A CATALYST BASED ON Y-VALEROLACTONE AND / OR ITS HYDROLYSIS PRODUCTS AND ITS USE IN A HYDROTREATMENT

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 at least one additive chosen from y- valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. The invention also relates to the process for preparing said catalyst and its use in a hydrotreatment and / or hydrocracking process.
公开号:FR3035601A1
申请号:FR1553914
申请日:2015-04-30
公开日:2016-11-04
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 which is additive with γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and / or 4-pentenoic acid, its method of preparation and its use in the field of hydrotreatment and / or hydrocracking.
[0002] 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 , 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 20 2003/70 / EC, pages L76 / 10-L76 / 19) has forced refiners to reduce very little strongly 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). On the other hand, the refiners are forced to use charges that are increasingly refractory to the hydrotreatment processes on the one hand because the crudes are heavier and therefore contain more and more impurities, on the other hand because of the increase of 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 shorter cycle times. These fillers require catalysts having hydrodesulphurizing and hydrogenating functions which are greatly improved compared to conventional 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. Before their use in a hydrotreatment and / or hydrocracking reaction, these catalysts are generally subjected to sulphidation in order to form the active species. The addition of an organic compound to the hydrotreatment catalysts to improve their activity has been recommended by those skilled in the art, especially for catalysts which have been prepared by impregnation followed by drying without subsequent calcination. These catalysts are often called "dried catalyst additives". 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 documents WO96 / 41848, WO001 / 76741, US4012340, US3954673, EP601722, and WO2005 / 035691. . The prior art more rarely refers to additives comprising ester functions (EP1046424, WO2006 / 077326). 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. US2014 / 0305842 discloses the use of heterocyclic compounds, containing oxygen or nitrogen in the ring, such as lactams, oxacycloalkanes or lactones. With regard to lactones in particular, this document mentions p-proprio-lactone, γ-butyrolactone and δ-valerolactone. However, none of the additive literature describes the use of γ-valerolactone or even 4-hydroxyvaleric acid or 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid which can be obtained directly or indirectly by hydrolysis of γ-valerolactone. Whatever the compounds chosen, the induced modifications do not always make it possible to sufficiently increase 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.
[0003] Therefore, it is essential for catalyst manufacturers to find new hydrotreatment and / or hydrocracking catalysts with improved performance.
[0004] The invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and at least one additive selected from among valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. The applicant has indeed found that the use of at least one additive selected from y-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid as an organic additive (s) on a catalyst containing at least one group VIII element and at least one group VIB element, it was possible to obtain a hydrotreatment and / or hydrocracking catalyst showing improved catalytic performance. Indeed, the catalyst according to the invention shows an increased activity compared to the catalysts not additivés and dried catalysts additives known.
[0005] 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. Likewise, the stability is increased because the cycle time is prolonged due to the necessary temperature reduction. The catalyst according to the present invention is also easier to prepare because of the high solubility of γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and 4-pentenoic acid in water or any other protic polar solvent. In addition, the catalyst according to the invention may be prepared from a biomass feedstock preferably containing predominantly γ-valerolactone (JC Serrano-Ruiz in Green Chem., 2010, 12, 574- 577 or by WRH Wright and R. Palkovits in ChemSusChem 2012, 5, 9, 1657-1667) while remaining at an acceptable cost price.
[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.
[0007] According to one variant, the molar ratio of Group VIII element to Group VIB element 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 P205 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. According to one variant, the total content of additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid is between 1 and 35% by weight based on the total weight of the catalyst.
[0008] Alternatively, the catalyst further contains an organic compound other than the additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-hydroxy acid. -pentenoic, said organic compound containing oxygen and / or nitrogen and / or sulfur. According to this variant, the 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 selected from triethylene glycol, diethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, citric acid, dimethylformamide, bicine, or tricine. According to one variant, the support contains from 0.1 to 50% by weight of zeolite. According to a variant, the catalyst is at least partially sulphurized. 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, is brought into contact with at least one component an additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus with an alumina-based support or silica or silica-alumina, or 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 at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid , so as to obtain a catalyst precursor, b) drying said catalyst catalyst scavenger from step a) at a temperature below 200 ° C, without calcining it later.
[0009] According to one variant, step a) is the following step: a ') 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, at least one additive selected from yvalerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus of to obtain a catalyst precursor. According to another variant, step a) comprises the following steps: a1) a support based on alumina or silica or silica-alumina is impregnated with at least one solution containing at least one element from group VIB, at minus 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 the dried impregnated support to obtain a calcined impregnated support, 3035601 7 a3) the dried and optionally calcined impregnated support obtained in step a2) is impregnated with an impregnating solution comprising at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor, a4) optionally, the precursor of catalyst obtained in step a3). According to another variant, step a) comprises the following steps: (a) preparing a support comprising at least at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid and 2-pentenoic acid; , 3-pentenoic acid or 4-pentenoic acid and optionally at least a portion of the phosphorus, a2 ') the support obtained in step a1') is impregnated with an impregnation solution comprising at least one element of group VIB, 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.
[0010] According to another variant, step a) comprises the following steps: a) a solution containing at least one element of group VIB, at least one element of group VIII, at least one compound, is contacted by co-impregnation; organic composition 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, the dried impregnated support coming from the step a2 ") with a solution of an organic compound containing oxygen and / or nitrogen and / or sulfur identical or different from that used in step a1" ") so as to obtain a precursor of catalyst, a4 ") optionally, the catalyst precursor is allowed to mature obtained in step a3 "), and at least one of the organic compounds of step a1" - or step a3 ") is selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. According to a variant, when it is desired to prepare the catalyst according to the invention from a regenerated catalyst, step a) of the preparation process comprises the following 10 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 impregnation solution comprising at least one less an additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor, a2 ") optionally the catalyst precursor obtained in step a1 '') is allowed to mature.
[0011] According to one variant, the total molar ratio of the additive (s) chosen (s) from yvalerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4- acid. The pentenoic group VIII element (s) is between 0.1 and 5.0 mol / mol. 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 for 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, the group 3035601 9 VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification. Hydroprocessing is understood to include 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 with at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid and 3-pentenoic acid. or 4-pentenoic acid. 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 at least one additive selected from among valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. 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.
[0012] 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 to at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid to obtain the catalyst. rejuvenated. 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 additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. The hydrogenating function of said catalyst, also called the active phase, is provided by at least one element of group VIB and at least one element of group VIII. The preferred group VIB elements are molybdenum and tungsten. The preferred group VIII elements are non-noble elements and in particular cobalt and nickel. Advantageously, the hydrogenating function is chosen from the group formed by the combinations of cobalt-molybdenum, nickel-1 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 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 can be advantageously used. The total content of Group VIB and Group VIII elements is advantageously greater than 6% by weight expressed as oxide based on 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 relative to the total weight of the product. 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.
[0013] The molar ratio of element of group VIII to element of group VIB in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0, 2 and 0.5. The catalyst according to the invention advantageously also comprises phosphorus as a dopant. The dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase. The phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed as P205, preferably between 0.2 and 15% by weight expressed as P205, and very preferably between 0.3 and 10% by weight. weight expressed in P205. The phosphorus molar ratio on the group VIB element 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 0.08 and 0.08. and 0.7 and very preferably between 0.08 and 0.5.
[0014] 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% by weight, and very preferably between 0.2 and 5% by weight.
[0015] 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 10% by weight. 5% 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. 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 a model Autopore III TM apparatus of the brand MicromériticsTM. The specific surface of the alumina support is advantageously between 5 and 400 m 2 g -1, preferably between 10 and 350 m 2 g -1, more preferably between 40 and 350 m 2. 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. 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% by weight. Silicon sources are well known to those skilled in the art. By way of example, mention may be made of silicic acid, silica in powder form or in colloidal form (silica sol), tetraethylorthosilicate Si (OEt) 4.
[0017] 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.
[0018] 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. 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) including phosphorus and / or at least one part of organic compound (s) containing oxygen (at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid or other additive containing oxygen) and / or nitrogen and / or sulfur which have been introduced outside the impregnations (introduced for example during the preparation of the support).
[0019] 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 at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. Y-valerolactone, 4-hydroxyvaleric acid and 2-pentenoic, 3-pentenoic and 4-pentenoic acids respectively correspond to the following formulas (a), (b), (c), (d) and (e) described below. after: (a) (b) o (d) HOW (e) HO 2-Pentenoic acid and 3-pentenoic acid may be in the form of the E-isomer or Z or a mixture of the two isomers. The presence of at least one additive selected from γ-valerolactone, hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4pentenoic acid on the catalyst makes it possible to observe an activity increased by in relation to the non-additive catalysts and the known additivated dried catalysts. Without being bound by any theory, it will be noted that 4-hydroxyvaleric acid or 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid can be obtained directly or indirectly by hydrolysis of the yvalérolactone. Indeed, γ-valerolactone can hydrolytically generate 4-hydroxy valeric acid as suggested by the work of Raghunath V. Chaudhari in Top Catal (2012) 55: 439-445 or by William N. Fishbein and Samuel P. Bessman in The Journal of Biological Chemistry, Vol. 241, No. 21, Issue of 15 November 10, pp. 4842 to 4847.1966. The latter can then be dehydrated in an acid medium (Langmuir, 2010,26 (21), pp. 16291-16298 by JQ Bond, DM Alonso, RM West, and JA Dumesic) leading to a mixture between 2-pentenoic acid, 3-pentenoic acid and / or 4-pentenoic acid. According to one variant, the presence of at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and / or 4-pentenoic acid on the catalyst may be due to the addition as such of the additive (s), alone or in admixture. According to another variant, the presence of at least one additive chosen from 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and / or 425 pentenoic acid on the catalyst may be due to hydrolysis of the γ-valerolactone 3035601 contained in the impregnating solution added to said catalytic precursor or support and optionally to a subsequent dehydration step. The total content of additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and / or pentenoic acid on the catalyst according to the invention is between 1 and 35% by weight, preferably between 2 and 30% by weight, and more preferably between 3 and 25% by weight relative to the total weight of the catalyst. During the preparation of the catalyst, the drying step (s) consecutive to the introduction of the additive (s) is (are) carried out at a temperature below 200 ° C. in order to preserve preferably at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of additive (s) introduced (s) calculated on the basis of the carbon remaining on the catalyst. The catalyst according to the invention may comprise in addition to the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid and or 4-pentenoic acid 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. Subsequently in the text, the term "said additives" will be understood to mean at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or acid. 4-pentenoic. More particularly, the catalyst according to the invention may further comprise one or more organic compounds containing oxygen other than said additives 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 organic compounds containing oxygen other than said additives, and / or one or more organic compounds containing nitrogen. Preferably, the organic compound contains at least 2 carbon atoms and at least one oxygen and / or nitrogen atom. Generally, the organic compound is chosen from a compound comprising one or more chemical 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 chosen from a compound comprising two alcohol functions and / or two carboxylic functions and / or two ester functions and / or at least one amide function.
[0020] The oxygen-containing organic compound may be one or more of compounds having one or more chemical functions selected from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function. 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, y-ketovaleric, C1-C4 dialkyl succinate, methyl acetoacetate, lactone, dibenzofuran, crown ether, orthophthalic acid, glucose and propylene carbonate. 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.
[0021] The organic compound containing oxygen and nitrogen may be one or more selected from compounds having one or more chemical functions selected from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate function. amine, nitrile, imide, amide, urea or oxime. By way of example, the oxygen and nitrogen containing organic compound may be one or more selected from the group consisting of 1,2-cyclohexanediaminetetraacetic 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 functional groups selected from thiol, thioether, sulfone or sulfoxide functions. 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.
[0022] Preferably, the organic compound contains oxygen, preferably it is selected from triethylene glycol, diethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, citric acid, dimethylformamide, bicine, or tricine. When (s) is / are present, the total content of organic compound (s) with additive function (s) (other than said additives) containing oxygen and / or nitrogen and / or sulfur on the catalyst according to the invention is between 1 and 30% by weight, preferably between 1.5 and 25% by weight, and more preferably between 2 and 20% by weight relative to the total weight of the catalyst.
[0023] Preparation method The catalyst according to the invention can be prepared according to any method of preparation of a supported catalyst additive with an organic compound known to those skilled in the art.
[0024] The catalyst according to the invention can 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, at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus with a carrier 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 Group VIII element and optionally phosphorus with at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-acid -pentenoic, so as to obtain a catalyst precursor, b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without calcining it later. The process for the preparation of a fresh catalyst, followed by the process of preparing a rejuvenated catalyst, will be described first. 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 the introduction of the additive chosen from γ-valerolactone, the acid 4-hydroxyvaleric, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid which can be carried out either at the same time as the impregnation of the metals (co-impregnation), or 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, can take place in one or more stages.
[0025] 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 additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid or any other organic compound containing oxygen and / or nitrogen and / or sulfur to preserve at least in part the additive (s) chosen from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid 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 at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid or any other organic compound containing oxygen and / or nitrogen and / or sulfur, especially after the impregnation of the elements of group VIB and VIII (post-impregnation), optionally 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 not then in an oxide form.
[0026] 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. impregnation agent 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 also comprises at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3 -pentenoic or 4-pentenoic acid. 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. Group VIB and Group VIII elements 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. 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, phosphomolybdic acid ( H3PMo12040) and their salts, and optionally silicomolybdic acid (H4SiMo12040) and its salts. Molybdenum sources may also be heteropoly compounds of the Keggin, Keggin Lacunary, Keggin substituted, Dawson, Anderson, Strandberg type, for example. Molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, Keggin lacunary 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, it is possible to use oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts. salts, and optionally silicotungstic acid (H4SiW12O40) and its salts. The sources of tungsten may also be heteropolycomposites of the Keggin, Keggin lacunary, Keggin substituted, Dawson type, for example. Oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of the Keggin, Keggin lacunary or substituted Keggin type are preferably used.
[0027] The precursors of the group VIII elements which may be used are advantageously selected from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of the group VIII elements, for example, nickel hydroxycarbonate, carbonate or the like. cobalt hydroxide are used in a preferred manner.
[0028] 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. Said phosphorus may advantageously be introduced alone or in admixture with at least one of the elements of group VIB and of group VIII, and this during any of the stages of impregnation of the hydrogenating function if this is introduced in several times. Said phosphorus may also be introduced, in whole or in part, during the impregnation of at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid if it is introduced separately from the hydrogenating function (case 3035601 22 of the post- and pre-impregnation described later) and this in the presence or absence of an organic compound containing oxygen and and / or nitrogen and / or sulfur other than said additives. 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. The preferred phosphorus precursor is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable. Phosphorus may also be introduced together with Group VIB element (s) as Keggin, Keggin lacunary, Keggin substituted or Strandberg heteropolyanions. The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid is advantageously introduced into a solution. of impregnation which, according to the method of preparation, may be the same solution or a solution different from that containing the elements of group VIB and VIII, in a total amount corresponding to: - a total molar ratio of the additive (s) selected from y-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid by Group VIB element (s) of the catalyst precursor between 0.2 to 2.0 mol / mol, preferably between 0.3 to 1.7 mol / mol, preferably between 0.5 and 1.5 mol / mol and very preferably, including between 0.8 and 1.2 mol / mol, calculated on the basis of the ingredients introduced into the impregnating solution (s), and - at a molar ratio t otal of the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid by element (s) group VIII of the catalyst precursor of between 0.1 to 5.0 mol / mol, preferably between 0.5 and 4.0 mol / mol, preferably between 1.0 and 3.0 mol / mol mol and very preferably, between 1.5 and 3.0 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s). Any impregnation 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 can also be advantageously chosen from the group formed by propylene carbonate, DMSO (dimethylsulfoxide), N-methylpyrrolidone (NMP) or sulfolane, alone or as a mixture. Preferably, a polar protic solvent is used. A list of the usual 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 472474. Very preferably, the solvent used is water or ethanol, and particularly preferably, the solvent is water. In one possible embodiment, the solvent may be absent in the impregnating solution. 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 manner as the introduction of phosphorus to various stages of preparation and 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 this 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 at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid and 3-pentenoic acid. or 4-pentenoic acid 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 containing oxygen and / or nitrogen and / or sulfur other than said additives. It can also be introduced as soon as the support is synthesized, 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. 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 precursors of the metals, the phosphorus precursor and the precursor (s) of the dopant (s), and also containing minus one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid in the co-impregnation mode). 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. When the catalyst further comprises an additional additive (in addition to the one or more additive (s) selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid) or a further group of additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives, it may be introduced into the impregnating solution of step a).
[0029] The total molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur other than said Group VIB element additives to the catalyst is between From 0.05 to 5 mol / mol, preferably from 0.1 to 4 mol / mol, preferably from 0.2 to 3 mol / mol, calculated on the basis of the components introduced into the solution or solutions ( s) impregnation. The total molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur other than said additives relative to the sum of yvalerolactone, 4-hydroxyvaleric acid , 2-pentenoic acid, 3-pentenoic acid and / or 4-pentenoic acid, is between 0.05 and 6 mol / mol, preferably between 0.1 and 5 mol mol, preferably between 0.2 and 4 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s). 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 ambient temperature. Generally a ripening time of from ten minutes to forty-eight hours and preferably from thirty minutes to five hours is sufficient. Longer durations are not excluded, but do not necessarily improve. In accordance with step b) of the preparation process according to the invention, the catalyst precursor obtained in step a) optionally matured is subjected to a drying step at a temperature below 200 ° C without subsequent calcination step . Any drying step subsequent to the introduction of said additives described in the present invention is carried out at a temperature below 200 ° C, preferably between 50 and 180 ° C, geographically between 70 and 150 ° C and very preferably between 75 and 130 ° C. The drying step is advantageously carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or 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. In a very preferred manner, 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 additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid and -pentenoic or 4-pentenoic acid introduced (s) during an impregnation step, preferably this amount is greater than 50% and even more preferably greater than 70%, calculated on the basis of the remaining carbon on the catalyst. When an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives is present, the drying step is carried out so as to preferably retain at least 30%, preferably at least 50%, and very 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.
[0030] Co-impregnation According to a first embodiment of step a) of the process for preparing the catalyst (fresh), the said components of the elements of group VIB, group VIII, of at least one additive are deposited. selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus on said support, by one or more steps of co-impregnation, that is to say that said components of group VIB elements, of group VIII, of at least one additive chosen from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid 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 element of group VIB, 10 at least one group VIII element, at least one additive selected from y-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus to obtain a catalyst precursor. The co-impregnation step (s) is (are) preferably carried out by dry impregnation or impregnation in excess of solution. When this first embodiment 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 period of maturation has been observed between impregnation and drying. Very preferably, during the preparation via co-impregnation, the group VIB and group VIII elements, at least one additive selected from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, the acid 3-pentenoic or 4-pentenoic acid, optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives are introduced in step a) in their entirety after forming said support, by dry impregnation of said support with an aqueous impregnating solution containing the precursors of the elements 3035601 28 elements group VIB and group VIII, at least one additive chosen from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid, optionally the phosphorus precursor , possibly the precursor dopant selected from boron and / or fluorine and optionally the organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives. 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 additive chosen from γ-valerolactone, the acid, is brought into contact with each other. 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid with a dried and optionally calcined impregnated support 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, so as to obtain a catalyst precursor. This second embodiment is a "post-impregnation" preparation of at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid. This is carried out for example by dry impregnation.
[0031] 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 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 least once. temperature below 200 ° C to obtain a dried impregnated support, and optionally dried dried impregnated support is calcined to obtain a calcined impregnated support, 3035601 29 a3) is impregnated dried and optionally calcined impregnated support obtained in step a2) by a impregnation solution comprising at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to to obtain a catalyst precursor, a4) optionally, the catalyst precursor obtained in step a3) is allowed to mature. 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. 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. ° C, very preferably between -30 ° C and optionally a maturation period was observed between impregnation and drying. Each intermediate drying stage, prior to the introduction of at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4- acid. pentenoic can be followed by a calcination step under the conditions described below for step a2).
[0032] 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 containing oxygen and / or nitrogen and / or sulfur other than said additives are introduced in step a1) in full after the shaping of said support, by dry impregnation of said support 3035601 30 an aqueous impregnation solution containing the precursors of the 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 containing the oxygen and / or nitrogen and / or sulfur other than said additives. 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 containing oxygen and / or nitrogen and and / or sulfur other than said additives may 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 750 ° 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 one additive chosen from yvalerolactone, 4-hydroxyvaleric acid and 2-pentenoic acid. , 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor.
[0033] The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid may advantageously be used. be deposited in one or more steps either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art. Preferably, said additive (s) is / are introduced (s) 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.
[0034] The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid is advantageously introduced ( s) in the impregnating solution of step a3) with the molar ratios per element of group VIB or group VIII described above.
[0035] When it is desired to further introduce an additional additive (in addition to the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3- pentenoic acid or 4-pentenoic acid) or a group of additional additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives, this may be introduced in the impregnating solution of step a1) and / or in the impregnating solution of step a3) or else by a further impregnation step at any time of the preparation process before final drying of step b), it being understood that no calcination step is carried out after its introduction. 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.
[0036] In accordance with 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 subsequent calcination step as described above.
[0037] Pre-impregnation According to a third embodiment of step a) of the catalyst preparation process (fresh) 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 at least one additive selected from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor. This third embodiment is a "pre-impregnation" preparation of at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid and 3-pentenoic acid. or 4-pentenoic acid. This is carried out for example by dry impregnation. 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 additive selected from y- valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally at least a portion of the phosphorus, a2 ') the support obtained in step is impregnated (a ') 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, optionally, the precursor of catalyst obtained in step a2 ').
[0038] In step a1 ') of the implementation by pre-impregnation, a support is prepared comprising at least at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid and 2-pentenoic acid. , 3-pentenoic acid or 4-pentenoic acid and optionally at least a portion of the phosphorus. The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid can be introduced (s). ) at any time during the preparation of the support, and preferably during the shaping or by impregnation on a support already formed.
[0039] If the introduction of at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid on the support previously shaped, then it can be performed 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, γ-valerolactone, 4-hydroxyvaleric acid, 2pentenoic acid, 3-pentenoic acid and / or 4-pentenoic acid which can be introduced at any time of extrusion mixing. 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 additive (s) 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 from the preparation of the support, and preferably during shaping or by impregnation on a support already formed as described above. If the phosphorus 3035601 is introduced alone to the shaping, that is to say without an additive chosen from yvalérolactone, 4-hydroxyvalérique acid, 2-pentenoic acid, 3-pentenoic acid or the 4-pentenoic acid 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 impregnations to dryness, and, preferably, by a single dry impregnation of said support, using 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.
[0040] When it is desired to further introduce an additional additive (in addition to the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3- pentenoic acid or 4-pentenoic acid) or a group of additional additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives, this may be introduced in the support of step al ') during shaping or impregnation, and / or in the impregnating solution of step a2') or by an additional impregnation step to 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.
[0041] 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.
[0042] 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 can be identical or different from that used for co-impregnation, since at least one of the organic compounds is selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, -pentenoic or 4-pentenoic acid. According to this alternative embodiment, the contacting according to step a) comprises the following successive steps: (a) a solution containing at least one element of group VIB is contacted by co-impregnation, at least a group VIII element, 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; in order 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"). contact the dried impregnated support from step a2 ") with a solution of an organic compound containing oxygen and / or nitrogen and / or sulfur identical or different from that used in step a ") 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 selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3- pentenoic acid or 4-pentenoic acid. The operating conditions described above are of course applicable in the context of this latter embodiment.
[0043] Process for the preparation of a rejuvenated 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 at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, acid 3 -pentenoic or 4-pentenoic acid so as to obtain a catalyst precursor, b) said catalyst precursor from step a) is dried at a temperature below 200 ° C, without calcining it later.
[0044] According to step a) a regenerated catalyst is contacted with at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or the acid 4-pentenoic, 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 hydrotreating 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 most often between 400 and 520 ° C, or erbre 420 and 520 ° C, or between 450 and 520 ° C, temperatures below 500 ° C is 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 respective proportion shown above. Following regeneration (calcination step) the hydrogenating function comprising the group VIB and group VIII elements of the regenerated catalyst is in an oxide form. It may also contain other dopants than phosphorus, as described above. According to this embodiment, the contacting according to step a) comprises the following successive steps: (a) impregnating 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 additive selected from γ-valerolactone, the acid 4-hydroxyvaleric, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor, a2 ") optionally, is allowed to mature the catalyst precursor obtained in step al "').
[0045] Preferably, the contacting of step a) is carried out by impregnating the regenerated catalyst with an impregnating solution comprising at least one additive chosen from γ-valerolactone, 4-hydroxyvaleric acid and 2-acid. pentenoic, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor.
[0046] The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid may advantageously be deposited (s) in one or more steps either by impregnation in excess, or by dry impregnation, or by any other means known to those skilled in the art. Preferably, the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid is / are introduced (s) 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 facilitates the implementation on an industrial scale.
[0047] The additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid is / are advantageously introduced into the impregnating solution with the molar ratios per element of group VIB or group VIII described above.
[0048] When it is desired to further introduce an additional additive (in addition to the additive (s) chosen from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3- pentenoic acid or 4-pentenoic acid) or a group of additional additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur other than said additives, this may be introduced in the impregnating solution of step al '' ') or else by a further impregnation step at any time of the preparation process before final drying of step b) it being understood that no does not perform a calcination step after its introduction. This compound is introduced in the proportions described above.
[0049] According to step a2 "), the catalyst precursor obtained in step a '' ') is optionally allowed to mature under the conditions described above. according to the invention, the catalyst precursor which has been optionally matured in step a2 ") is subjected to a drying step at a temperature below 200 ° C without a subsequent calcination step, as described below. above. 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 modes 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 the 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 therefore advantageously subjected to a sulphurization step, without an intermediate calcination step. Said dried catalyst is advantageously sulphurized ex situ or in situ. The sulfurizing agents are H2S gas or any other sulfur-containing compound used for activating the 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. Hydrotreatment and / or Hydrocracking Process Finally, another object of the invention is the use of the catalyst according to the invention or prepared according to the preparation process according to the invention in hydrotreatment and / or hydrotreating processes. hydrocracking of hydrocarbon cuts. The catalyst according to the invention and preferably having previously undergone a sulfurization step is advantageously used for the hydrotreatment and / or hydrocracking reactions of hydrocarbon feedstocks such as petroleum cuts, coal cuts or the 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 and 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 with the catalysts of the prior art. This catalyst can also advantageously be used during the pretreatment of catalytic cracking or hydrocracking feeds, or the hydrodesulfurization of residues or the high hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel according to the English terminology).
[0050] 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, feeds from thermal or catalytic conversion processes, lignocellulosic feedstocks or more generally biomass feedstocks, alone or as a mixture. The feeds which are treated, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy loads, they most often also contain metals.
[0051] The operating conditions used in the processes employing the hydrotreatment 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 501/50001 / let preferably 80 to 20001/1.
[0052] According to a first mode of use, said hydrotreatment process according to the invention is a hydrotreatment process, and in particular hydrodesulfurization (HDS) of a 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 to eliminate the sulfur compounds present in said diesel fuel cup so as to reach the environmental standards in force, namely a sulfur content of up to 10 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 English terminology), a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology). Saxon), 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.
[0053] 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 ° C. MPa and more preferably between 3 MPa and 8 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock, expressed as hydrogen volume, measured under normal conditions of temperature and pressure, per volume of liquid feed, 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 the catalyst charged to the reaction unit implementing the hydrotreatment process according to the invention. The reaction unit employing the hydrotreating process of said diesel fuel cutter 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 hydrotreatment process (in particular hydrodesulfurization, hydrodeaazoation, hydrogenation of aromatics) and / or hydrocracking of a cut of vacuum distillate produced in the presence of at least one catalyst according to the invention. Said hydrotreatment and / or hydrocracking process, otherwise known as the hydrocracking or hydrocracking pretreatment method according to the invention, is intended, as the case may be, to eliminate the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to effect pretreatment before conversion into catalytic cracking or hydroconversion processes, or hydrocracking the distillate cut which would have possibly been previously pretreated if necessary. A wide variety of feeds can be processed by the hydrotreatment and / or hydrocracking processes of vacuum distillates described above. Generally they contain at least 20% volume and often at least 80% volume of compounds boiling above 340 ° C at atmospheric pressure. The 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 deasphalted oils. 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 feedstocks treated in the processes according to the invention is usually greater than 200 ppm by weight, preferably between 500 and 10,000 ppm by weight. The sulfur content of the 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 charges described above, at a temperature above 200 ° C., often between 250 ° C. and 480 ° C. advantageously between 320 ° C. and 450 ° C., preferably between 330 ° C. and 435 ° C., under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the volume velocity being between 0.1 and 20.0 h-1 and preferably 0.1-6.0 h-1, preferably 0.2-3.0 h-1, and the amount of hydrogen introduced is such that the volume ratio of 1 liter of hydrogen / 1 liter of hydrocarbon, expressed as a 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 the more 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 atmospheric pressure. greater than 15% d, 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 fraction 3035601. unconverted, or in a so-called two-step hydrocracking scheme, optionally in combination with a hydrorefining catalyst located upstream of the catalyst of the present invention. According to a third mode of use, said hydrotreatment and / or hydrocracking process according to the invention is advantageously 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 process for hydrotreatment and / or hydrocracking according to US Pat. The invention is a process for hydrotreating (in particular hydrodesulfurization) a gasoline cut in the presence of at least one catalyst according to the invention. Unlike other hydrotreatment processes, the hydrotreatment (including the hydrodesulphurization) of gasolines must make it possible to respond to a double antagonistic constraint: to ensure a deep hydrodesulfurization 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 type cut. Very preferably, the gasoline cut is an olefinic gasoline cut resulting for example from a catalytic cracking unit (Fluid Catalytic Cracking according to the English terminology).
[0054] The hydrotreatment process consists in bringing the hydrocarbon fraction into contact 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 of between 230.degree. At 330 ° C., at a total concentration of between 1 and 5 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 load between 100 and 600 NI / 1, preferably between 200 and 400 NI / 1.
[0055] The process for the hydrotreatment of gasolines can be carried out in one or more series reactors of the fixed bed or 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 from the first hydrodesulfurization reactor before treating said effluent in the process. second hydrodesulphurization reactor. The following examples demonstrate the significant increase in activity on the catalysts prepared according to the process according to the invention compared to the catalysts of the prior art and specify the invention without however limiting its scope.
[0056] 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 of 230 m 2 / g, a pore volume obtained by mercury porosimetry of 0.78 ml / g and a mean pore diameter of 11.5 nm defined as the median diameter by volume. by mercury porosimetry and which is in the form "extruded", cobalt, molybdenum and phosphorus are added. The impregnating solution is prepared by dissolving 90 ° C. of molybdenum oxide (2434 g) and cobalt hydroxide (5.34 g) in 7.47 g of a 85% phosphoric acid solution. % in water. After dry impregnation, the extrudates are allowed to mature in a saturated water atmosphere for 12 hours at room temperature and then dried at 90 ° C for 16 hours. The dried catalyst precursor thus obtained is denoted C1. Calcination of catalytic precursor Cl at 450 ° C for 2 hours leads to calcined catalyst C2. The final composition of the catalysts C1 and C2 expressed in the form of oxides and referred to the dry catalyst mass is then as follows: MoO3 = 22.5 ± 0.2% by weight, CoO = 4.1 ± 0.1% by weight and P2O5 = 4.0 ± 0.1% by weight. EXAMPLE 2 Preparation of CoMoP catalysts on alumina C3 and C4 (not in accordance with the invention), C5 and C6 (in accordance with the invention) by co-impregnation.
[0057] On the alumina support previously described in Example 1 and which is in the "extruded" form, cobalt, molybdenum and phosphorus are added. The impregnating solution is prepared by dissolving molybdenum oxide (28.13 g) and cobalt hydroxide (6.62 g) at 90 ° C. in 7.88 g of a phosphoric acid solution. 85% in water. After homogenization of the above mixture, 37.79 g of citric acid was added before adjusting the volume of 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 2.8 mol / mol. After dry impregnation, the extrudates are allowed to mature in a saturated water atmosphere for 12 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 the catalyst C3, expressed as oxides and relative to the dry catalyst mass is then as follows: MoO3 = 22.7 ± 0.2% by weight, CoO = 4.2 ± 0.1% by weight and P2O5 = 3.8 ± 0.1% by weight. Catalyst C4 is prepared analogously to catalyst C3, but after homogenization of the metal solution containing cobalt, molybdenum and phosphorus, triethylene glycol (TEG) is added, again in a proportion of 1 mole per mole of molybdenum. or 2.8 moles per mole of cobalt. Catalyst C4 was allowed to mature in a saturated water atmosphere for 12 hours at room temperature and then dried at 120 ° C for 16 hours. The final composition of the catalyst C4, expressed in the form of oxides and based on the dry catalyst mass, is then as follows: Mo03 = 22.6 ± 0.2% by weight, CoO = 4.1 ± 0.1% by weight and P2O5 = 3.9 ± 0.1% by weight.
[0058] Catalysts C5 and C6 according to the invention are prepared as follows. On the alumina support described in Example 1 and which is in the "extruded" form, cobalt, molybdenum and phosphorus are added. An impregnating solution was prepared by dissolving 90 ° C of molybdenum oxide (78.75 g) and cobalt hydroxide (18.54 g) in 22.08 g of an acid solution. 85% phosphoric in water. After homogenization of the above mixture, γ-valerolactone was added to the solution in an equimolar proportion relative to the molybdenum, ie 2.8 moles per mole of cobalt to yield the catalyst C5. Similarly, 4-hydroxyvaleric acid was added to the solution in an equimolar ratio to molybdenum or 2.8 moles per mole of cobalt to yield the C6 catalyst. 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 12 hours at room temperature and then dried at 120 ° C for 16 hours. The final composition of the catalyst C5, expressed in oxide form and relative to the mass of dry catalyst, is then as follows: MoO 3 = 22.4 ± 0.2% by weight, CoO = 4.0 ± 0.1% by weight and P2O5 = 4.0 ± 0.1% by weight. The final composition of the catalyst C6, expressed in oxide form and relative to the mass of dry catalyst, is then as follows: MoO 3 = 22.3 ± 0.2% by weight, CoO = 3.8 ± 0.1 25% by weight and P2O5 = 4.2 ± 0.1% by weight. Example 3 Preparation of the CoMoP catalyst on C7 alumina (according to the invention) by pre-impregnation.
[0059] On the alumina support described above in Example 1 and which is in the "extruded" form, 24.7 g of the γ-valerolactone diluted in water are added in order to obtain a volume solution. total equal to the pore volume of the support. The solution thus formed is then dry-impregnated onto the support before a maturation time of 3 hours in a saturated atmosphere of water and at room temperature, followed by drying at 120 ° C. for 2 hours. The modified support is then impregnated with a new impregnation solution prepared by hot dissolving the molybdenum oxide (27.00 g) and cobalt hydroxide (6.36 g) in 7.57 g of 85% phosphoric acid solution in water, taking care to adjust by adding water the volume of the latter solution to the pore volume of the previous modified support. After dry impregnation, the extrudates were allowed to mature in a saturated water atmosphere for 3 h at room temperature, and then dried at 120 ° C for 16 hours to yield catalyst C7. The final composition of the catalyst C6 expressed in the form of oxides and based on the dry catalyst mass is then as follows: MoO 3 = 22.5 ± 0.2% by weight, CoO = 4.1 ± 0.1% by weight and P2O5 = 4.0 ± 0.1% by weight. The amounts involved are such that the amount of γ-valerolactone is one mole per mole of molybdenum and 2.8 moles per mole of cobalt. EXAMPLE 4 Preparation of CoMoP catalysts on C8 alumina (not in accordance with the invention) and C9 (in accordance with the invention) by co-impregnation (low organic compound / Mo ratio) On the alumina support previously described in FIG. In Example 1, which is in the "extruded" form, cobalt, molybdenum and phosphorus are added as for the preparation of catalyst C3. However, during the preparation of the impregnating solution, the mole ratio of citric acid / molybdenum is here equal to 0.25 mol / mol, ie 0.70 mole of citric acid per mole of cobalt. After dry impregnation, the extrudates are allowed to mature in a saturated water atmosphere for 12 hours at room temperature and then dried at 120 ° C for 16 hours. The dried catalytic precursor thus obtained is denoted C8. The final composition of catalyst C8, expressed in the form of oxides and based on the dry catalyst mass, is then as follows: MoO 3 = 22.5 ± 0.2% by weight, CoO = 4.0 ± 0.1% weight and P2O5 = 3.9 ± 0.1% by weight). On the alumina support previously described in Example 1 and in the "extruded" form, cobalt, molybdenum and phosphorus are added as for the preparation of catalyst C5. However, during the preparation of the impregnation solution, the mole ratio of γ-valerolactone relative to molybdenum was set at 0.25 mol / mol, ie 0.70 mole of γ-valerolactone per mole of cobalt. After dry impregnation, the extrudates were allowed to mature in a saturated water atmosphere for 12 hours at room temperature, and then dried at 120 ° C for 16 hours. The dried catalyst precursor thus obtained is denoted C9. The final composition of the catalyst C9, expressed in oxide form and relative to the dry catalyst mass, is then as follows: MoO 3 = 22.3 ± 0.2% by weight, CoO = 4.1 ± 0.1% by weight and P2O 5 = 4.3 ± 0.1% by weight.
[0060] EXAMPLE 5 Evaluation of Diesel Catalyst HDS Catalysts C1, C2, C3, C4, and C8 (Not in Accordance with the Invention) and C5, C6, C7 and C9 (in Accordance with the Invention) Catalysts C1, C2, C3, C4 and C8 (not in accordance with the invention) and C5, C6, C7 and C9 (in accordance with the invention) were tested in diesel HDS. Characteristics of the diesel fuel used: density at 15 ° C: 0.8522 g / cm3, sulfur: 1.44% by weight. - Simulated Distillation: 155 ° C - PI: - 10%: 247 ° C - 50%: 315 ° C 25 - 90%: 392 ° C - mp: 444 ° C The test is conducted in a fixed bed isothermal pilot reactor crossed, the fluids circulating from bottom to top. After sulphurisation in situ at 350 ° C. in the unit under 3035601 pressure using the gas oil of the test, 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 241 / h and a feed 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 sulfur target is reached for a lower temperature and thus 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.
[0061] Table 1 clearly shows the gain on the catalytic effect provided by yvalerolactone, but also by 4-hydroxyvaleric acid. Indeed, the catalysts C5, C6 and C7 (according to the invention) have activities greater than those obtained for all the other catalysts evaluated at the same molar proportions of organic compound (1 mol / molmo).
[0062] Gain is also maximized, at the same amount of additive, catalysts C5 and C6 are more active than catalysts C3 and C4 respectively obtained with citric acid or TEG and which are less active. The activity of the catalyst C7 remains much greater than that of the base catalyst C2 or a dried catalyst C1 without γ-valerolactone or 4-hydroxyvaleric acid.
[0063] The advantage of the catalyst according to the invention remains significant at a lower proportion of organic compound, as shown by the catalyst C9, thus having an intrinsic efficiency of γ-valerolactone higher than that of the other compounds for which it is necessary to introduce a greater proportion of compound to observe a significant catalytic effect.
[0064] Table 1: Activity relating to iso-volume in hydrodesulfurization of gas oil of catalysts C1, C2, C3, C4 and C8 (not in accordance with the invention) and C5, C6, C7 and C9 (in accordance with the invention) by relative to the catalyst C2 (non-compliant) Catalyst Compound Mode of introduction of the organic compound Heat treatment Activity HDS (organic comparison used and (post- / co- / pre-prepregation or according to the molar ratio / Mo the invention) Cl (comp) none Not applicable Dried 120 ° C Base + 1.1 ° C C2 (comp) n / a N / A Calcium Base C3 (comp) Citric acid - 1.0 CO Dry 120 ° C Base - 3.1 ° C C4 (comp) TEG - 1.0 CO Dried 120 ° C Base - 5.3 ° C C5 (inv) y-valerolactone -1.0 CO Dried 120 ° C Base - 7.3 ° C C6 (inv) 4-hydroxyvaleric acid -1.0 CO Dried 120 ° C Base - 6.8 ° C C7 (inv) y-valerolactone -1.0 PRE Dried 120 ° C Base - 6.2 ° C C8 (comp) Citric Acid - 0.25 CO Dried 120 ° C Base -2, 2 ° C C9 (inv) y-valerolactone - 0.25 CO Dried 120 ° C Base - 4.4 ° C

权利要求:
Claims (18)
[0001]
REVENDICATIONS1. Catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB, and at least one additive chosen from γ-valerolactone, acid 4 - hydroxyvaleric acid
[0002]
2-pentenoic acid
[0003]
3-pentenoic or acid
[0004]
4- pentenoic. 2. The catalyst according to claim 1, 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 element content of group VIII is included between 1 and 10% weight expressed as Group VIII metal oxide relative to the total weight of the catalyst. 3. Catalyst according to claim 1 or 2, wherein the molar ratio of Group VIII element to Group VIB element in the catalyst is between 0.1 and 0.8. 4. Catalyst according to one of claims 1 to 3, which further contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed in 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.
[0005]
5. Catalyst according to one of claims 1 to 4, wherein the total content of additive (s) selected from y-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or the 4-pentenoic acid is between 1 and 35% by weight relative to the total weight of the catalyst.
[0006]
The catalyst according to one of claims 1 to 5, which further contains an organic compound other than the additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3- pentenoic acid or pentenoic acid, said organic compound containing oxygen and / or nitrogen and / or sulfur.
[0007]
7. Catalyst according to claim 6, in which the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate. amine, nitrile, imide, oxime, urea and amide.
[0008]
The catalyst of claim 7, wherein the organic compound is selected from triethylene glycol, diethylene glycol, ethylenediaminetetraacetic acid, maleic acid, citric acid, dimethylformamide, bicine, or tricine.
[0009]
9. Catalyst according to one of claims 1 to 8, wherein the carrier contains from 0.1 to 50% by weight of zeolite.
[0010]
10. Catalyst according to one of claims 1 to 9, characterized in that it is at least partially sulphurized.
[0011]
11. Process for the preparation of a catalyst according to one of claims 1 to 10 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 of group VIII, at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus with a carrier at alumina or silica or silica-alumina base, or a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one component of a group VIB element is brought into contact with each other; at least one component of a group VIII element and optionally phosphorus with at least one additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid, so as to obtain a catalyst precursor, b) dry said catalyst precursor from step a) at a temperature below 200 ° C without calcining it later. 5
[0012]
12. Process according to claim 11, in which step a) is the following step: a ') is impregnated with 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, at least one additive selected from yvalerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid and optionally phosphorus so as to obtain a catalyst precursor.
[0013]
13. The method of claim 11, wherein step a) comprises the following steps: a1) impregnating a support based on alumina or silica or silica-alumina 15 with at least one solution containing at least one element group VIB, 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 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 one additive selected from y- valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid so as to obtain a catalyst precursor, a4) optionally, one leaves matu obtain the catalyst precursor obtained in step a3). 3035601 55
[0014]
14. The process as claimed in claim 11, wherein step a) comprises the following steps: a) preparing a support comprising at least one additive chosen from yvalerolactone, 4-hydroxyvaleric acid and 2-pentenoic acid; , 3-pentenoic acid or 4-pentenoic acid and optionally at least a portion of the phosphorus, a2 ') is impregnated with the support obtained in step a1') by an impregnation solution comprising at least one element of group VIB, 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.
[0015]
15. The process according to claim 11, 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 a support impregnated, 20 a2 ") the impregnated support from step a" ") is dried at a temperature below 200 ° C, without subsequently calcining it to obtain a dried impregnated support, a3") the dried impregnated support is brought into contact with from step a2 ") with a solution of an 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 precursor is allowed to mature the catalyst value obtained in step a3 "), 3035601 56 and at least one of the organic compounds of step a1" - or step a3 ") is selected from γ-valerolactone, 4-hydroxyvaleric acid , 2-pentenoic acid, 3-pentenoic acid or 4-pentenoic acid.
[0016]
16. The process according to claim 11, wherein step a) comprises the following steps: a) a regenerated catalyst containing a support based on alumina or silica or silica-alumina is impregnated, 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 additive selected from γ-valerolactone, 4-hydroxyvaleric acid, 2-pentenoic acid, 3-pentenoic acid or 4pentenoic acid so as to obtain a catalyst precursor, a2 ") optionally, the catalyst precursor obtained in step a" ') is allowed to ripen.
[0017]
17. Method according to one of claims 11 to 16, wherein the total molar ratio of the additive (s) selected (s) from y-valerolactone, 4-hydroxyvaleric acid 2-pentenoic acid, the acid 3-pentenoic or 4pentenoic acid per element (s) of group VIII is between 0.1 and 5.0 mol / mol. 20
[0018]
18. Use of the catalyst according to one of claims 1 to 10 or prepared according to one of claims 10 to 17 in a process for hydrotreating and / or hydrocracking of hydrocarbon cuts.

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TW201701950A|2017-01-16|

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WO2016173759A1|2016-11-03|

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RU2705382C2|2019-11-07|

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JP2018520842A|2018-08-02|

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CN107530690A|2018-01-02|

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US10399070B2|2019-09-03|

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TWI700122B|2020-08-01|

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FR3035601B1|2017-04-21|

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RU2017134939A3|2019-07-17|

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EP3288678A1|2018-03-07|

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US20180290131A1|2018-10-11|

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JP6706629B2|2020-06-10|

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法律状态:
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2016-11-04| PLSC| Search report ready|Effective date: 20161104 |

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2018-04-13| PLFP| Fee payment|Year of fee payment: 4 |

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2020-04-29| PLFP| Fee payment|Year of fee payment: 6 |

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2021-04-27| PLFP| Fee payment|Year of fee payment: 7 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1553914A|FR3035601B1|2015-04-30|2015-04-30|A CATALYST BASED ON Y-VALEROLACTONE AND / OR ITS HYDROLYSIS PRODUCTS AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|FR1553914A| FR3035601B1|2015-04-30|2015-04-30|A CATALYST BASED ON Y-VALEROLACTONE AND / OR ITS HYDROLYSIS PRODUCTS AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|

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RU2017134939A| RU2705382C2|2015-04-30|2016-03-11|CATALYST BASED ON γ-VALEROLACTONE AND/OR HYDROLYSIS PRODUCTS THEREOF AND USE THEREOF DURING HYDROPROCESSING AND/OR HYDROCRACKING METHOD|

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JP2017556749A| JP6706629B2|2015-04-30|2016-03-11|Catalysts based on γ-valerolactone and/or its hydrolysis products and their use in hydrotreating and/or hydrocracking processes|

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EP16712275.3A| EP3288678A1|2015-04-30|2016-03-11|CATALYST CONTAINING y-VALEROLACTONE AND/OR THE HYDROLYSIS PRODUCTS THEREOF, AND USE THEREOF IN A HYDROPROCESSING AND/OR HYDROCRACKING METHOD|

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PCT/EP2016/055326| WO2016173759A1|2015-04-30|2016-03-11|Catalyst containing γ-valerolactone and/or the hydrolysis products thereof, and use thereof in a hydroprocessing and/or hydrocracking method|

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CN201680024883.7A| CN107530690A|2015-04-30|2016-03-11|Catalyst based on γ valerolactones and/or its hydrolysate and its purposes in hydrotreating and/or method for hydrogen cracking|

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US15/570,661| US10399070B2|2015-04-30|2016-03-11|Catalyst containing γ-valerolactone and/or the hydrolysis products thereof, and use thereof in a hydroprocessing and/or hydrocracking method|

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TW105110148A| TWI700122B|2015-04-30|2016-03-30|CATALYST BASED ON γ-VALEROLACTONE AND/OR ITS HYDROLYSIS PRODUCTS AND USE THEREOF IN A HYDROTREATMENT AND/OR HYDROCRACKING PROCESS|