FR2793704A1 - Bifunctional hydrocracking catalyst composition for hydroconversion of petroleum charges contains partially amorphous zeolite Y, matrix and hydro-dehydrogenating metal with other promoter elements - Google Patents

Abstract

The invention relates to a hydrocracking catalyst comprising at least one matrix, a partially amorphous Y zeolite, at least one metal selected from the group formed by the metals of group VIB and of group VIII of the periodic table, optionally at least one element chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA, and optionally at least one element from group VIIB. The invention also relates to the use of this catalyst in the hydrocracking of hydrocarbon feedstocks.

Description

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The present invention relates to a hydrocracking catalyst containing at least one matrix, a partially amorphous Y zeolite, at least one hydrodehydrogenating metal preferably selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table, optionally at least one element selected from the group formed by phosphorus, boron and silicon, optionally at least one group VIIA element, and optionally at least one group VIIB element. The invention also relates to the use of this catalyst in hydrocracking hydrocarbon feeds, and more particularly to obtain high viscosity oils having viscosity indexes (VI) greater than 95-100, preferably between 95-150 and more. especially between 120-140.

Hydrocracking of heavy oil cuts is a very important process of refining which makes it possible to produce, from excessively heavy and unrecoverable heavy loads, the lighter fractions such as gasolines, fuels and light gas oils that the refiner seeks in order to adapt his production to the structure of the request. Certain hydrocracking processes also make it possible to obtain a highly purified residue that can constitute excellent bases for oils. Compared to catalytic cracking, the advantage of catalytic hydrocracking is to provide middle distillates, jet fuels and gas oils, of very good quality. The gasoline produced has a much lower octane number than that resulting from catalytic cracking.

The catalysts used in hydrocracking are all of the bifunctional type associating an acid function with a hydrogenating function. The acid function is provided by supports with large surface areas (generally 150 to 800 m2.g-1) with superficial acidity, such as halogenated alumina (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides. amorphous silica-aluminas and zeolites. The hydrogenating function is provided either by one or more metals of group VIII of the periodic table of elements, or by a combination of at least one metal of group VIB of the periodic table and at least one metal of group VIII.

 The equilibrium between the two acid and hydrogenating functions is the fundamental parameter which governs the activity and the selectivity of the catalyst. A weak acid function and a strong hydrogenating function give low active catalysts, working at generally high temperature (greater than or equal to 390 ° C.), and at space velocity

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 weak feed (the VVH expressed in volume of feedstock to be treated per unit volume of catalyst per hour is generally less than or equal to 2 h -1) but with a very good selectivity in middle distillates. Conversely, a strong acid function and a low hydrogenating function give active catalysts but have lower selectivities in middle distillates. The search for a suitable catalyst will therefore be centered on a judicious choice of each of the functions to adjust the activity / selectivity couple of the catalyst.

Thus, it is a major advantage of hydrocracking to have a great flexibility at various levels: flexibility in the catalysts used, which brings flexibility of the feedstock to be treated and the level of products obtained. An easy parameter to control is the acidity of the catalyst support.

Conventional catalysts for catalytic hydrocracking are for the most part constituted by weakly acidic supports, such as amorphous silica-aluminas, for example. These systems are more particularly used to produce middle distillates of very good quality, and again, when their acidity is very low, oil bases.

In low acid carriers, there is the family of amorphous silica-aluminas.

Many catalysts in the hydrocracking market are based on silicalumin associated with either a Group VIII metal or, preferably, when the heteroatomic content of the feedstock to be treated exceeds 0.5% by weight, to a combination of sulphides of Group VIB and VIII metals. These systems have a very good selectivity in middle distillates, and the products formed are of good quality. These catalysts, for the less acidic of them, can also produce lubricating bases. The disadvantage of all these catalytic systems based on amorphous support is, as we said, their low activity.

Catalysts comprising zeolite Y of FAU structural type, or beta type catalysts in turn have a higher catalytic activity than amorphous silica-aluminas, but have selectivities in light products which are higher. In the prior art, the zeolites used for the preparation of hydrocracking catalysts are characterized by several quantities such as their framework SiO 2 / Al 2 O 3 molar ratio, their crystalline parameter, their porous distribution, their specific surface area, their capacity for recovery in

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 sodium ion, or their ability to adsorb water vapor. Thus, in the applicant's previous patents (French patents FR-A-2,754,742 and FR-A-2,754,826), a zeolite whose crystalline parameter is between 24.15 and 24.38 (1 = 0.1 nm) is used. SiO2 / Al2O3 molar ratio of framework between 500 and 21, the sodium content less than 0.15% by weight, the recovery capacity in sodium ion greater than 0.85g Na / 100g zeolite, the specific surface area greater than 400m2 / g , the water vapor adsorption capacity of greater than 6% and 1 to 20% of the pore volume is contained in pores with a diameter of between 20 and 80 °.

In US Pat. No. 4,857,170, it is described the use in hydrocracking of a modified zeolite with a crystalline parameter of less than 24.35, but whose degree of crystallinity is not or only slightly affected by the modifying treatments.

Moreover, the prior art shows that it has always been sought to maintain in the zeolites used crystalline fractions (or degree of crystallinity) and high peak rates.

The research work carried out by the applicant on numerous zeolites and microporous solids led him to discover that, on the contrary and surprisingly, a catalyst containing at least one zeolite Y of partially crystallized FAU structural type makes it possible to achieve selectivities in middle distillate (kerosene and gas oil) significantly improved compared to catalysts containing a zeolite Y known in the prior art.

 In addition, the same work enabled the applicant to note that, surprisingly, samples of zeolite Y differently modified although having characteristics identical to or very similar to those cited in the prior art may, on the other hand, exhibit peak levels. different and different crystalline fractions, and have different reactivities.

 More specifically, the subject of the invention is a composition comprising at least one matrix and at least one element chosen from the group formed by the elements of group VIII and of group VIB, said catalyst being characterized in that it contains a zeolite Y partially amorphous.

 The term "partially amorphous Y zeolite" used in the present invention, a solid having:

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a peak level which is less than 0.40, preferably less than about 0.30, a crystalline fraction expressed relative to a sodium reference zeolite Y (Na) which is less than about 60% Preferably, the partially amorphous Y zeolites, solids used in the composition of the catalyst according to the invention have the following other characteristics: iii / an overall Si / Al ratio greater than 15, preferably less than about 50% greater than 20 and less than
150, -iv / Si / AlIV framework ratio greater than or equal to the overall Si / Al ratio, -v / a pore volume at least equal to 0.20 ml / g of solid including a fraction, between 8% and 50 %, consists of pores with a diameter of at least 5 nm (nm) or 50.

Peak levels and crystalline fractions are determined by X-ray diffraction, using a procedure derived from the ASTM method D3906-97 Determination of Relative X-ray Diffraction Intensities of Faujasite-Type-Containing Materials. This method may be referred to for the general conditions of application of the procedure and, in particular, for the preparation of samples and references.

 A diffractogram is composed of the characteristic lines of the crystallized fraction of the sample and of a background, caused essentially by the diffusion of the amorphous or microcrystalline fraction of the sample (a weak diffusion signal is linked to the apparatus, air The peak rate of a zeolite is the ratio, in a predefined angular zone (typically 8 to 40 when copper Ka radiation is used, I = 0.154 nm), of the area of the zeolite lines (peaks) on the overall area of the diffractogram (peaks + background). This peak / peak ratio is proportional to the amount of crystallized zeolite in the material.

 To estimate the crystalline fraction of a sample of zeolite Y, the peak level of the sample will be compared to that of a reference considered as 100% crystalline (NaY for example). The peak level of a perfectly crystalline NaY zeolite is of the order of 0.55 to 0.60.

 The peak level of a conventional USY zeolite is 0.45 to 0.55, its crystalline fraction relative to a perfectly crystalline NaY is from 80 to 95%. The peak rate of the

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 solid subject of the present invention is less than 0.4 and preferably less than 0.35. Its crystalline fraction is therefore less than 70%, preferably less than 60%.

The zeolites are prepared according to the techniques generally used by dealumination.

The Y zeolites generally used in hydrocracking catalysts are manufactured by modifying commercially available Na-Y zeolite. This modification leads to zeolites said stabilized, ultra-stabilized or dealuminated. This modification is carried out by combining three types of operations known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack. The hydrothermal treatment is perfectly defined by the conjunction of operating variables such as temperature, duration, total pressure and the partial pressure of water vapor. This treatment has the effect of extracting the aluminum-aluminum framework of the zeolite from the aluminum atoms. The consequence of this treatment is an increase in the framework SiO 2 / Al 2 O 3 molar ratio and a decrease in the parameter of the crystalline mesh.

Ion exchange generally takes place by immersion of the zeolite in an aqueous solution containing ions capable of binding to the cationic exchange sites of the zeolite. The sodium cations present in the zeolite are thus removed after crystallization.

The acid etching operation involves contacting the zeolite with an aqueous solution of a mineral acid. The severity of the acid attack is adjusted by acid concentration, duration and temperature. This treatment, carried out on a hydrothermally treated zeolite, has the effect of eliminating the aluminum species extracted from the framework and which clog the microporosity of the solid.

The partially amorphous Y zeolite used in the catalysts according to the invention is at least partly in the hydrogen or acid (H +) or ammonium (NH 4 +) or cationic form, said cation being chosen from the group formed by the groups IA, IB, IIA ,
IIB, IIIA, IIIB (including rare earths), Sn, Pb and Si, it is preferably at least partly in H + form or it can also be used at least partly in cationic form (as defined above ).

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The partially amorphous Y zeolite will preferably be used at least partly in acidic form (and preferably in whole H form) or partially exchanged with cations, for example alkaline and / or alkaline earth cations.

The catalyst, which comprises at least one partially amorphous Y zeolite, also contains a hydrogenating function. The hydrogenating function as defined above preferably comprises at least one metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table of Elements.

The catalyst of the present invention may contain at least one noble or non-noble group VIII element such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. Among the Group VIII metals it is preferred to employ non-noble metals such as iron, cobalt, nickel. The catalyst according to the invention may contain at least one group VIB element, preferably tungsten and molybdenum. Advantageously, the following combinations of metals are used: nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, nickel-tungsten, cobalt-tungsten, the preferred combinations are: nickel-molybdenum, cobalt-molybdenum, nickel- tungsten. It is also possible to use combinations of three metals, for example nickel-cobalt-molybdenum.

 The catalyst of the present invention also contains at least one amorphous or poorly crystallized porous mineral matrix of oxide type. Nonlimiting examples include aluminas, silicas, silica-aluminas. It is also possible to choose aluminates. It is preferred to use matrices containing alumina, in all these forms known to those skilled in the art, and even more preferably aluminas, for example gamma-alumina.

 In one embodiment of the invention, the catalyst preferably contains at least one element selected from the group formed by boron, silicon and phosphorus.

 The catalyst optionally contains at least one element of group VIIA, preferably chlorine and fluorine, and optionally at least one element of group VIIB.

 Boron, silicon and / or phosphorus may be in the matrix, the zeolite or are preferably deposited on the catalyst and then mainly located on the matrix.

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The element introduced, and in particular silicon, mainly located on the matrix of the support can be characterized by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with an X analysis of the components of the catalysts, or even by establishing a distribution map of the elements present in the catalyst by electron microprobe.

The catalyst of the present invention generally contains, in% by weight with respect to the total mass of the catalyst: from 0 to 60%, advantageously from 0.1 to 60%, preferably from 0.1 to 50% and even more preferably from 0 to 1 to 40% of at least one hydro-dehydrogenating metal preferably selected from the group consisting of Group VIB and Group VIII metals, 0.1 to 99 and preferably 0.1 to 99%, preferably from 1 to 98% of at least one amorphous or poorly crystallized porous mineral matrix of the oxide type, said catalyst also contains from 0.1 to 99%, preferably from 0.1 to 99.8%, preferably from 0.1 to 99.8%; at 90%, preferably from 0.1 to 80% of partially amorphous Y zeolite, said catalyst optionally containing from 0 to 20%, preferably from 0.1 to 15% and even more preferably from
0.1 to 10% of at least one promoter element selected from the group consisting of silicon, boron and phosphorus, and preferably boron and / or silicon.

0 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to
10% of at least one element selected from group VIIA, preferably fluorine.

0 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to
10% of at least one element selected from group VIIB.

 The Group VIB, Group VIII and Group VIIB metals of the catalyst of the present invention may be present in whole or in part in the metal and / or oxide and / or sulfide form.

 This catalyst can be prepared by any of the methods well known to those skilled in the art. Advantageously, it is obtained by mixing the matrix and the zeolite and the mixture is shaped. The hydrogenating element is introduced during mixing, or preferably after shaping. The shaping is followed by calcination, the hydrogenating element is introduced before or after this calcination.

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The preparation ends with a calcination at a temperature of 250 to 600 C.

One of the preferred methods according to the present invention is to knead the partially amorphous Y zeolite powder in a wet gel of alumina for a few tens of minutes, then to pass the paste thus obtained through a die to form extrudates of diameter between 0.4 and 4 mm.

The hydrogenating function can be introduced only in part (for example, combinations of metal oxides of groups VIB and VIII) or in full at the time of mixing of the zeolite, ie partially amorphous Y zeolite, with the oxide gel chosen as the matrix.

The hydrogenating function may be introduced by one or more ion exchange operations on the calcined support consisting of a partially amorphous Y zeolite, dispersed in the chosen matrix, using solutions containing the precursor salts of the chosen metals.

The hydrogenating function can be introduced by one or more impregnation operations of the shaped and calcined support, with a solution containing at least one precursor of at least one oxide of at least one metal chosen from the group formed by metals. groups VIII and the Group VIB metals, the precursor (s) of at least one oxide of at least one Group VIII metal being preferably introduced after those of group VIB or at the same time as the latter, if the catalysts contain at least one Group VIB metal and at least one Group VIII metal.

In the case where the catalyst contains at least one group VIB element, for example molybdenum, it is for example possible to impregnate the catalyst with a solution containing at least one group VIB element, to dry, to calcine.

The impregnation of molybdenum can be facilitated by the addition of phosphoric acid in the ammonium paramolybdate solutions, which also makes it possible to introduce the phosphorus so as to promote the catalytic activity.

In a preferred embodiment of the invention, the catalyst contains as promoter at least one element selected from silicon, boron and phosphorus. These elements are introduced on a support already containing at least one partially amorphous Y zeolite, at least one matrix, as defined above, and at least one

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 metal selected from the group consisting of Group VIB metals and Group VIII metals.

In the case where the catalyst contains boron, silicon and phosphorus and optionally the element chosen from group VIIA of the halide ions and optionally at least one element chosen from group VIIB, these elements may be introduced into the catalyst at various levels of preparation and various ways.

The impregnation of the matrix is preferably carried out by the "dry" impregnation method well known to those skilled in the art. The impregnation can be carried out in a single step by a solution containing all the constituent elements of the final catalyst.

The P, B, Si and the element chosen from the group VIIA halide ions may be introduced by one or more impregnation operations with excess of solution on the calcined precursor.

In the case where the catalyst contains boron, a preferred method according to the invention consists in preparing an aqueous solution of at least one boron salt such as ammonium biborate or ammonium pentaborate in an alkaline medium and in the presence of of hydrogen peroxide and to proceed to a so-called dry impregnation, in which the pore volume of the precursor is filled with the solution containing the boron.

In the case where the catalyst contains silicon, a solution of a silicon-type silicon compound will be used.

In the case where the catalyst contains boron and silicon, the deposition of boron and silicon can also be done simultaneously using a solution containing a boron salt and a silicon-type silicon compound. Thus, for example in the case where for example the precursor is a nickel-molybdenum type catalyst supported on a support containing zeolite Y partially amorphous zeolite and alumina, it is possible to impregnate this precursor with the solution Rhodorsil E1P aqueous ammonium biborate and silicone from the company Rhône Poulenc, to carry out drying, for example at 80 ° C., then to impregnate with an ammonium fluoride solution, to carry out a drying, for example at 80 ° C. C, and

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 carry out a calcination for example and preferably in air in crossed bed, for example at 500 C for 4 hours.

In the case where the catalyst contains at least one element of group VIIA, preferably fluorine, it is possible, for example, to impregnate the catalyst with an ammonium fluoride solution, to carry out drying, for example at 80 ° C., and to carry out a calcination for example and preferably in air in crossed bed, for example at 500 C for 4 hours.

Other impregnation sequences can be used to obtain the catalyst of the present invention.

In the case where the catalyst contains phosphorus, it is for example possible to impregnate the catalyst with a solution containing phosphorus, to dry, to calcine.

In the case where the elements contained in the catalyst, ie at least one metal selected from the group consisting of Group VIII metals and Group VIB, optionally boron, silicon, phosphorus, at least one element in group VIIA, at least one group VIIB element are introduced in several impregnations of the corresponding precursor salts, an intermediate catalyst drying step is generally carried out at a temperature generally of between 60 and 250 ° C. and an intermediate calcination stage of the catalyst is generally carried out at a temperature of between 250 and 600 C.

In order to complete the preparation of the catalyst, the wet solid is allowed to stand under a humid atmosphere at a temperature of between 10 and 80 ° C., and then the wet solid obtained is dried at a temperature of between 60 and 150 ° C., and finally the solid obtained at a temperature of between 150 and 800 C.

 Sources of Group VIB elements that can be used are well known to those skilled in the art. For example, among the sources of molybdenum and tungsten, it is possible to use oxides and hydroxides, molybdic and tungstic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid,

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 silicotungstic acid and their salts. Oxides and ammonium salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate are preferably used.

The sources of group VIII elements that can be used are well known to those skilled in the art. For example, for non-noble metals, nitrates, sulphates, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates, will be used. For the noble metals will be used halides, for example chloride, nitrates, acids such as chloroplatinic acid, oxychlorides such as ammoniacal oxychloride ruthenium.

The preferred phosphorus source is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable. The phosphorus may for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family.

Many sources of silicon can be used. Thus, it is possible to use ethyl orthosilicate Si (OEt) 4, siloxanes, polysiloxanes, halide silicates such as ammonium fluorosilicate (NH4) 2SiF6 or sodium fluorosilicate Na2SiF6. Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously employed. The silicon may be added, for example, by impregnation of ethyl silicate in solution in a water / alcohol mixture. Silicon can be added, for example, by impregnating a silicone-type silicon compound suspended in water.

The source of boron may be boric acid, preferably orthoboric acid H3BO3, biborate or ammonium pentaborate, boron oxide, boric esters. The boron may for example be introduced in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture.

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 Sources of VIIA group elements 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. It is also possible to use hydrolysable compounds which can release fluoride anions in water, such as ammonium fluorosilicate (NH4) 2 SiF6, silicon tetrafluoride SiF4 or sodium tetrafluoride Na2SiF6. The fluorine may be introduced for example by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.

The sources of group VIIB elements that can be used are well known to those skilled in the art. Ammonium salts, nitrates and chlorides are preferably used.

The catalysts thus obtained, in oxides form, can optionally be brought at least partly in metallic or sulphide form.

The catalysts obtained by the present invention are shaped into grains of different shapes and sizes. They are generally used in the form of cylindrical or multi-lobed extrusions such as bilobed, trilobed, straight or twisted polylobed, but may optionally be manufactured and used in the form of crushed powder, tablets, rings, beads. , wheels. They have a specific surface area measured by nitrogen adsorption according to the BET method (Brunauer, Emmett, Teller, J. Am Chem Soc., Vol 60, 309-316 (1938)) of between 50 and 600 m 2 / g, porous volume measured by mercury porosimetry of between 0.2 and 1.5 cm 3 / g and a pore size distribution that can be monomodal, bimodal or polymodal.

 The catalysts thus obtained are used for the conversion of hydrocarbon feeds (in the broad sense of transformation) and in particular by hydrocracking.

 The catalysts obtained by the present invention are used for the hydrocracking of hydrocarbon feeds such as petroleum cuts. The charges used in the process are gasolines, kerosene, gas oils,

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 vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, waste oils, residues or deasphalted crudes, fillers from thermal or catalytic conversion processes and mixtures thereof. They contain heteroatoms such as sulfur, oxygen and nitrogen and possibly metals.

The catalysts thus obtained are advantageously used for hydrocracking, in particular heavy hydrocarbon fractions of vacuum distillate type, deasphalted or hydrotreated residues or the like. The heavy cuts preferably consist of at least 80% by volume of compounds whose boiling points are at least 350 C and preferably between 350 and 580 C (that is to say corresponding to compounds containing at least 15 to 20 carbon atoms). They usually contain heteroatoms such as sulfur and nitrogen. The nitrogen content is usually between 1 and 5000 ppm by weight and the sulfur content between 0.01 and 5% by weight.

The hydrocracking conditions such as temperature, pressure, hydrogen recycling rate, hourly space velocity, may be very variable depending on the nature of the load, the quality of desired products and facilities available to the refiner. The temperature is generally greater than 200 C and often between 250 C and 480 C. The pressure is greater than 0.1 MPa and often greater than 1 MPa. The hydrogen recycling rate is at least 50 and often between 80 and 5000 normal liters of hydrogen per liter of charge. The hourly volume velocity is generally between 0.1 and 20 volume of charge per volume of catalyst per hour.

The catalysts of the present invention are preferably subjected to a sulphurization treatment making it possible, at least in part, to transform the metal species into sulphide before they come into contact with the charge to be treated. This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any method already described in the literature.

 A conventional sulfurization method well known to those skilled in the art consists of heating in the presence of hydrogen sulphide at a temperature of between 150 and 800 ° C., preferably between 250 and 600 ° C., generally in a crossed-bed reaction zone.

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 The catalyst of the present invention can be advantageously used for the hydrocracking of vacuum distillate-type cuts heavily loaded with sulfur and nitrogen. The desired products are middle distillates and / or oils. Advantageously, the hydrocracking is used in combination with a prior hydrotreatment step in a process for the improved production of middle distillates together with the production of oil bases having a viscosity number between 95 and 150.

In a first embodiment or partial hydrocracking still called mild hydrocracking, the conversion level is less than 55%. The catalyst according to the invention is then employed at a temperature generally greater than or equal to 230 ° C. and preferably 300 ° C., generally at most 480 ° C., and often between 350 ° C. and 450 ° C.. greater than 2 MPa and preferably 3 MPa, it is less than 12 MPa and preferably less than 10 MPa.

The amount of hydrogen is at least 100 normal liters of hydrogen per liter of charge and often between 200 and 3000 normal liters of hydrogen per liter of charge. The hourly volume velocity is generally between 0.1 and 10h-1.

Under these conditions, the catalysts of the present invention exhibit better activity in conversion, hydrodesulphurization and hydrodenitrogenation than commercial catalysts.

In a second embodiment, the process is carried out in two stages, the catalyst of the present invention being used for partial hydrocracking, advantageously under conditions of moderate hydrogen pressure, for example sections of the vacuum distillate type. loaded with sulfur and nitrogen which have been previously hydrotreated. In this hydrocracking mode, the conversion level is less than 55%. In this case, the petroleum fraction conversion process takes place in two stages, the catalysts according to the invention being used in the second stage. The catalyst of the first step can be any hydrotreatment catalyst contained in the state of the art. This hydrotreatment catalyst advantageously comprises a matrix preferably based on alumina and at least one metal having a hydrogenating function. The hydrotreatment function is provided by at least one metal or metal compound, alone or in combination, chosen from Group VIII and Group VIB metals, such as chosen from nickel, cobalt, molybdenum and tungsten, in particular . In addition, this catalyst may optionally contain phosphorus and optionally boron.

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 The first step generally takes place at a temperature of 350-460 ° C, preferably 360 ° -450 ° C, a total pressure of at least 2 MPa; preferably 3 MPa, an hourly space velocity of 0.1-5h-1 and preferably 0.2-2h-1 and with an amount of hydrogen of at least 100NI / NI of charge, and preferably 260-3000NI / NI charge.

For the conversion step with the catalyst according to the invention (or second stage), the temperatures are in general greater than or equal to 230 ° C. and often between 300 ° C. and 480 ° C., preferably between 330 ° C. and 450 ° C. The pressure is generally at least 2 MPa and preferably 3 MPa, it is less than 12 MPa and preferably less than 10 MPa. The amount of hydrogen is at least 1001/1 of charge and often between 200 and 30001/1 of hydrogen per liter of charge. The hourly volume velocity is generally between 0.15 and 10.1 hours. Under these conditions, the catalysts of the present invention have a better activity in conversion, hydrodesulfurization, hydrodenitrogenation and better selectivity in middle distillates than commercial catalysts. The life of the catalysts is also improved in the moderate pressure range.

In another two-step embodiment, the catalyst of the present invention can be used for hydrocracking under high hydrogen pressure conditions of at least 5 MPa. The treated slices are, for example, vacuum distillate type with a high sulfur and nitrogen load which have been previously hydrotreated. In this hydrocracking mode, the conversion level is greater than 55%. In this case, the petroleum fraction conversion process takes place in two stages, the catalyst according to the invention being used in the second stage.

The catalyst of the first step can be any hydrotreatment catalyst contained in the state of the art. This hydrotreatment catalyst advantageously comprises a matrix preferably based on alumina and at least one metal having a hydrogenating function. The hydrotreatment function is provided by at least one metal or metal compound, alone or in combination, chosen from Group VIII and Group VIB metals, such as chosen from nickel, cobalt, molybdenum and tungsten, in particular . In addition, this catalyst may optionally contain phosphorus and optionally boron.

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The first step generally takes place at a temperature of 350-460 ° C., preferably 360 ° -450 ° C., a pressure greater than 3 MPa, an hourly space velocity of 0.1-5 h -1 and preferably 0.2-2 h -1 and with a quantity of hydrogen of at least 100NI / NI charge, and preferably 260-3000NI / NI charge.

For the conversion step with the catalyst according to the invention (or second stage), the temperatures are in general greater than or equal to 230 ° C. and often between 300 ° C. and 480 ° C. and preferably between 300 ° C. and 440 ° C. The pressure is generally greater than 5 MPa and preferably greater than 7 MPa. The amount of hydrogen is at least 1001/1 of charge and often between 200 and 30001/1 of hydrogen per liter of charge. The hourly volume velocity is generally between 0.15 and 10h-1.

Under these conditions, the catalysts of the present invention have a better conversion activity and a better selectivity in middle distillates than commercial catalysts, even for zeolite contents considerably lower than those of commercial catalysts.

In a process for producing oils advantageously using the hydrocracking process according to the invention, it is operated according to the teaching of US Pat. No. 5,525,209 with a first hydrotreating step under conditions making it possible to reach an effluent having a Viscosity index 90-130 and reduced nitrogen content and polyaromatic compounds. In a subsequent hydrocracking step, the effluent is treated according to the invention and so as to adjust the value of the viscosity index to that desired by the operator.

The following examples illustrate the present invention without, however, limiting its scope.

EXAMPLE 1 Preparation of a Hydrocracking Catalyst Support Containing a Partially Amorphous Y-Zeolite A commercial ultrastable dealuminated zeolite USY having an overall Si / Al molar ratio of 15.2, with a Si / Al ratio of 29, crystalline parameter equal to 24.29%, containing 0.30% by weight of Na, having a peak level of 0.48 and having a crystalline fraction of 85%, is amorphized by a hydrothermal treatment.

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 620 C for 5h in the presence of a partial pressure of water vapor equal to 0.5 bar absolute. The zeolite is then subjected to an acid attack carried out under the following conditions: normality of the acid 0. 85N, duration of 3h and temperature equal to 95 C. A last hydrothermal treatment identical to the first with a partial pressure of water vapor equal to 0. 02bars is applied to the zeolite. At the end of these treatments, the partially amorphous zeolite has a peak level of 0.26, a crystalline fraction of 44%, an overall Si / Al ratio of 72, and a Si / AlIV ratio of 80, a volume of porous 0.35ml of liquid nitrogen per gram of which 29% consist of pores whose diameters are at least equal to 5 nanometers (50).

A hydrocracking catalyst support containing this zeolite Y is manufactured in the following manner: 60 g of the partially amorphous Y zeolite described above are mixed with 40 g of a matrix composed of ultrafine tabular boehmite or alumina gel. marketed under the name SB3 by Condéa Chemie Gmbh. This powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) and kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices of diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air.

EXAMPLE 2 Preparation of hydrocracking catalysts, containing a partially amorphous Y zeolite, in accordance with the invention The support extrudates containing a partially amorphous Y zeolite of Example 1 are dry impregnated with an aqueous heptamolybdate solution. ammonium, dried overnight at 120 ° C. under air and finally calcined under air at 550 ° C.

The oxide weight contents of the Y, Mo catalyst obtained are given in Table 1.

The Y1Mo catalyst was then impregnated with an aqueous solution containing ammonium biborate to obtain a deposit of approximately 1.7% by weight of B203. After maturation at ambient temperature in an atmosphere saturated with water, the impregnated extrudates are dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air. A catalyst named Y1MoB is obtained. In the same way, a catalyst Y, MoSi was then prepared by impregnating the catalyst Y, Mo with a Rhodorsil EP1 silicone emulsion (Rhone-Poulenc) so as to deposit about 2.0% of SiO 2. The impregnated extrusions are then dried

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 overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air.

Finally, a catalyst Y, MoBSi was obtained impregnation of the catalyst Y, Mo by an aqueous solution containing the ammonium biborate and the Rhodorsil EP1 silicone emulsion (Rhone-Poulenc). The impregnated extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air.

The support extrudates, containing a partially amorphous Y zeolite, prepared in Example 1 are impregnated dry with an aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate, dried overnight at 120 ° C. under air and finally calcined in air at 550 ° C. The oxide weight contents of the catalyst Y, NiMo obtained are given in Table 3.

The extrudates are impregnated dry with an aqueous solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, dried overnight at 120 ° C. in air and finally calcined in air at 550 ° C. The contents The weight of oxides of Y1NiMoP catalyst obtained are given in Table 3.

We then impregnated the catalyst sample Y, NiMoP with an aqueous solution containing ammonium biborate. After maturation at ambient temperature in a saturated water atmosphere, the impregnated extrudates are dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air. A catalyst named Y, NiMoPB is obtained.

A catalyst Y, NiMoPSi was obtained by the same procedure as the catalyst Y, NiMoPB above but replacing in the impregnation solution the boron precursor by the Rhodorsil EP1 silicone emulsion.

Finally, Y, NiMoPBSi catalyst was obtained by the same procedure as the above catalysts but using an aqueous solution containing ammonium biborate and Rhodorsil EP1 silicone emulsion. Fluorine is then added to this catalyst by impregnation with a hydrofluoric acid solution diluted so as to deposit about 1% by weight of fluorine. After drying overnight at
120 C and calcination at 550 ° C. for 2 hours in dry air gives the catalyst Y, NiMoPBSiF. The final oxide contents of the Y, NiMo catalysts are shown in Table 1.

<Desc / Clms Page number 19>

<Tb>
<Tb>

Table <SEP> 1 <SEP>: <SEP> Characteristics <SEP> of <SEP> catalysts <SEP> Y1Mo <SEP> and <SEP> Y, NiMo
<tb> Catalyst <SEP> Y1Mo <SEP> Y1MoB <SEP> Y, MoSi <SEP> Y1MoBSi
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 14.3 <SEP> 14.5 <SEP> 14.2 <SEP> 14.1
<tb> B2O3 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.5 <SEP> 0 <SEP> 1.6
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 50.7 <SEP> 49.7 <SEP> 52.3 <SEP> 51.4
<tb> Complement <SEP> to <SEP> 100% <SEP> 35.0 <SEP> 34.3 <SEP> 33.5 <SEP> 32.9
<tb> compound <SEP> mostly <SEP> of
<tb> Al2O3 <SEP> (% <SEP> wt)
<tb> Table <SEP> 1 <SEP> continued
<tb> Catalyst <SEP> Y, <SEP> Y, <SEP> Y, <SEP> Y, <SEP> Y, <SEP> Y,
<tb> NiMo <SEP> NiMoP <SEP> NiMoPB <SEP> NiMoPSi <SEP> NiMoPBSi <SEP> NiMoPBSiF
<tb> MoO3 <SEP> (% <SEP> wt) <SEP> 13.5 <SEP> 13.9 <SEP> 12.8 <SEP> 12.9 <SEP> 12.9 <SEP> 12.85
<tb> NiO <SEP> (% <SEP> wt) <SEP> 3.05 <SEP> 2.2 <SEP> 2.95 <SEP> 2.9 <SEP> 3.0 <SEP> 2.95
<tb> P2O5 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 4.4 <SEP> 4.3 <SEP> 4.5 <SEP> 4.5 <SEP> 4.4
<tb> B203 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 0 <SEP> 1.4 <SEP> 0 <SEP> 1.5 <SEP> 1.6
<tb> SiO2 <SEP> (% <SEP> wt) <SEP> 49.4 <SEP> 47.0 <SEP> 46.5 <SEP> 48.6 <SEP> 47.9 <SEP> 47.3
<tb> F <SEP> (% <SEP> wt) <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 1.0
<tb> Complement <SEP> to <SEP>
<tb> 100% <SEP> Compound <SEP> 34.05 <SEP> 32.5 <SEP> 32.05 <SEP> 31.1 <SEP> 30.2 <SEP> 29.9
<tb> mainly
<tb> of <SEP> Al2O3 <SEP> (% <SEP> wt)
<Tb>
Catalyst Y, NiMoP was then impregnated with an aqueous solution containing manganese nitrate. After maturation at ambient temperature in an atmosphere saturated with water, the impregnated extrudates are dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air. A catalyst named Y, NiMoPMn is obtained. This catalyst is then impregnated with an aqueous solution containing the ammonium biborate and the Rhodorsil EP1 (Rhone-Poulenc) silicone emulsion. The impregnated extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air and the catalyst Y, NiMoPMnBSi is obtained. Fluorine is then added to this catalyst by impregnation with a hydrofluoric acid solution diluted so as to deposit about 1% by weight of fluorine. After drying overnight at 120 ° C and

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 calcination at 550 ° C. for 2 hours in dry air gives the catalyst Y, NiMoPMnBSiF. The weight contents of these catalysts are shown in Table 2.

Table 2: Characteristics of catalysts Y, NiMo containing manquesis

<Tb>
<tb> Catalyst <SEP> Y, <SEP> Y, <SEP> Y,
<tb> NiMoPMn <SEP> NiMoPMnBSi <SEP> NiMoPMnBSiF
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 12.6 <SEP> 12.1 <SEP> 12.2
<tb> NiO <SEP> (% <SEP> wt) <SEP> 3.1 <SEP> 2.9 <SEP> 2.8
<tb> Mn02 <SEP> (% <SEP> wt) <SEP> 2.1 <SEP> 2.1 <SEP> 2.2
<tb> P2O5 <SEP> (% <SEP> wt) <SEP> 4.4 <SEP> 4.5 <SEP> 4.9
<tb> B203 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.2 <SEP> 1.4
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 46.0 <SEP> 47.1 <SEP> 46.4
<tb> F <SEP> (% wt) <SEP> 0 <SEP> 0 <SEP> 1.0
<tb> Supplement <SEP> to
<tb> 100% <SEP> Compound <SEP> 31.8 <SEP> 30.1 <SEP> 29.1
<tb> predominantly <SEP> of <SEP> 31.8 <SEP> 30.1 <SEP> 29.1
<tb> AI203 <SEP> (% <SEP> wt)
<Tb>
Electron microprobe analysis of Y, NiMoPSi, Y, NiMoPBSi, Y, NiMoPBSiF catalysts (Table 3) and Y, NiMoPMnBSi, Y, NiMoPMnBSiF catalysts (Table 3a) shows that the silicon added to the catalyst according to US Pat. The invention is located primarily on the matrix and is in the form of amorphous silica.

Example 3 Preparation of a Support Containing a Y1 Zeolite and a Silica-Alumina We manufactured a silica-alumina powder by co-precipitation having a composition of 2% SiO 2 and 98% Al 2 O 3. A hydrocracking catalyst support containing this silica-alumina and the partially amorphous Y zeolite of Example 1 was then manufactured. For this purpose, 50% by weight of the partially amorphous Y zeolite of Example 1 is used which is mixed with 50% by weight of a matrix composed of the silica alumina prepared above. This powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) and kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices of

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 diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours in air.

EXAMPLE 4 Preparation of Hydrocracking Catalysts Containing a Partially Amorphous Y Zeolite and a Silica-Alumina The support extrudates containing a silica-alumina and a partially amorphous Y zeolite of Example 3 are dry-impregnated with an aqueous solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, dried overnight at 120 ° C. in air and finally calcined in air at 550 ° C. The weight contents of oxides of the catalyst Y1-SiAl-NiMoP obtained are shown in Table 4.

We impregnated the Y1-SiAl-NiMoP catalyst sample with an aqueous solution containing ammonium biborate so as to impregnate 1.5% mass of 8203. After maturation at room temperature in a saturated water atmosphere, the impregnated extrusions are dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air. A catalyst named Y, -SiAI-NiMoPB is obtained which therefore contains silicon in the silica-alumina matrix.

The characteristics of the Y, -SiAl-NiMo catalysts are summarized in Table 3.

Catalyseur Y1-SiAI-NiMoP Y1-SiAI-NiMoP8

TABLE 3 Characteristics of Y1-SiAl-NiMo Catalysts

Catalyst Y1-SiAI-NiMoP Y1-SiAI-NiMoP8

<Tb>
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 13.1 <SEP> 13.5
<tb> NiO <SEP> (% <SEP> wt) <SEP> 2.9 <SEP> 2.7
<tb> P2O5 <SEP> (% <SEP> wt) <SEP> 4.7 <SEP> 4.9
<tb> B2O3 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.4
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 47.6 <SEP> 46.5
<tb> Complement <SEP> to <SEP> 100%
<tb> compound <SEP> predominantly <SEP> from <SEP> 11-7
<tb> AI203 <SEP> (% <SEP> wt) <SEP> 31.7 <SEP> 31.0
<Tb>
Example 5 Preparation of a Support Containing a Zeolite of the Prior Art

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 A hydrocracking catalyst support containing a zeolite Y has been manufactured in large quantities so that different catalysts can be prepared based on the same support. For this purpose, 20.5% by weight of the same USY commercial zeolite is used as that used in Example 1. This zeolite is mixed with 79.5% by weight of a matrix composed of ultrafine tabular boehmite or alumina gel. marketed under the name SB3 by Condéa Chemie Gmbh. This powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) and kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices of diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours in air. Cylindrical extrudates 1.2 mm in diameter are thus obtained, having a specific surface area of 223 m 2 / g and a monomodal pore size distribution centered on 10 nm.

EXAMPLE 6 Preparation of hydrocracking catalysts containing zeolite Y of Example 5 The support extrudates containing a dealuminated Y zeolite of Example 5 are dry-impregnated with an aqueous solution of a mixture of ammonium heptamolybdate , nickel nitrate and orthophosphoric acid, dried overnight at 120 C in air and finally calcined in air at 550 C. The oxide weight contents of the YNiMoP catalyst obtained are shown in Table 5. The final YNiMoP catalyst contains Particularly, 16.3% by weight of zeolite Y of 2,429 nm mesh ratio SiO2 / Al2O3 overall of 30.4 and SiO2 / Al2O3 framework ratio of 58.

We impregnated the YNiMoP catalyst sample with an aqueous solution containing ammonium biborate. After maturation at ambient temperature in an atmosphere saturated with water, the impregnated extrudates are dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air. A NiMoP / alumina-Y catalyst doped with boron is obtained.

 A YNiMoPSi catalyst was obtained by the same procedure as the YNiMoPB catalyst above but replacing in the impregnation solution the boron precursor by the Rhodorsil EP1 (Rhone-Poulenc) silicone emulsion.

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Finally, a YNiMoPBSi catalyst was obtained impregnating the catalyst with an aqueous solution containing the ammonium biborate and the Rhodorsil EP1 silicone emulsion (Rhône-Poulenc). The other steps of the procedure are the same as those indicated above. The characteristics of YNiMo catalysts are summarized in Table 4.

Table 4: Characteristics of YNiMo catalysts (not in accordance with the invention)

<Tb>
<tb> Catalyst <SEP> YNiMo <SEP> YNiMoP <SEP> YNiMoPB <SEP> YNiMoPSi <SEP> YNiMoPBSi
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 13.5 <SEP> 12.9 <SEP> 12.7 <SEP> 12.7 <SEP> 12.5
<tb> NiO <SEP> (% <SEP> wt) <SEP> 3.1 <SEP> 3.0 <SEP> 2.9 <SEP> 2.9 <SEP> 2.8
<tb> P205 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 4.4 <SEP> 4.3 <SEP> 4.3 <SEP> 4.2
<tb> B203 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 0 <SEP> 1.8 <SEP> 0 <SEP> 1.8
<tb> SiO2 <SEP> (% <SEP> Wt) <SEP> 16.2 <SEP> 15.4 <SEP> 15.2 <SEP> 17.0 <SEP> 16.7
<tb> Supplement <SEP> to
<tb> 100% <SEP> composed
<tb> predominantly <SEP> of <SEP> 67.2 <SEP> 64.3 <SEP> 63.1 <SEP> 63.1 <SE> 62.0
<tb> Al2O3 <SEP> (% <SEP> wt)
<Tb>
The electron microprobe analysis of YNiMoPSi and YNiMoPBSi catalysts (Table 5) shows that the silicon added to the catalyst according to the invention is mainly located on the matrix and is in the form of amorphous silica.

Example 7 Comparison of the Hydrocracking Catalysts of a Partially Converted Vacuum Diesel Fuel

The catalysts whose preparations are described in the preceding examples are used under the conditions of hydrocracking at moderate pressure on a petroleum feedstock whose main characteristics are as follows:
Density (20/4) 0.921
Sulfur (% wt) 2.46
Nitrogen (ppm by weight) 1130
Simulated distillation initial point 365 C point 10% 430 C

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50% point 472 C 90% point 504 C end point 539 C pour point + 39 C The catalytic test unit consists of two fixed-bed reactors with up-flow flow. reactor, the one in which the feedstock passes first, is introduced the first hydrotreatment catalyst HTH548 sold by the company Procatalyse comprising a group VI element and a group VIII element deposited on alumina In the second reactor, that in The feedstock is passed last, a hydrocracking catalyst is introduced as described above, 40 ml of catalyst are introduced into each of the reactors and the two reactors are operated at the same temperature and at the same pressure. test unit are as follows:
Total pressure 5 MPa
Hydroprocessing catalyst 40 cm3
40 cc hydrocracking catalyst
400 C temperature
Hydrogen flow rate 20 l / h
Charge rate 40 cm3 / h Both catalysts undergo an in situ sulphurization step before reaction.

It should be noted that any in situ or ex situ sulphurization method is suitable. Once the sulfurization is complete, the charge described above can be transformed.

Catalytic performances are expressed by hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) conversions. These catalytic performances are measured on the catalyst after a period of stabilization, generally at least 48 hours, has been observed.

The hydrodesulphurization conversion HDS is taken equal to: HDS = (Sinitial - Seffluent) / Sinitial * 100 = (24600 - Sement) / 24600 * 100 The conversion to hydrodenitrogenation HDN is taken equal to: HDN = (Ninitial - Neffluent) / Ninitial * 100 = (1130 - Neffluent) / 1130 * 100

<Desc / Clms Page number 25>

 In the following table, we have reported the conversion to hydrodesulfurization HDS and conversion to hydrodenitrogenation HDN for the catalysts.

Table 5 Catalytic Activities of Catalysts in Partial Hydrocracking at 400 ° C.

<Tb>
<tb> References <SEP> Composition <SEP> HDS <SEP> HDN
<tb> (%) <SEP> (%)
<tb> YNiMoP <SEP> NiMoP / Y <SEP> - <SEP> Al2O3 <SEP> 99.43 <SEP> 96.6
<tb> YNiMoPB <SEP> NiMoPBIY <SEP> 99.57 <SEP> 97.4
<tb> YNiMoPSi <SEP> NiMoPSi / Y <SEP> 99.85 <SEP> 98.3
<tb> Y1-SiAl-NiMoP <SEP> NiMoP / <SEP> Y1-SiAl <SEP> 98.6 <SEP> 96.6
<tb> Y1-SiAl-NiMoPB <SEP> NiMoPB / <SEP> YrSiAI <SEP> 98.7 <SEP> 97.8
<tb> Y, NiMo <SEP> NiMo / <SEP> Y1-Al2O3 <SEP> 98.6 <SEP> 95.1
<tb> Y, NiMoP <SEP> NiMoP / <SEP> Y, <SEP> 99.3 <SEP> 97.0
<tb> Y, NiMoPB <SEP> NiMoPB / <SEP> Y, <SEP> 99.7 <SEP> 97.8
<tb> Y, NiMoPSi <SEP> NiMoPSi / <SEP> Y, <SEP> 99.8 <SEP> 98.7
<tb> YiNiMoPBSi <SEP> NiMoPBSi / <SEP> Y, <SEP> 99.8 <SEP> 99.0
<Tb>
The results in Table 6 show that the use of a catalyst according to the invention, containing a partially amorphous Y zeolite, is more active in hydrodesulfurization and hydrodenitrogenation than the catalysts of the prior art and that on the other hand the addition of at least one element selected from the group formed by B, Si and P provides an improvement in the performance of the catalyst according to the invention.

In addition, the results in Table 6 show that it is advantageous to introduce the silicon onto the already prepared catalyst (YiNiMo series) rather than in the form of a silicon-containing support obtained from a silica-alumina ( Y1-SiAlNiMo series). It is therefore particularly advantageous to introduce the silicon on a precursor already containing the elements of group VIB and / or VIII and possibly at least one of the elements P, B and F.

Example 8 Comparison of Hydrocracking Catalysts of a High Conversion Vacuum Diesel Fuel Catalysts whose preparations are described in the preceding examples are used under the conditions of high conversion hydrocracking (60-100%). The

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petroleum filler is a hydrotreated vacuum distillate whose main characteristics are as follows:
Density (20/4) 0.869
Sulfur (ppm by weight) 502
Nitrogen (ppm by weight) 10
Simulated distillation initial point 298 C point 10% 369 C point 50% 427 C point 90% 481 C end point 538 C This feedstock was obtained by hydrotreating a vacuum distillate on an HR360 catalyst sold by the company Procatalyse, comprising an element group VIB and a group VIII element deposited on alumina.

To the hydrotreated feedstock is added a sulfur compound precursor of H2S and a nitrogen compound precursor of NH3 in order to simulate the partial pressures of H2S and NH3 present in the second hydrocracking step. The feed thus prepared is injected into the hydrocracking test unit which comprises a fixed-bed reactor with up-flow of the feed ("up-flow"), into which 80 ml of catalyst is introduced. Before injection of the feedstock, the catalyst is sulphurized with an n-hexane / DMDS + aniline mixture up to 320 C. It should be noted that any in situ or ex situ sulphurization method is suitable. Once the sulphurization has been carried out, the charge described above can be transformed. The operating conditions of the test unit are as follows:
Total pressure 9 MPa
Catalyst 80 cm3
Temperature 360-420 C
Hydrogen flow rate 80 l / h
Charging rate 80 cm3 / h

<Desc / Clms Page number 27>

 The catalytic performances are expressed by the temperature which makes it possible to reach a crude conversion level of 70% and by the crude distillate average selectivity of 150-380 C. These catalytic performances are measured on the catalyst after a stabilization period, usually at least 48 hours, has been respected.

The gross conversion CB is taken as equal to: minus CB =% by weight of 380 C of the effluent The gross selectivity SB in middle distillate is taken as equal to: SB = 100 * weight of the fraction (150 C-380 C) / weight fraction 380 C less than the effluent The average distillates obtained are composed of products having a boiling point between 150 and 380 C.

The reaction temperature is set so as to reach a gross conversion CB equal to 70% by weight. In the following table 6, we have reported the reaction temperature and the crude selectivity for the catalysts described in Tables 3 and 3a, as well as the values of the viscosity numbers determined on the 380 C + fractions after solvent dewaxing.

Table 6 shows that the use of a catalyst according to the invention containing partially amorphous Y zeolite leads to higher middle distillate crude selectivities than those of the non-compliant prior art catalysts. On the other hand, the addition of at least one element selected from the group formed by P, B and Si to the catalysts according to the invention also leads to an increase in activity. There is also the improvement brought by the presence of manganese or fluorine on the activity.

In addition, it is clear that the viscosity indices of the fractions 380 C + obtained with the catalysts according to the invention are significantly improved.

In general, the addition of at least one element selected from the group P, B, Si, VIIB, VIIA to the catalyst containing the partially amorphous Y zeolite and the group VIB element to the catalyst according to the invention makes it possible to to improve activity in

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 conversion, which results in a decrease in the reaction temperature necessary to achieve 70% conversion.

Table 6: Catalytic Activities of Hydrocracking Catalysts

<Tb>
<tb> high <SEP> conversion <SEP> (70%)
<tb> Reference <SEP> Composition <SEP> Selectivity <SEP> Raw <SEP> Index <SEP> of
<tb> Reference <SEP> Composition <SEP> T (C) <SEP> in <SEP> distillate <SEP> viscosity <SEP> VI
<tb> average <SEP> 380 C +
<tb> (150-380 C) <SEP> Dewaxing
<tb> (% <SEP> wt)
<tb> YNiMo <SEP> NiMoN <SEP> - <SEP> Al2O3 <SEP> 375 <SEP> 65.8 <SEQ> 112
<tb> YNiMo <SEP> P <SEP> NiMoP / Y <SEP> - <SEP> Al2O3 <SEP> 374 <SEP> 66.4 <SEP> 115
<tb> YNiMo <SEP> PB <SEP> NiMoPBIY <SEP> - <SEP> A1203 <SEP> 374 <SEP> 67.1 <SEP> 116
<tb> YNiMo <SEP> PSi <SEP> NiMoPSi / Y <SEP> - <SEP> A1203 <SEP> 374 <SEP> 68.0
<Tb>

Y, MoB MoBIY, - Ait03 386 69,4

Y, MoB MoBIY, - Ait03 386 69.4

<Tb>
<tb> Y1MoSi <SEP> MoSi / Y1 <SEP> - <SEP> Al2O3 <SEP> 385 <SEP> 69.6
<tb> Y, <SEP> MoBSi <SEP> MoBSi / Y, <SEP> - <SEP> Al2O3 <SEP> 384 <SEP> 70.1
<tb> Y1NiMo <SEP> NiMo / Y1 <SEP> - <SEP> AI203 <SEP> 387 <SEP> 70.3 <SEP> 123
<tb> Y1NiMoP <SEP> NiMoP / Y1 <SEP> - <SEP> Al2O3 <SEP> 384 <SEP> 71.1 <SEP> 124
<tb> Y, NiMoPB <SEP> NiMoPB / Yi <SEP> - <SEP> AI203 <SEP> 384 <SEP> 71.8 <SEP> 120
<tb> Y, NiMoPSi <SEP> NiMoPSi / Y1 <SEP> - <SEP> Al2O3 <SEP> 382 <SEP> 72.5
<tb> Y, <SEP> NiMoPBSi <SEP> NiMoPBSi / Y1 <SEP> - <SEP> AI203 <SEP> 380 <SEP> 72.6
<tb> Y, NiMoPBSiF <SEP> NiMoPBSiF / Y1 <SEP> - <SEP> Al2O3 <SEP> 376 <SEP> 72.3
<tb> YiNiMoPMn <SEP> NiMoPMn / Y1 <SEP> - <SEP> AI203 <SEP> 382 <SEP> 72.0
<tb> Y, NiMoPMnBSi <SEP> NiMoPMnBSi / Y1 <SEP> - <SEP> Al2O3 <SEP> 380 <SEP> 71.9
<tb> Y, NiMoPMnBSi <SEP> NiMoPMnBSlF / Y1 <SEP> - <SEP> Al2O3 <SEP> 377 <SEP> 71.7
<tb> F
<Tb>

Claims (18)

 1. Catalyst comprising at least one matrix and at least one partially armorphe Y zeolite having a peak level of less than 0.4 and a crystalline fraction, expressed relative to a reference zeolite in sodium form (Na), which is lower at 60%. 2- Catalyst according to claim 1 further comprising at least one hydro-dehydrogenating element. 3- Catalyst according to one of the preceding claims wherein the zeolite has: - an overall Si / Al ratio greater than 15, - a Si / AlIV framework ratio greater than or equal to the overall Si / Al ratio, - a pore volume at less than 0.20 ml / g of solid, of which a fraction of between 8% and 50% consists of pores having a diameter of at least 5 nm. 4. Catalyst according to claim 2 wherein the hydro-dehydrogenating element is selected from group VIII elements and group VI B. 5. Catalyst according to one of the preceding claims further comprising at least one element selected from the group consisting of phosphorus, boron, silicon. 6. Catalyst according to claim 5 wherein the element is deposited on the catalyst and mainly located on the matrix. 7- Catalyst according to one of the preceding claims further comprising at least one group VIIA element. 8. Catalyst according to one of the preceding claims also containing at least one element of group VII B. 9- Catalyst according to claim wherein the element of group VII B is manganese. <Desc / Clms Page number 30> 10- Catalyst according to one of the preceding claims containing in% by weight relative to the total mass of the catalyst: - 0.1 to 99.9 of at least one amorphous or poorly crystallized porous mineral matrix of oxide type, - 0, 1 to 99.9% of partially amorphous Y zeolite - 0 to 60% of at least one hydro-dehydrogenating element - 0 to 20% of at least one element selected from the group formed by boron, silicon, phosphorus ; 0 to 20% of at least one element of group VII A - 0 at 20% of at least one element of group VII B. 11- Catalyst according to one of the preceding claims wherein the matrix is selected from alumina, silica-alumina, aluminates, silica. 12- hydrocarbon feed conversion process with a catalyst according to one of the preceding claims. 13- Method according to claim 12 for hydrocracking with a catalyst comprising at least one matrix and at least one partially armorphe Y zeolite having a peak level of less than 0.4 and a crystalline fraction expressed relative to a reference zeolite in form sodium (Na) which is less than 60%. and also comprising at least one hydro-dehydrogenating element.  14- Method according to claim 13 for hydrocracking at a temperature greater than 200 ° C., a pressure greater than 0.1 MPa, a space velocity of 0.1-20h-1 and a hydrogen recycle of at least 50NI / I load.  15- The method of claim 14 wherein the pressure is greater than greater than 2 MPa and less than 12 MPa, the temperature of at least 230 C, the space velocity of 0.1-10h-1 and the recycling of hydrogen at least 100NI / I of charge, the conversion being less than 55%.  16. The method of claim 14 wherein the pressure is at least 5 MPa and the conversion greater than 55%. <Desc / Clms Page number 31>  17-. Process according to one of Claims 12 to 16, in which the catalyst is previously sulphurized. 18- Method according to one of claims 14 to 17 wherein the feed is subjected to hydrotreating before being hydrocracked.