of groups VIB and VIII simultaneously, either by mixing them with the constituents of the carrier before forming, or by impregnating an already formed carrier with both the organic compound(s) and the salts of metals of groups VIB and VIII. One or other of the operations can be followed by drying, carried out under conditions such that at least a part of the organic compounds is conserved in the catalyst. It is also possible to incorporate the organic compounds of formula (I) only after the salts of metals of groups VIB and VIII. One or other of these steps can optionally be followed by drying and/or calcination under conditions such that at least a part of the compounds is conserved in the catalyst. The organic compound(s) of formula (I) can be introduced into the catalyst in liquid and/or particulate solid form and/or in the form of a solution or suspension in an appropriate solvent. A subject of the invention is also a method of in situ or ex situ activation of a hydroprocessing catalyst as described above. This activation is carried out by placing the catalyst in the presence, simultaneously or successively, of hydrogen and at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds. A preferred sulfurization agent is dimethyl disulfide (DMDS). The sulf urization agent can be introduced in the form of a gas or in a form diluted in a solvent, or as an additive for the feedstock to be hydroprocessed. Finally, a subject of the invention is the use of the catalyst thus activated in situ or ex situ, for the hydroprocessing and/or hydrocracking of hydrocarbons, in particular of hydrocarbons derived from petroleum fractions with a boiling point of between 40 and 560°C. The examples given in the remainder of the present description are aimed at illustrating and not at limiting the invention. EXAMPLE 1 - Improvement in the activity of an existing commercial catalyst Example 1-1 In the present example, a method of preparing a catalyst according to the invention is described. The starting material is a commercial catalyst (catalyst A), consisting of a combination containing 3% by weight of cobalt and 10% by weight of molybdenum on an alumina carrier, available on the market and commonly used by refiners in hydrodesulfurization units. The modification of this catalyst A with a compound of formula (I) is carried out in the following way: 250 g of catalyst A are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 138 g of 2-butene-1,4-diol are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to slowly rotate (20 rpm} for 16 hours. A catalyst with a dry appearance is thus obtained. After 20 days at ambient temperature, 100 ml of this catalyst are loaded into the reactor of a pilot unit for desulfurization of diesel oil for the purpose of carrying out an activity test as described in example 1-2 below. After loading, the catalyst is subjected to heat treatment at 180°C for 2 hours, and then at 150°C for 14 hours, the whole under a stream of nitrogen of 20 1/h. The catalyst thus obtained is called catalyst B. Example 1-2 In the present example, the hydrodesulfurization and hydrodenitrogenation activity of catalyst B having undergone a modification according to the invention (example 1-1) is compared with that of catalyst A not having undergone any modification treatment. Each of catalysts A (nonmodified) and B (modified according to the invention) is sulfurized with a diesel oil with added dimethyl disulfide (DMDS) according to the procedure recommended by the manufacturer of the catalyst. After sulfurization and stabilization of catalysts A and B, a feedstock comprising a mixture of 70% by weight of diesel oil and 30% by weight of a hydrocarbon fraction of LCO (light cycle oil) type derived from catalytic cracking is introduced. The characteristics of this feedstock, before hydroprocessing, are indicated in table I.I below. TABLE I.I (Table Removed) The hydroprocessing reaction is carried out under a pressure of 27*105 Pa (27 bar) with a hydrogen/hydrocarbon (H2/HC) ratio of 250 Nl/1 at a volume velocity per hour (VVH) of 1 h~3 . The desulfurization activities are compared by determining, for each catalyst, the reaction temperature corresponding to a degree of desulfurization of 99%. The lower this temperature, for catalyst B according to the invention, in comparison with the corresponding temperature for the reference catalyst A, the more active this catalyst is in desulfurization. The results obtained are represented in table 1-2 in the form of a temperature difference (AT) relative to the reference temperature of catalyst A (THos) • They correspond to the temperature required to reach a degree of desulfurization of 99%. TABLE 1.2 (Table Removed) It is noted that catalyst B according to the invention makes it possible to reach a degree of desulfurization of 99% at a temperature 7°C lower than that required for catalyst A. It therefore has a hydrodesulfurization activity greater than that of catalyst A.To compare the denitrogenation activities, the residual nitrogen content for a given reaction temperature THDN is measured for each catalyst. The lower this residual nitrogen content, the more active the catalyst is in denitrogenation. The results obtained are represented in table 1-3. TABLE 1.3 (Table Removed) It is noted that catalyst B according to the invention makes it possible to reduce the residual nitrogen content of the feedstock to a greater extent than catalyst A, thereby showing that it is also more active in denitrogenation. EXAMPLE II - Rejuvenation of a regenerated catalyst Catalyst C is a highly effective commercial CoMo catalyst available on the market. After one in-unit cycle, it is discharged and regenerated (combustion of the residual sulfur and coke under air) . A regenerated catalyst of this type generally exhibits an activity reduced by a few degrees to more than ten or so degrees depending on the severity of the in-unit cycle, the amount of pollutants (Na, V, Ni, Pb, As, Si, etc.) that it contains, the alteration of its physical characteristics (specific surface area, pore volume, etc.) and the guality of the regeneration. An industrially regenerated catalyst C is considered. This catalyst is called catalyst D. Example II-l (according to the invention) In the present example, a method of rejuvenating a catalyst according to the invention is described. Catalyst D is modified with a compound of formula (I) in the following way: 255 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 120 g of 2-butene-l,4-diol are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to rotate slowly (20 rpm) for 16 hours. A catalyst with a dry appearance is thus obtained. After 20 days at ambient temperature, 100 ml of this catalyst are loaded into the reactor of a pilot unit for desulf urization of diesel oil for the purpose of carrying out an activity test as described in example II-4 below. After loading, the catalyst is subjected to heat treatment at 180°C for 2 hours under a stream of nitrogen of 20 Nl/h. The catalyst thus obtained is called catalyst E. Example II-2 (according to the invention) In the present example, a method of rejuvenating a catalyst according to the invention is described. Catalyst D is modified with a compound of formula (I) in the following way: 300 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 54 g (0.6 mol) of 2-butene-l,4-diol diluted in 94 ml of water are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to mature for 48 hours and then heat-treated in the rotary evaporator for 2 h at 140°C under nitrogen (GHSV 83 h"1) . A catalyst with a dry appearance is thus obtained. The catalyst thus obtained is called catalyst F. Example II-3 (comparative) In the present example, a method of rejuvenating a catalyst is described, according to a procedure identical to that applied in example II-2, but replacing the 2-butene-l,4-diol with an equivalent amount (in moles) of a diol that does not contain a carbon=carbon double bond: ethylene glycol . Ethylene glycol is one of the molecules most commonly cited in the prior art for the preparation and improvement of performance levels of HDS catalysts. Catalyst D modified with a saturated diol - ethylene glycol - is considered. Catalyst D is modified in the following way: 300 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 40 g (0.6 mol) of ethylene glycol diluted in 108 ml of water are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to mature for 48 hours and then heat-treated for 2 h at 140°C. A catalyst with a dry appearance is thus obtained. The catalyst thus obtained is called catalyst G. Example II-4 (Evaluation of catalytic activities) In the present example, the hydrodesulfurization and hydrodenitrogenation activity of catalysts E, F and G having undergone a modification (examples II-l to II-3) is compared with that of catalyst D having undergone no modification treatment. The amounts of catalyst loaded are always equal to 100 ml. The reference catalyst D is dried in the reactor for 4 h at 120°C under a flow rate of 10 Nl/h of nitrogen. Catalyst C and the modified catalysts are not subjected to drying. Each of the modified or nonmodified catalysts is sulfurized using a diesel oil with an added 2.5% by weight of dimethyl disulfide (DMDS) according to the procedure recommended by the manufacturer of the catalyst. After sulfurization, and then stabilization under direct-distillation diesel oil, a feedstock comprising a mixture of 80% by weight: of diesel oil and 20% by weight of a hydrocarbon fraction of LCO (light cycle oil) type derived from catalytic cracking is introduced. The characteristics of this feedstock, before hydroprocessing, are indicated in table II-l below. TABLE II.1 (Table Removed) The hydroprocessing reaction is carried out under a pressure of 27x105 Pa (27 bar) with a hydrogen/hydrocarbon (H2/HC) ratio of 250 Nl/1 at a volume velocity per hour (VVH) of 1 hT1. In order to compare the desulfurization activities, the reaction temperature is adjusted, for each catalyst, to a value corresponding to a degree of desulfurization of 99.5%. The lower this temperature in comparison with the corresponding temperature for the reference catalyst, the more active the catalyst under consideration is in desulfurization. The results obtained are represented in table II.2 in the form of a difference in temperature (AT) relative to the reference temperature of catalyst C (THos) corresponding to the temperature required to reach a degree of desulfurization of 99.5%. TABLE II.2 (Table Removed) It is noted that catalyst E according to the invention makes it possible to reach a degree of desulfurization of 99.5% at a temperature that is 3°C lower than that required for catalyst C. It therefore has a hydrodesulfurization activity greater than that of catalyst C, despite the fact that it was prepared from catalyst D, which is less active by 9°C compared with catalyst C. The gain in activity compared with the starting catalyst D is therefore 12°C. Catalyst F according to the invention makes it possible to reach a degree of desulfurization of 99.5% at a temperature that is 1°C above that required for catalyst C. It thus has a hydrodesulfurization activity that is barely less than that of catalyst C. The gain in activity compared with the starting catalyst D is therefore 8°C. The comparative catalyst G reaches a degree of desulfurization of 99.5% only at a temperature that is 10.5°C higher than that required for catalyst C. It therefore has a hydrodesulfurization activity which is much less than that of catalyst C and even slightly less than that of the starting catalyst D. The loss in activity compared to the starting catalyst D is 1.5°C. It is seen in these examples that the treatment according to the invention makes it possible to recover an activity equivalent to (+1°C), or even greater than (-3°C), that of the fresh catalyst, although the regenerated catalyst exhibits an activity which is very much less than that of this same catalyst when fresh. On the other hand, the use of ethylene glycol under the same conditions results in a loss of activity of the regenerated catalyst instead of the expected improvement. CLAIMS 1. A hydroprocessing catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB of the Periodic Table of Elements, characterized in that it also comprises at least one organic compound selected from the alkenediols of formula (I) (Formula Removed) in which RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C2o alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0. 2. The catalyst as claimed in claim 1, characterized in that the organic compound of formula (I) is selected from the group formed by 2,3-dihydroxy-2-butenedioic acid, 4-cyclopentene-l, 3-diol, 3-hexene-2,5-diol, pyrocatechol, 1,2-benzenedimethanol, 2,3-dihydroxy- naphthoquinone, 2,3-butene-l,4-diol, tetrahydroxyquinone, 3,4-dihydroxybenzonitrile and 2,3- dihydroxybenzaldehyde, and is preferably 2,3-butene- 1,4-diol. 3. The catalyst as claimed in either of the preceding claims, characterized in that it comprises at least 0.001 mol of at least one organic compound of formula (I) per mole of metals of groups VIB and VIII. 4. The catalyst as claimed in claim 3, characterized in that it comprises from 0.001 to 10 mol of at least one organic compound of formula (I) per mole of metals of groups VIB and VIII. 5. A method for preparing a hydroconversion catalyst as claimed in one of the preceding claims, comprising bringing a catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB into contact with' at least one organic compound selected from the alkenediols of formula (I) (Formula Removed) in which RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, Ci-C20 alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0. V 6. The method of preparation as claimed in claim 5, characterized in that the organic compound of formula (I) is selected from the group formed by 2,3-dihydroxy- 2-butenedioic acid, 4-cyclopentene-l, 3-diol, 3-hexene- 2,5-diol, pyrocatechol, 1,2-benzenedimethanol, 2,3- dihydroxynaphthoquinone , 2,3-butene-l,4-diol, tetrahydroxyquinone, 3, 4-dihydroxybenzonitrile and 2,3- dihydroxybenzaldehyde, and is preferably 2,3-butene- 1,4-diol. 7. The method of preparation as claimed in either of claims 5 and 6, characterized in that the catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB is a regenerated catalyst. 8. The method of preparation as claimed in claims 5 to 7, such that the bringing into contact is followed by at least one maturation step, at a temperature generally of from 0 to 100°C, the duration of which is between a few minutes and a few years, said maturation step being optionally followed by at least one heat treatment step, at a temperature of from 50 to 250°C, and lasting from a few minutes to several days. 9. The method of preparation as claimed in one of claims 5 to 8, characterized in that the catalyst is brought into contact with the compound(s) of formula (I) in the presence of at least one solvent and/or of at least one acid. 10. The method of preparation as claimed in the preceding claim, characterized in that the organic compound(s) of formula (I) is (are) at least partially soluble in the solvent used. 11. The method of preparation as claimed in claim 9 or 10, characterized in that the solvent is selected from water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert- butanol, polyethylene glycol (PEG), most commonly of molecular weight from 118 (triethylene glycol) to 1000, white spirit and petroleum .ether. 12. The method of preparation as claimed in one of claims 5 to 11, characterized in that the catalyst is brought into contact with the compound(s) of formula (I) ex situ, outside the hydroprocessing reactor. 13. The method of preparation as claimed in one of claims 5 to 12, characterized in that the catalyst is brought into contact with the compound(s) of formula (I) in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds, generally in a hydroprocessing reactor. 14. A method for the in situ or ex situ activation of a hydroprocessing catalyst as claimed in any one of claims 1 to 4, characterized in that said catalyst is placed in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds. 15. The method of activation as claimed in the preceding claim, characterized in that the sulfurization agent is dimethyl disulfide. 16. The use of the hydroprocessing catalyst activated by means of a method as claimed in claim 14 or 15, for the hydroprocessing and/or hydrocracking of hydrocarbons, in particular of hydrocarbons derived from petroleum fractions with a boiling point of between 40 and 560°C.

Full Text

HYDROPROCESSING CATALYST, METHOD FOR THE PREPARATION THEREOF AND USE OF THE SAME
The present invention relates to a hydroprocessing catalyst, to the method for the preparation thereof and to the use of this catalyst in a method of hydroprocessing and/or hydrocracking hydrocarbons, in particular hydrocarbons derived from petroleum fractions with a boiling point range of between 40 and 560°C.
Currently, the demand for desulfurized, denitrogenated and dearomatized hydrocarbon compounds is increasing and manufacturers are developing catalysts which are increasingly effective with respect to the purification of hydrocarbons. However, these new catalysts are much more expensive and are accessible only from a limited number of producers. In addition, from their first regeneration, these catalysts exhibit an activity that is often much lower than their initial activity in the fresh state under the same operating conditions. An additional specific rejuvenation treatment sometimes makes it possible to recover an activity similar to the initial activity and thus makes it possible to reuse the catalyst for a further cycle of deep hydrodesulfurization and the production of distillates having sulfur contents of less than 10 ppm. Several rejuvenation treatments are proposed on the market. They generally combine regeneration steps under specific conditions, and chemical and thermal treatments, and can be associated with ex situ sulfurizations of the catalyst.
Numerous "conventional" catalysts, based on carriers formed of refractory oxide(s) and containing a combination of group VIB and VIII metals are today used in refineries, in the fresh or regenerated state, either in hydroprocessing or in hydrocracking. If it

proves to be impossible to significantly increase their activity in desulfurization and/or denitrogenation, these catalysts will have to be recovered, stored or destroyed when the specifications imposed with regard to fuels become so restrictive that it will no longer be possible to use them. This storage or elimination of solids could also be subject to environmental and safety restrictions and could generate significant additional costs for refiners.
The Applicant has therefore sought, firstly, to render known catalysts based on refractory oxide(s) and on group VIB and VIII metals more effective, and to confer on them desulfurization and denitrogenation activities that are at least equivalent to those of the best catalysts on the market, and, secondly, to improve the activity of regenerated hydroprocessing catalysts in order to increase the number of recycling cycles and to delay the point at which they are discarded and destroyed.
All hydroprocessing or hydrocracking catalysts containing metals in the oxide state, in order to be active, must necessarily be sulfurized before use. This sulfurization can be carried out either in situ in the hydroprocessing reactor of the refinery, or ex situ. The sulfurization can be carried out by means of hydrogen sulfide, mercaptans, organic sulfides, polysulfides and/or elemental sulfur, these compounds being introduced alone, as a mixture with a solvent, or at the same time as the feedstock.
Before this sulfurization step, some of these catalysts are premodified by a treatment with chelating or complexing organic compounds.
The sulfurization and the premodification can be carried out in situ, i.e. in the hydroprocessing/hydro-

conversion reactor, or else ex situ, i.e. in a dedicated reactor. A premodification ex situ combined with a sulf urization in situ in the hydroprocessing/hydroconversion reactor can also be envisioned.
The range of chelating or complexing organic compounds that can be used is quite broad. It is thus known practice to modify these catalysts by means of acids of thioglycolic type, or else thioalcohols, thioacetone compounds and thiodiazoles, or thiocyanates as proposed, in particular, by the following applications: EP 289211, EP 300629, EP 338788, EP 357295, EP 456592, EP 478365 and EP 506206. Other catalysts have been modified by treatment with alcohol-acid organic compounds (EP 482817), optionally etherified mono-, di-or polyalcohols (EP 601722, US 3954673, US 4012340, WO 01/76741), compounds of urea type, polyamines, EDTA, hydrazine and other nitrogenous compounds (EP 181035, EP 335754, EP 1043069, WO 01/76741, US 3954673 and US 4012340). Catalysts modified with C2-Ci4 monoesters are described in patent applications EP 466 568 and EP 1046424.
All these compounds are aimed at improving the effectiveness of the catalysts in hydroprocessing, more particularly in hydrodesulfurization. However, these modifications do not always make it possible to sufficiently increase the performance levels of the catalyst in order to face up to the specifications regarding sulfur contents in fuels which are continually becoming more and more restrictive for refiners. Thus, for example, according to the guidelines of the European Parliament and of the European Council, European Community countries must produce diesel fuel containing less than 50 ppm of sulfur from 2005 and less than 10 ppm by 2008-2011, while the 2004 standard is 350 ppm. Similarly, for all

the countries of North America, the sulfur content of diesel must go from 500 ppm to 15 ppm from 2006. Certain countries such as Germany are ahead of the European legislation and already make it obligatory to sell diesel at less than 10 ppm. Similar restrictions already apply to petrol and the other fuels. This change in specifications imposes restrictions on the production by refineries, and refiners must bow to these restrictions at the cost of often ruinously expensive investments in hydroprocessing or hydrocracking units and/or, much more economically, through improving the desulfurization performance levels of the current catalysts and the possibility of recycling them several times at their highest performance level.
With this aim, the Applicant has designed a new type of hydroprocessing catalyst, based on refractory oxides and on metals of groups VIB and VIII of the Periodic Table of Elements, which exhibit, after sulfurization, a greatly improved activity in desulfurization and in denitrogenation.
The subject of the present invention is thus a hydrocarbon hydroprocessing catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB of the Periodic Table of Elements, characterized in that it also comprises at least one organic compound selected from the alkenediols of formula (I)
(Formula Removed)

RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C20 alkylaryl or C7-C20 arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and O.
In fact, the Applicant has established that the presence on the catalysts of at least one organic compound of formula (I) considerably increases the effectiveness of the catalysts in desulfurization and in denitrogenation, after activation by sulfurization under known conditions. By using these new catalysts for hydrocarbon hydroprocessing, it is possible, in comparison with equivalent catalysts that have not undergone any premodification, to reduce the desulfurization reaction temperature by approximately 5 to 25°C, for a given residual sulfur content and all operating conditions being otherwise identical (pressure, amount of hydrogen and volume velocity per hour (VVH) ) . Such a gain in activity makes it possible to envision obtaining residual sulfur contents that are much less than 50 ppm, or even less than 10 ppm, in processed hydrocarbons, by varying the operating conditions. If the unit is already able to produce a low-sulfur petroleum fraction, this gain in activity will make it possible to reduce the temperature of the reactor for producing the desired sulfur content, and thus to keep the unit operational for an additional period that may be as long as several months.
By way of examples of preferred compounds of formula
(I), mention may be made of 2,3-dihydroxy-2-butenedioic
acid, 4-cyclopentene-l,3-diol, 3-hexene-2,5-diol,
pyrocatechol, 1,2-benzenedimethanol, 2,3-dihydroxy-

napthoquinone, 2,3-butene-l, 4-diol, tetrahydroxy-quinone, 3,4-dihydroxybenzonitrile and 2,3-dihydroxy-benzaldehyde.
In a preferred embodiment of the present invention, the compound of formula (I) is 2,3-butene-l,4-diol.
Preferably, the basic catalyst is a catalyst consisting of a refractory oxide carrier of alumina, silica or silica-alumina type containing from 0.1% to 10% by weight of at least one metal of group VIII, preferably nickel and/or cobalt, and from 1% to 20% by weight of at least one metal of group VIB, preferably molybdenum.
The catalyst may be a fresh, i.e. nonregenerated, catalyst originating directly from a manufacturer, but the pretreatment according to the invention with one or more compounds of formula (I) is also advantageous when it involves a catalyst regenerated by means of an appropriate chemical or thermal treatment, for example by means of calcination.
It is nevertheless known that, due to a specific method of preparation, certain fresh catalysts can be more or less refractory to the recommended treatments. Similarly, for the same reasons or subsequent to specific operating conditions experienced in the unit, regenerated catalysts can prove to be more or less refractory to these treatments.
The catalyst according to the invention preferably contains at least 0.001 mol of organic compound(s) of formula (I), in particular from 0.001 mol to 10 mol, preferably from 0.01 to 6 mol, and even more preferably from 0.1 to 3 mol of compound (s) of formula (I) per mole of metals of groups VIB and VIII.

A subject of the invention is also a method for preparing the modified hydroprocessing catalyst described above. This method of modification comprises bringing a catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII in the oxide state and at least one metal of group VIB in the oxide state into contact with at least one organic compound selected from the alkenediols of formula (I):
(Formula Removed)
in which
RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C20 alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0.
According to the invention, the bringing into contact is generally and preferably an impregnation.
When the compound(s) of formula (I) is (are) liquid(s) at the impregnation temperature, the bringing into contact with the catalyst can be carried out in the absence of solvent. The bringing of the nonmodified catalyst into contact with the organic compound of formula (I) is preferably carried out by bringing the catalyst into contact with a solution containing the organic agent. The volume of solution may be less than, equal to or greater than the pore volume of the catalyst. The method using a volume of solution less than or equal to the pore volume of the catalyst is

sometimes called "dry impregnation". When the volume of solution is greater than the pore volume of the catalyst, the excess solution will be eliminated after the adsorption of the organic compound of formula (I) onto the catalyst.
The catalyst can be brought into contact with the compound (s) of formula (I) or (II) in the presence of at least one solvent.
When the bringing into contact is carried out in the presence of solvent, the organic compound(s) of formula (I) is (are) preferably at least partially soluble in the solvent used. The choice of the solvent is of particular importance in the implementation of the method. The selection of the solvent is based on various criteria, such as its solvent capacity for the compound(s) of formula (I), its dispersing effect on the compound(s) of formula (I), its wetting effect on the surface of the catalyst and its availability on the market under economically acceptable conditions.
Among the solvents that will advantageously be used in the invention, mention may be made of water, supercritical fluids such as carbon dioxide, aromatic, aliphatic or alicyclic solvents, petroleum fractions, mono- and polyhydroxylated solvents such as ethanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propyiene glycol, polyethylene glycol (PEG), glycerol, alkyl esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, N-methylpyrrolidone, solvents containing an amide function such as dimethylacetamide, solvents containing a nitrile function such as acetonitrile, alkyl carbonates such as ethyl carbonate, ethers such as tetrahydrofuran, sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, acids such as acetic

acid, and halogenated solvents, or a mixture of several of these solvents.
Among these solvents, preference is in particular given to water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert-butanol, polyethylene glycol (PEG), most commonly of molecular weight from 118 (triethylene glycol) to 1000, white spirit and petroleum ether.
The organic compound(s) of formula (I) can optionally be introduced in the presence of at least one acid, generally selected from carboxylic acids, hydrocarboxylic acids and polyacids (such as formic acid, acetic acid, glycolic acid, lactic acid, tartaric acid, maleic acid, citric acid, glyceric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, L-(+)-ascorbic acid, salicylic acid, oxalic acid, orthophthalic acid, succinic acid, glyoxylic acid, etc.), thiocarboxylic acids (such as thiobenzoic acid, mercaptoacetic acid, 1- and 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thioglycolic acid, thiodiglycolic acid, dithiodiglycolic acid, etc.), aminocarboxylic acids (nitrilotriacetic acid, EDTA - for "ethylenediaminetetraacetic acid", etc.). It has already been possible to mention some of these acids previously as solvents. Among these acids, the acids particularly preferred are lactic acid, maleic acid, tartaric acid, citric acid, succinic acid, oxalic acid, thioacetic acid, thioglycolic acid, nitriloacetic acid and EDTA.
The acid(s) can be introduced with the compound(s) of formula (I) or separately, if, for example, the mixture obtained is not homogeneous. In this case, it may be advantageous to use a solvent which allows the simultaneous introduction of the acid(s) with the

compound(s) of formula (I), the solvent then ensuring dissolution of all the organic compounds present. Finally, it is also possible, when the acid(s) is (are) introduced separately (before or after, preferably before) from the compound of formula (I), to use a solvent different than that used to introduce the compound of formula (I).
The bringing into contact of the catalyst, optionally predried at between 10 and 600°C, preferably between 15 and 300°C, more preferably from 20 to 180°C, with a solution of one or more compounds of formula (I) during the impregnation step can last from 1 minute to 7 days, preferably from 10 minutes to 8 hours, at a temperature of between 0°C and 200°C, preferably at ambient temperature, at a low pressure of between atmospheric pressure and 5 bar, preferably at atmospheric pressure. When a solution of acid(s) is introduced before the solution of organic compound(s) of formula (I), the operating conditions for the impregnation with the acid(s) are similar to those for the impregnation with the organic compound(s) of formula (I). In the optional case where the catalyst is dried, it is possible to advantageously take advantage of the residual heat of the catalyst to carry out a hot impregnation.
At the end of the impregnation step, the catalyst can be subjected, optionally after elimination of an excess of impregnation solution, to an optional maturation step at a temperature generally of from 0 to 100°C, preferably ambient temperature (approximately 20°C) to 80°C, generally at atmospheric pressure or up to pressures that are generally used in hydroprocessing or hydroconversion methods, the duration of which may be between a few minutes and a few years, when the catalyst would remain stored in vats. Preferably, the maturation step can last from a few minutes to 2 days. An optional thermal treatment, consecutive to the

maturation step, can be carried out at temperatures of from 50°C to 250°C, preferably from 60 to 180°C, lasting from a few minutes to several days, preferably from 30 minutes to 3 hours, under an inert or noninert atmosphere, with or without gas flow, generally at atmospheric pressure or up to pressures that are generally used in hydroprocessing or hydroconversion methods.
The optional maturation and thermal treatment steps can be omitted when the catalyst is loaded directly into the hydroprocessing or hydroconversion unit.
The catalyst modified by impregnation with the compound(s) of formula (I) is completely stable at ambient temperature and when exposed to the air. The modification of the catalyst can consequently be carried out ex situ, i.e. outside a hydroprocessing, generally hydroconversion, reactor, and this is a preferred embodiment of the method according to the invention. The ex situ implementation of the method according to the invention can optionally be combined with an ex situ sulfurization of the modified catalyst according to the invention. This allows the refiner to purchase a product immediately ready for use and to reduce as much as possible the time lost when initiating the unit.
It is also advantageous to carry out the step of modification of the catalyst with the compound(s) of formula (I) ex situ, and to sulfurize the modified catalyst in situ in the hydroprocessing reactor. In this case, the catalyst can be placed in the processing unit more easily since, unlike the sulfurized catalyst, there is no risk of the nonsulf urized catalyst self-igniting .

Yet another variant consists in carrying out both the modification of the catalyst and the subsequent sulfurization in situ. In this case, the method of preparation according to the invention is characterized in that the catalyst is brought into contact with the compound(s) of formula (I) or (II) in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds, generally in a hydroprocessing reactor.
It should be noted that, even when the modification of the catalyst with the compound (s) of formula (I) is carried out in situ in the hydroprocessing reactor, these two operations generally constitute two separate steps carried out one after the other, the bringing into contact with the compound(s) of formula (I) always preceding the sulfurization step. However, these two steps can also be carried out simultaneously.
In addition to the impregnation of the organic compounds into the pores of a fresh or regenerated catalyst, it is also possible to introduce said organic compounds during the manufacturing/forming of the catalyst. It is, for example, possible to incorporate the organic compound(s) of formula (I) into the carrier, even before the deposition of the compounds of metals of groups VIB and VIII. This can be done by mixing one or more organic compounds with the constituents of the carrier before the forming of the latter, or else by impregnating the carrier formed with the organic compounds.
Another possibility consists in introducing the organic compound(s) and the compounds of metals of groups VIB and VIII simultaneously, either by mixing them with the

constituents of the carrier before forming, or by impregnating an already formed carrier with both the organic compound(s) and the salts of metals of groups VIB and VIII. One or other of the operations can be followed by drying, carried out under conditions such that at least a part of the organic compounds is conserved in the catalyst.
It is also possible to incorporate the organic compounds of formula (I) only after the salts of metals of groups VIB and VIII. One or other of these steps can optionally be followed by drying and/or calcination under conditions such that at least a part of the compounds is conserved in the catalyst.
The organic compound(s) of formula (I) can be introduced into the catalyst in liquid and/or particulate solid form and/or in the form of a solution or suspension in an appropriate solvent.
A subject of the invention is also a method of in situ or ex situ activation of a hydroprocessing catalyst as described above. This activation is carried out by placing the catalyst in the presence, simultaneously or successively, of hydrogen and at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds. A preferred sulfurization agent is dimethyl disulfide (DMDS).
The sulf urization agent can be introduced in the form of a gas or in a form diluted in a solvent, or as an additive for the feedstock to be hydroprocessed.
Finally, a subject of the invention is the use of the catalyst thus activated in situ or ex situ, for the

hydroprocessing and/or hydrocracking of hydrocarbons, in particular of hydrocarbons derived from petroleum fractions with a boiling point of between 40 and 560°C.
The examples given in the remainder of the present description are aimed at illustrating and not at limiting the invention.
EXAMPLE 1 - Improvement in the activity of an existing commercial catalyst
Example 1-1
In the present example, a method of preparing a catalyst according to the invention is described.
The starting material is a commercial catalyst (catalyst A), consisting of a combination containing 3% by weight of cobalt and 10% by weight of molybdenum on an alumina carrier, available on the market and commonly used by refiners in hydrodesulfurization units.
The modification of this catalyst A with a compound of formula (I) is carried out in the following way: 250 g of catalyst A are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 138 g of 2-butene-1,4-diol are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to slowly rotate (20 rpm} for 16 hours. A catalyst with a dry appearance is thus obtained.
After 20 days at ambient temperature, 100 ml of this catalyst are loaded into the reactor of a pilot unit for desulfurization of diesel oil for the purpose of carrying out an activity test as described in example 1-2 below. After loading, the catalyst is subjected to heat treatment at 180°C for 2 hours, and

then at 150°C for 14 hours, the whole under a stream of nitrogen of 20 1/h. The catalyst thus obtained is called catalyst B.
Example 1-2
In the present example, the hydrodesulfurization and hydrodenitrogenation activity of catalyst B having undergone a modification according to the invention (example 1-1) is compared with that of catalyst A not having undergone any modification treatment.
Each of catalysts A (nonmodified) and B (modified according to the invention) is sulfurized with a diesel oil with added dimethyl disulfide (DMDS) according to the procedure recommended by the manufacturer of the catalyst.
After sulfurization and stabilization of catalysts A and B, a feedstock comprising a mixture of 70% by weight of diesel oil and 30% by weight of a hydrocarbon fraction of LCO (light cycle oil) type derived from catalytic cracking is introduced. The characteristics of this feedstock, before hydroprocessing, are indicated in table I.I below.
TABLE I.I
(Table Removed)

The hydroprocessing reaction is carried out under a pressure of 27*105 Pa (27 bar) with a hydrogen/hydrocarbon (H2/HC) ratio of 250 Nl/1 at a volume velocity per hour (VVH) of 1 h~3 .
The desulfurization activities are compared by determining, for each catalyst, the reaction temperature corresponding to a degree of desulfurization of 99%. The lower this temperature, for catalyst B according to the invention, in comparison with the corresponding temperature for the reference catalyst A, the more active this catalyst is in desulfurization.
The results obtained are represented in table 1-2 in the form of a temperature difference (AT) relative to the reference temperature of catalyst A (THos) • They correspond to the temperature required to reach a degree of desulfurization of 99%.
TABLE 1.2
(Table Removed)
It is noted that catalyst B according to the invention makes it possible to reach a degree of desulfurization of 99% at a temperature 7°C lower than that required for catalyst A. It therefore has a hydrodesulfurization activity greater than that of catalyst A.To compare the denitrogenation activities, the residual nitrogen content for a given reaction temperature THDN is measured for each catalyst. The lower this residual nitrogen content, the more active the catalyst is in denitrogenation.
The results obtained are represented in table 1-3.
TABLE 1.3

(Table Removed)
It is noted that catalyst B according to the invention makes it possible to reduce the residual nitrogen content of the feedstock to a greater extent than catalyst A, thereby showing that it is also more active in denitrogenation.
EXAMPLE II - Rejuvenation of a regenerated catalyst
Catalyst C is a highly effective commercial CoMo catalyst available on the market. After one in-unit cycle, it is discharged and regenerated (combustion of the residual sulfur and coke under air) . A regenerated catalyst of this type generally exhibits an activity reduced by a few degrees to more than ten or so degrees depending on the severity of the in-unit cycle, the amount of pollutants (Na, V, Ni, Pb, As, Si, etc.) that it contains, the alteration of its physical characteristics (specific surface area, pore volume, etc.) and the guality of the regeneration.
An industrially regenerated catalyst C is considered. This catalyst is called catalyst D.
Example II-l (according to the invention)
In the present example, a method of rejuvenating a catalyst according to the invention is described.
Catalyst D is modified with a compound of formula (I) in the following way: 255 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 120 g of 2-butene-l,4-diol are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to rotate slowly (20 rpm) for 16 hours. A catalyst with a dry appearance is thus obtained.
After 20 days at ambient temperature, 100 ml of this catalyst are loaded into the reactor of a pilot unit for desulf urization of diesel oil for the purpose of carrying out an activity test as described in example II-4 below. After loading, the catalyst is subjected to heat treatment at 180°C for 2 hours under a stream of nitrogen of 20 Nl/h. The catalyst thus obtained is called catalyst E.
Example II-2 (according to the invention)
In the present example, a method of rejuvenating a catalyst according to the invention is described.
Catalyst D is modified with a compound of formula (I) in the following way: 300 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 54 g (0.6 mol) of 2-butene-l,4-diol diluted in 94 ml of water are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to mature for 48 hours and then heat-treated in the rotary evaporator for 2 h at 140°C under nitrogen (GHSV 83 h"1) . A catalyst with a dry appearance is thus obtained. The catalyst thus obtained is called catalyst F.
Example II-3 (comparative)
In the present example, a method of rejuvenating a catalyst is described, according to a procedure identical to that applied in example II-2, but replacing the 2-butene-l,4-diol with an equivalent amount (in moles) of a diol that does not contain a carbon=carbon double bond: ethylene glycol . Ethylene glycol is one of the molecules most commonly cited in the prior art for the preparation and improvement of performance levels of HDS catalysts.
Catalyst D modified with a saturated diol - ethylene glycol - is considered. Catalyst D is modified in the following way: 300 g of catalyst D are placed in the round-bottomed flask of a rotary evaporator rotating at 45 rpm. 40 g (0.6 mol) of ethylene glycol diluted in 108 ml of water are injected, over 35 minutes, into the heart of the catalyst. The impregnated solid is left to mature for 48 hours and then heat-treated for 2 h at 140°C. A catalyst with a dry appearance is thus obtained. The catalyst thus obtained is called catalyst G.
Example II-4 (Evaluation of catalytic activities)
In the present example, the hydrodesulfurization and hydrodenitrogenation activity of catalysts E, F and G having undergone a modification (examples II-l to II-3) is compared with that of catalyst D having undergone no modification treatment.
The amounts of catalyst loaded are always equal to 100 ml.
The reference catalyst D is dried in the reactor for 4 h at 120°C under a flow rate of 10 Nl/h of nitrogen.
Catalyst C and the modified catalysts are not subjected to drying.
Each of the modified or nonmodified catalysts is sulfurized using a diesel oil with an added 2.5% by weight of dimethyl disulfide (DMDS) according to the procedure recommended by the manufacturer of the catalyst.
After sulfurization, and then stabilization under direct-distillation diesel oil, a feedstock comprising a mixture of 80% by weight: of diesel oil and 20% by weight of a hydrocarbon fraction of LCO (light cycle oil) type derived from catalytic cracking is introduced. The characteristics of this feedstock, before hydroprocessing, are indicated in table II-l below.
TABLE II.1

(Table Removed)
The hydroprocessing reaction is carried out under a pressure of 27x105 Pa (27 bar) with a hydrogen/hydrocarbon (H2/HC) ratio of 250 Nl/1 at a volume velocity per hour (VVH) of 1 hT1.
In order to compare the desulfurization activities, the reaction temperature is adjusted, for each catalyst, to a value corresponding to a degree of desulfurization of 99.5%. The lower this temperature in comparison with the corresponding temperature for the reference catalyst, the more active the catalyst under consideration is in desulfurization.
The results obtained are represented in table II.2 in the form of a difference in temperature (AT) relative to the reference temperature of catalyst C (THos) corresponding to the temperature required to reach a degree of desulfurization of 99.5%.
TABLE II.2

(Table Removed)
It is noted that catalyst E according to the invention makes it possible to reach a degree of desulfurization of 99.5% at a temperature that is 3°C lower than that required for catalyst C. It therefore has a hydrodesulfurization activity greater than that of catalyst C, despite the fact that it was prepared from catalyst D, which is less active by 9°C compared with catalyst C. The gain in activity compared with the starting catalyst D is therefore 12°C.
Catalyst F according to the invention makes it possible to reach a degree of desulfurization of 99.5% at a temperature that is 1°C above that required for catalyst C. It thus has a hydrodesulfurization activity

that is barely less than that of catalyst C. The gain in activity compared with the starting catalyst D is therefore 8°C.
The comparative catalyst G reaches a degree of desulfurization of 99.5% only at a temperature that is 10.5°C higher than that required for catalyst C. It therefore has a hydrodesulfurization activity which is much less than that of catalyst C and even slightly less than that of the starting catalyst D. The loss in activity compared to the starting catalyst D is 1.5°C.
It is seen in these examples that the treatment according to the invention makes it possible to recover an activity equivalent to (+1°C), or even greater than (-3°C), that of the fresh catalyst, although the regenerated catalyst exhibits an activity which is very much less than that of this same catalyst when fresh. On the other hand, the use of ethylene glycol under the same conditions results in a loss of activity of the regenerated catalyst instead of the expected improvement.

CLAIMS
1. A hydroprocessing catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB of the Periodic Table of Elements, characterized in that it also comprises at least one organic compound selected from the alkenediols of formula (I)
(Formula Removed)
in which
RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, C7-C2o alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0.
2. The catalyst as claimed in claim 1, characterized
in that the organic compound of formula (I) is selected
from the group formed by 2,3-dihydroxy-2-butenedioic
acid, 4-cyclopentene-l, 3-diol, 3-hexene-2,5-diol,
pyrocatechol, 1,2-benzenedimethanol, 2,3-dihydroxy-
naphthoquinone, 2,3-butene-l,4-diol,
tetrahydroxyquinone, 3,4-dihydroxybenzonitrile and 2,3-
dihydroxybenzaldehyde, and is preferably 2,3-butene-
1,4-diol.
3. The catalyst as claimed in either of the preceding
claims, characterized in that it comprises at least
0.001 mol of at least one organic compound of formula
(I) per mole of metals of groups VIB and VIII.

4. The catalyst as claimed in claim 3, characterized
in that it comprises from 0.001 to 10 mol of at least
one organic compound of formula (I) per mole of metals
of groups VIB and VIII.
5. A method for preparing a hydroconversion catalyst
as claimed in one of the preceding claims, comprising
bringing a catalyst comprising a carrier based on at
least one refractory oxide, at least one metal of group
VIII and at least one metal of group VIB into contact
with' at least one organic compound selected from the
alkenediols of formula (I)
(Formula Removed)
in which
RI represents a C2-C10, preferably C2-C4, alkenylene group, a C6-C18 arylene group or a C7-C18 alkylene-arylene group, and each R2 independently represents a hydrogen atom or a C1-C18 alkyl, C1-C18 alkenyl, C6-C18 aryl, C3-C8 cycloalkyl, Ci-C20 alkylaryl or C7-C2o arylalkyl group, or the two R2 groups together form a C2-C18 divalent group, it being possible for the carbon chain of the R2 groups to contain or bear one or more heteroatoms selected from S, N and 0.
V
6. The method of preparation as claimed in claim 5,
characterized in that the organic compound of formula
(I) is selected from the group formed by 2,3-dihydroxy-
2-butenedioic acid, 4-cyclopentene-l, 3-diol, 3-hexene-
2,5-diol, pyrocatechol, 1,2-benzenedimethanol, 2,3-
dihydroxynaphthoquinone , 2,3-butene-l,4-diol,
tetrahydroxyquinone, 3, 4-dihydroxybenzonitrile and 2,3-
dihydroxybenzaldehyde, and is preferably 2,3-butene-
1,4-diol.

7. The method of preparation as claimed in either of
claims 5 and 6, characterized in that the catalyst
comprising a carrier based on at least one refractory
oxide, at least one metal of group VIII and at least
one metal of group VIB is a regenerated catalyst.
8. The method of preparation as claimed in claims 5
to 7, such that the bringing into contact is followed
by at least one maturation step, at a temperature
generally of from 0 to 100°C, the duration of which is
between a few minutes and a few years, said maturation
step being optionally followed by at least one heat
treatment step, at a temperature of from 50 to 250°C,
and lasting from a few minutes to several days.
9. The method of preparation as claimed in one of
claims 5 to 8, characterized in that the catalyst is
brought into contact with the compound(s) of formula
(I) in the presence of at least one solvent and/or of
at least one acid.
10. The method of preparation as claimed in the
preceding claim, characterized in that the organic
compound(s) of formula (I) is (are) at least partially
soluble in the solvent used.
11. The method of preparation as claimed in claim 9 or
10, characterized in that the solvent is selected from
water, toluene, xylenes, ethylene glycol, diethylene
glycol, triethylene glycol, glycerol, ethanol, tert-
butanol, polyethylene glycol (PEG), most commonly of
molecular weight from 118 (triethylene glycol) to 1000,
white spirit and petroleum .ether.
12. The method of preparation as claimed in one of
claims 5 to 11, characterized in that the catalyst is

brought into contact with the compound(s) of formula (I) ex situ, outside the hydroprocessing reactor.
13. The method of preparation as claimed in one of
claims 5 to 12, characterized in that the catalyst is
brought into contact with the compound(s) of formula
(I) in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS2, mercaptans, sulfides and/or polysulfides, and hydrocarbon fractions with a boiling point of less than 400°C containing sulfur compounds, generally in a hydroprocessing reactor.
14. A method for the in situ or ex situ activation of
a hydroprocessing catalyst as claimed in any one of
claims 1 to 4, characterized in that said catalyst is
placed in the presence of hydrogen and of at least one
sulfurization agent preferably selected from hydrogen
sulfide, elemental sulfur, CS2, mercaptans, sulfides
and/or polysulfides, and hydrocarbon fractions with a
boiling point of less than 400°C containing sulfur
compounds.
15. The method of activation as claimed in the
preceding claim, characterized in that the
sulfurization agent is dimethyl disulfide.
16. The use of the hydroprocessing catalyst activated
by means of a method as claimed in claim 14 or 15, for
the hydroprocessing and/or hydrocracking of
hydrocarbons, in particular of hydrocarbons derived
from petroleum fractions with a boiling point of
between 40 and 560°C.

Documents:

5592-delnp-2007-Abstract-(23-05-2013).pdf

5592-delnp-2007-abstract.pdf

5592-delnp-2007-Assignment-(21-05-2010).pdf

5592-delnp-2007-Claims-(16-12-2013).pdf

5592-delnp-2007-Claims-(23-05-2013).pdf

5592-delnp-2007-claims.pdf

5592-delnp-2007-Correspondence Others-(16-12-2013).pdf

5592-delnp-2007-correspondence-other.pdf

5592-DELNP-2007-Correspondence-Others-(16-03-2009).pdf

5592-delnp-2007-Correspondence-Others-(21-05-2010).pdf

5592-delnp-2007-Correspondence-Others-(23-05-2013).pdf

5592-delnp-2007-Correspondence-Others-(30-12-2008).pdf

5592-delnp-2007-description (complete).pdf

5592-delnp-2007-form-1.pdf

5592-delnp-2007-form-13-(16-03-2009).pdf

5592-delnp-2007-Form-18-(30-12-2008).pdf

5592-delnp-2007-Form-2-(16-12-2013).pdf

5592-delnp-2007-Form-2-(23-05-2013).pdf

5592-delnp-2007-form-2.pdf

5592-delnp-2007-Form-3-(16-12-2013).pdf

5592-delnp-2007-Form-3-(23-05-2013).pdf

5592-delnp-2007-form-3.pdf

5592-delnp-2007-form-5.pdf

5592-DELNP-2007-GPA-(16-03-2009).pdf

5592-delnp-2007-GPA-(23-05-2013).pdf

5592-DELNP-2007-Others-Document-(16-03-2009).pdf

5592-delnp-2007-Petition-137-(23-05-2013).pdf

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Patent Number

258998

Indian Patent Application Number

5592/DELNP/2007

PG Journal Number

08/2014

Publication Date

21-Feb-2014

Grant Date

20-Feb-2014

Date of Filing

19-Jul-2007

Name of Patentee

TOTAL RAFFINAGE MARKETING

Applicant Address

TOUR TOTAL, 24, COURS MICHELET, 92800 PUTEAUX, FRANCE.

Inventors:

#	Inventor's Name	Inventor's Address
1	GEORGES FREMY	CHEMIN DE COULOMME, 64390 SAUVETERRE DE BEARN, FRANCE
2	FRANCIS HUMBLOT	720, ROUTE DU TUS, 64300 LANNEPLAA,FRANCE
3	THIERRY CHOLLEY	DIEWEG 36C, B-1180 BRUXELLES, BELGIUM.
4	JEAN-PIERRE DATH	RUE D'ATH, 53, B-7970 BELOEIL HAINAULT, BELGIUM
5	CLAUDE BRUN	5, CLOS SAINT PIERRE, 64320 IDRON, FRANCE

PCT International Classification Number

B01J 23/88

PCT International Application Number

PCT/FR2006/000054

PCT International Filing date

2006-01-19

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0500577	2005-01-20	France