EP2794100A1

EP2794100A1 - Catalyst including at least one nu-86 zeolite, at least one usy zeolite, and a porous inorganic matrix, and method for the hydroconversion of hydrocarbon feedstocks using said catalyst

Info

Publication number: EP2794100A1
Application number: EP12813400.4A
Authority: EP
Inventors: Audrey Bonduelle; Emmanuelle Guillon; Magalie Roy-Auberger
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2011-12-22
Filing date: 2012-11-23
Publication date: 2014-10-29
Also published as: RU2640585C2; JP6236399B2; WO2013093225A1; JP2015502853A; CN103998130B; BR112014014787A2; CN103998130A; US20150231615A1; US9718050B2; FR2984759B1; RU2014130040A; FR2984759A1; KR20140113983A; CA2858049A1; KR102024961B1; CA2858049C; MX2014007368A

Abstract

The invention relates to a catalyst including at least one metal selected from the group consisting of metals from Group VIB and Group VIII of the periodic table, alone or in a mixture, and a support including at least one NU-86 zeolite, at least one Y zeolite, and at least one porous inorganic matrix containing at least aluminum and/or at least silicon. The invention also relates to a method for the hydrocracking of hydrocarbon feedstocks using said catalyst.

Description

CATALYST COMPRISING AT LEAST ONE NU-86 ZEOLITE, AT LEAST ONE USY ZEOLITE AND A POROUS MINERAL MATRIX AND PROCESS FOR HYDROCONVERSION OF

HYDROCARBON LOADS USING THIS CATALYST

Hydrocracking of heavy oil cuts is a key refining process that makes it possible to produce lighter fractions, such as gasolines, light fuel oils and fuels, which the refiner seeks in order to adapt his production to the request. Certain hydrocracking processes also make it possible to obtain a highly purified residue that can constitute excellent bases for oils.

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 of large areas (150 to 800 m2.g-1 generally) having a high acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), the combinations of oxides of boron and aluminum 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 VI B of the periodic table and at least one metal of group VIII, implemented in the presence of sulfur.

The equilibrium between the two acid and hydrogenating functions governs the activity and the selectivity of the catalyst. A weak acid function and a strong hydrogenating function give low active catalysts, operating at generally high temperature (greater than or equal to 390 ° C.), and at low feed space velocity (the WH expressed in volume of charge to be treated by unit of catalyst volume per hour is generally less than or equal to 2 h ^-1 ) but endowed with a very good selectivity in middle distillates Conversely, a strong acid function and a low hydrogenating function give active catalysts but having minus good selectivities in middle distillates The development of active and selective catalysts remains a major area of improvement for hydrocracking processes.

Depending on the operating conditions and the nature of the charges to be converted, the conventional catalysts for catalytic hydrocracking may consist of weakly acidic supports. In moderately acidic carriers, there is the family of silica-aluminas. Many catalysts in the hydrocracking market are based on silica-alumina associated with either a Group VIII metal or, preferably, when the heteroatomic poison contents of the feedstock to be treated exceed 0.005% 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 zeolites, for their part, have a higher catalytic activity than amorphous silica-aluminas, but often have selectivities in light products which are higher. The prior art mentions numerous patent applications. Non-exhaustive are the patents relating to the use of zeolites USY (Ultra-stable-Y) (US 5,171,422) or zeolite Beta (US 6,524,470, US 6,231,750).

The patent application FR 2 755 958 also describes the use of a catalyst comprising at least one matrix and the NU-86 zeolite and at least one active phase in a process for hydrocracking hydrocarbon feeds.

Certain patents are furthermore related to the use of so-called composite catalysts associating a zeolite and a silica-alumina, such as, for example, US Pat. Nos. 4,419,271 and 6,902,664. These combinations make it possible to partially adjust the activity and / or the selectivity of the hydrocracking catalysts.

The research carried out by the applicant on numerous zeolites and microporous solids led him to discover that a catalyst composed of at least one NU-86 zeolite, and at least one Y zeolite and a porous mineral matrix containing at least aluminum or at least silicon make it possible to improve the conversion activity of conventional hydrocracking catalysts while increasing the yield of middle distillates.

More particularly, an object of the present invention relates to a catalyst comprising at least one metal selected from the group consisting of metals of group VIB and group VIII of the Periodic Table, taken alone or as a mixture and a support comprising at least one zeolite NU-86, at least one zeolite Y and at least one porous mineral matrix containing at least aluminum and / or at least silicon.

Another object of the present invention relates to a process for hydrocracking hydrocarbon feedstocks using said catalyst.

An advantage of the present invention is to provide a specific catalyst and a process for hydroconversion of hydrocarbon feeds using said catalyst to increase the yields of middle distillates.

Detailed description of the catalyst

The catalyst according to the present invention comprises and preferably consists of at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table, taken alone or as a mixture and a support comprising at least one at least one zeolite Y and at least one porous mineral matrix comprising at least one of aluminum and / or at least silicon.

According to the invention, the support of said catalyst comprises and is preferably composed of at least one NU-86 zeolite, at least one Y zeolite and at least one porous mineral matrix. containing at least aluminum or at least silicon. - zeolite NU-86

The NU-86 zeolite in hydrogen form, designated H-NU-86 and obtained by calcination and / or ion exchange of the crude NU-86 zeolite synthesis and its method of preparation is described in patent EP-0463768 A2. Said NU-86 zeolite is characterized by structural data of X-ray diffraction defined by Casci et al. in the patent application EP463.768. Zeolite NU-86 is generally synthesized in the presence of sodium cations and an organic structuring agent which is either octamethonium dibromide or nonamethonium di bromide.

Zeolite NU-86 contains silicon and at least one element T selected from the group formed by aluminum, iron, gallium, boron and germanium, preferably T is aluminum.

Zeolite NU-86 does not have a defined structural type, according to the rules of ΙΊΖΑ (International Zeolite Association).

The structural type of this zeolite has not yet been formally attributed by the International Zeolite Association. However, following the work published by the 9th International Congress on Zeolites by JL Casci, PA Box and MD Shannon ("Proceedings of the 9th International Zeolite Conference, Montreal 1992, Eds R. von Ballmoos et al., 1993 by Butterworth) it appears according to its properties: the NU-86 zeolite has a three-dimensional microporous system, this three-dimensional microporous system consists of straight channels whose pore opening is delimited by 11 T atoms (tetrahedral atoms: Si, Al, Ga, Fe ..), straight channels delimited alternately by apertures at 10 and 12 atoms T and sinusoidal channels also delimited alternately by apertures at 10 and 12 atoms T.

The term pore opening with 10, 11 or 12 tetrahedral atoms (T) is understood to mean pores consisting of 10, 11 or 12 oxygen atoms.

The NU-86 zeolite included in the catalyst according to the invention is at least partly, preferably almost completely, in acid form, that is to say in hydrogen (H ⁺ ) form, the sodium content being preferably such that the atomic ratio Na / T is less than 10%, preferably less than 5%, more preferably less than 1%.

The NU-86 zeolite used according to the invention has a Si / T molar ratio of less than 150, preferably less than 100, preferably less than 50, very preferably less than 35, more preferably less than 20 and even more preferably, less than 15. The Si / Al ratio can be obtained on synthesis, without post-modification treatment. It can also be obtained by the dealumination techniques known to those skilled in the art such as, for example, a steam treatment, that is to say a thermal treatment under steam and / or acid treatment. Patent Application EP 0.939.673 describes embodiments of dealumination of zeolite NU-86.

Preferably, the NU-86 used in the invention does not undergo a dealumination step before it is formed in the catalyst support according to the present invention.

- zeolite Y

The zeolite Y is of structural type FAU defined according to the rules of ΙΊΖΑ. The Y zeolites generally used in hydrocracking catalysts are manufactured by modifying commercially available NaY zeolites. This modification leads to zeolites said stabilized, ultra-stabilized or dealuminated, de-liquefied. This modification can be carried out by at least one of the dealumination techniques, for example by a hydrothermal treatment, by acid attack or by a desilication treatment (basic treatment). Zeolites are prepared according to the techniques generally used by dealumination. The successive treatment or modifications of zeolites Y are intended to adapt the acidity and mesoporosity of the zeolite. Examples of the type of modification of zeolites are described in the book by C. Marcilly, Catalyze acid-basique, Technip editions 2003.

The acid etching operation consists, for example, in putting the zeolite in contact 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 characteristics of the Y zeolite used in the invention are advantageously: an overall Si / Al atomic ratio of between about 2.5 and 100 and preferably between about 2.5 and 80, still more preferably between 3 and 50 and more preferably most preferred between 5 and 25,

a sodium content of less than 0.15% by weight determined on the zeolite calcined at 1100 ° C., a crystalline parameter has elemental mesh of between 24.58 A and 24.20 A and preferably between 24.38 A and 24.24 A,

a specific surface area determined by the BET method of greater than about 300 m ² / g and preferably greater than 400 m ² / g, preferably greater than 500 m ² / g and more preferably greater than 700 m ² / g. an initial mesoporous volume measured by nitrogen porosimetry greater than 0.05 ml. g ^"1 , preferably greater than 0.07 ml. g ^-1 , and more preferably greater than 0.1 ml. g ^{"and 1} and even more preferably greater than 0.13 ml. ^{g" 1.}

^• In addition, the Y zeolite used in the invention is partially amorphous and preferably is prepared according to techniques generally used for the dealumination or desilication, from Y zeolites commercially available. Preferably, the zeolite Y included in the support of the catalyst according to the invention is a dealuminated zeolite called USY.

The dealuminated USY zeolite used according to the invention may optionally and preferably have a weight fraction of extra-initial network aluminum atom greater than 5%, preferably greater than 10%, preferably greater than 15%, and preferably even more preferred greater than 20% by weight relative to the total weight of the aluminum present in the zeolite.

Said zeolite Y entering into the composition of the catalyst according to the invention is advantageously calcined and exchanged by at least one treatment with a solution of at least one ammonium salt so as to obtain the ammonium form of the zeolites which, once calcined, lead to the hydrogen form of said zeolites. This treatment can be performed before the modification of the zeolites (dealumination, steaming, desilication ...) or after the modification of said zeolites.

Said zeolite Y used according to the invention is at least partly, preferably almost completely, in acid form, that is to say in hydrogen (H ⁺ ) form. The atomic ratio Na / T is generally less than 10% and preferably less than 5% and even more preferably less than 1%.

A preferred zeolite Y used according to the invention is a zeolite Y having undergone a particular hydrothermal treatment as described in patent application US-A-5,601,798. Said treatment has the effect of increasing the mesoporosity of zeolites Y, USY , VUSY and SDUSY, which zeolites are particularly advantageous in combination with zeolite Y and the porous mineral matrix comprising at least aluminum and / or at least silicon described above.

- The porous mineral matrix

According to the invention, the porous mineral matrix entering the composition of the catalyst support according to the invention comprises at least aluminum and / or at least silicon.

Preferably, said matrix comprises at least one aluminum oxide or at least one silicon oxide. Said matrix may advantageously be acidic or not. Said matrix may advantageously be mesostructured or not.

Said porous mineral matrix may advantageously be chosen from transition aluminas, doped alumina, preferably phosphorus, boron and / or fluorine, silicalite and silicas, alumina-silicates, preferably amorphous or poorly crystallized, crystallized non-zeolitic molecular sieves such as silicoaluminophosphates, aluminophosphates, ferrosilicates, titanium silicoaluminates, borosilicates, chromosilicates and transition metal aluminophosphates, alone or as a mixture .

In the case where said porous mineral matrix is chosen from transition aluminas, silicalite and silicas such as, for example, mesoporous silicas, said matrix is not acidic. By transition alumina is meant, for example, an alpha phase alumina, a delta phase alumina, a gamma phase alumina or a mixture of alumina of these different phases.

In the case where said porous mineral matrix is chosen from aluminosilicates, preferably amorphous or poorly crystallized, crystallized non-zeolitic molecular sieves such as silicoaluminophosphates, aluminophosphates, ferrosilicates, titanium silicoaluminates, borosilicates, chromosilicates and aluminophosphates of transition metals, doped alumina, preferably phosphorus, boron and / or fluorine, said matrix is acidic. Any known silica-alumina or aluminosilicate known to those skilled in the art is suitable for the invention.

The acidic porous mineral matrix may also advantageously contain, in addition to at least one of the above-mentioned oxide compounds, at least one synthetic or natural simple clay of 2: 1 dioctahedral phyllosilicate or 3: 1 trioctahedral phyllosilicate type such as kaolinite , antigorite, chrysotile, montmorillonnite, beidellite, vermiculite, talc, hectorite, saponite, laponite. These clays can be optionally delaminated.

Said porous mineral matrix preferably contains a content of cationic impurities of less than 0.1% by weight, preferably less than 0.05% by weight and even more preferably less than 0.025% by weight. The content of cationic impurities means the total content of alkali. The matrix preferably contains an anionic impurities content of less than 1% by weight, preferably less than 0.5% by weight and even more preferably less than 0.1% by weight.

In the case where said porous mineral matrix comprises at least silicon, the weight by weight content of SiO ₂ in said porous mineral matrix is advantageously between 1% and 99% by weight, preferably between 5% and 95% by weight, preferably between 10% and 90% by weight, more preferably between 10 and 50% by weight and even more preferably between 20 and 50% by weight.

Preferably, said porous mineral matrix is chosen from alumina and silica-alumina.

The support of the catalyst according to the invention advantageously has a pore volume of between 0.1 and 1.2 ml / g and preferably between 0.2 and 1 ml / g. The specific surface area of said support is advantageously between 50 and 1000 m ² / g and preferably between 100 and 600 m ² / g. Said support is shaped so that it is advantageously in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates whose specific shape can result from a crushing step. Very advantageously, said support is in the form of balls or extrudates.

- The hydrogenating function

The catalyst according to the invention also comprises at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table, alone or as a mixture.

The Group VIB and Group VIII metals may be present at least in part in the form selected from the metal form and / or oxide and / or sulfide.

Group VIII metals are advantageously chosen from noble or non-noble metals, preferably from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum alone or mixture and preferably, said group VIII metals are selected from nickel, cobalt and iron, platinum and palladium alone or in mixture.

Non-noble Group VIII metals are preferably selected from nickel, cobalt and iron. The noble Group VIII metals are preferably selected from platinum and palladium alone or in admixture.

Group VIB metals are preferably selected from tungsten and molybdenum alone or as a mixture.

Advantageously, the following combinations of metals are used: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, cobalt-tungsten, the preferred combinations are: nickel-molybdenum, cobalt-molybdenum, cobalt-tungsten, nickel-tungsten and still more preferably nickel-moybdenum and nickel-tungsten.

Preferably, said catalyst comprises at least one Group VIB hydro-dehydrogenating metal in combination with at least one Group VIII non-noble metal.

In the case where the catalyst comprises at least one Group VIB metal in combination with at least one Group VIII non-noble metal, the Group VIB metal content is advantageously comprised, in oxide equivalent, of between 5 and 40% by weight per relative to the total mass of said catalyst, preferably between 10 and 35% by weight and very preferably between 15 and 30% by weight and the non-noble metal content of group VIII is advantageously comprised, in oxide equivalent, between 0 , 5 and 10% by weight relative to the total mass of said catalyst, preferably between 1 and 8% by weight and very preferably between 1, 5 and 6% by weight.

In the case where the catalyst comprises at least one noble group VIII metal, the noble metal content of group VIII is advantageously comprised, in oxide equivalent, of between 0.05 and 5% by weight. relative to the total mass of said catalyst, preferably between 0.1 and 2% by weight and very preferably between 0.1 and 1% by weight.

The catalyst according to the invention may also optionally comprise at least one element of group VI IA, preferably chosen from chlorine and fluorine alone or as a mixture.

Preferably, said catalyst optionally comprises a content of group VIIA element of between 0 to 10%, preferably between 0.1 to 8% and more preferably between 0.1 to 5% by weight of the metal element relative to to the total mass of said catalyst.

The catalyst according to the present invention may also optionally comprise promoters of the active phase, preferably chosen from doping elements and organic compounds. Said entities may advantageously be added at different stages of the preparation of the catalyst according to the invention.

- The doping elements

The catalyst according to the present invention may also optionally comprise at least one doping element chosen from boron, silicon and phosphorus alone or as a mixture. The term "doping element" means an added element which in itself has no catalytic character but which increases the catalytic activity of the catalyst.

Said catalyst optionally comprises a content of doping element of between 0 to 10%, preferably between 0.5 to 8% and more preferably between 0.5 to 6% by weight oxide relative to the total mass of said catalyst. The silicon content, doping element, is not taken into account in the total silicon content in the zeolite or in the matrix.

Said doping element may advantageously be introduced alone or as a mixture during the synthesis of said support used in the invention. It can also be introduced by impregnation of the support after shaping, before or after drying, before or after calcination.

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

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

The catalyst according to the present invention may also optionally comprise at least one organic additive. The term organic additive is understood to mean an organic molecule which in itself has no catalytic character but which increases the catalytic activity of the catalyst.

The organic compounds used as promoting elements for the hydrogenating function are preferably chosen from chelating agents, non-chelating agents, reducing agents and additives known to those skilled in the art. Said organic compounds are advantageously chosen from optionally etherified mono-, di- or polyalcohols, carboxylic acids, sugars, non-cyclic mono, di or polysaccharides such as glucose, fructose, maltose, lactose or sucrose, esters, ethers, crown ethers, cyclodextrins and compounds containing sulfur or nitrogen such as nitriloacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine, alone or as a mixture.

Said catalyst optionally comprises an organic additive content of between 0 to 30%, preferably between 5 to 30% and more preferably between 10 to 30% by weight relative to the total weight of said catalyst.

- The catalyst

The catalyst according to the present invention advantageously comprises, in% by weight with respect to the total mass of the catalyst:

0.2 to 10%, preferably 0.2 to 8%, preferably 0.5 to 5% by weight, of at least one NU-86 zeolite,

0.4 to 40%, preferably 0.5 to 30%, preferably 1 to 20% by weight of at least one Y zeolite,

from 0.5 to 50%, preferably from 0.5 to 40%, and still more preferably from 0.5 to 30% of at least one hydro-dehydrogenating metal selected from the group consisting of group VIB and group VIII,

- 1 to 99% and preferably 2 to 98%, preferably 5 to 95% of at least one porous mineral matrix comprising at least aluminum and / or at least silicon.

Said catalyst optionally comprises:

from 0 to 10%, preferably from 0.5 to 8% and even more preferably from 0.5 to 6% by weight of oxide of at least one doping element chosen from silicon introduced as an element; dopant, boron and phosphorus, and preferably boron and / or silicon. The silicon content, doping element, is not taken into account in the total silicon content in the zeolite or in the matrix. 0 to 10%, preferably 0.1 to 8% and even more preferably 0.1 to 5% by weight of at least one member selected from group VIIA, preferably fluorine, the percentage being expressed in weight percentage of the metal element.

from 0 to 30% by weight and preferably from 10 to 30% by weight of at least one organic additive as described above.

- Formatting supports and / or catalysts

The support can be shaped by any technique known to those skilled in the art. The shaping can be carried out for example by extrusion, by pelletization, by the method of coagulation in drop ("oil-drop"), by rotating plate granulation or by any other method well known to those skilled in the art.

The shaping can also be carried out in the presence of the various constituents of the catalyst and extrusion of the obtained mineral paste, by pelletizing, shaped into beads at the rotating bezel or drum, drop coagulation, "oil-drop", "oil-up", or any other known method of agglomeration of a powder containing alumina and optionally other ingredients selected from those mentioned above.

The shaping can be performed by any method well known to those skilled in the art. Advantageously, it is obtained by mixing the zeolites and at least one porous mineral matrix and the mixture is shaped. The hydrogenating element or elements are introduced during the mixing, or preferably after shaping. The shaping is followed by calcination, the hydrogenating element or elements are introduced before or after this calcination, preferably after.

One of the preferred methods according to the present invention is to mix the powders of zeolites NU-86 + Y in a wet gel for a few tens of minutes, then to pass the paste thus obtained through a die to form extrudates with a diameter between 0 , 4 and 4 mm

Furthermore, these supports implemented according to the present invention may have been treated as is well known to those skilled in the art by additives to facilitate the shaping and / or improve the final mechanical properties of the supports. By way of example of additives, there may be mentioned in particular cellulose, carboxymethylcellulose, carboxy-ethylcellulose, tall oil, xanthan gums, surfactants, flocculating agents such as polyacrylamides, carbon black, starches, stearic acid, polyacrylic alcohol, polyvinyl alcohol, biopolymers, glucose, polyethylene glycols, etc.

The adjustment of the characteristic porosity of the supports of the invention is partially carried out during this step of shaping the support particles. The compacted packing density of the supports, after calcination, is advantageously greater than 0.5 g / cm ³ and preferably greater than 0.6 g / cm ³ .

Thermal treatments of the support

The shaped support is then advantageously subjected to one or more heat treatments.

Said support advantageously undergoes a drying step. Said drying step is carried out by any technique known to those skilled in the art. Preferably, the drying is carried out under air flow. Said drying can also be advantageously carried out under a stream of any oxidizing, reducing or inert gas. Drying is advantageously carried out under reduced pressure. Preferably, the drying is preferably carried out between 50 and 180 ° C, preferably between 60 and 150 ° C and most preferably between 80 and 130 ° C.

Said support, optionally dried, then preferably undergoes a calcination step.

Said calcination step is advantageously carried out in the presence of molecular oxygen, for example by conducting an air sweep, at a temperature of less than or equal to 1100 ° C. At least one calcination step can advantageously be carried out after any one of the steps of the preparation. Said calcination step may advantageously be carried out in a crossed bed, in a licked bed or in a static atmosphere. For example, the furnace used may be a rotating rotary kiln or a vertical kiln with radial traversed layers. The calcination conditions: temperature and time depend mainly on the maximum temperature of use of the catalyst. Preferably, said calcination step is carried out for more than one hour at 200 ° C at less than one hour at 1100 ° C. The calcination can advantageously be carried out in the presence of water vapor. The final calcination may optionally be carried out in the presence of an acidic or basic vapor. For example, the calcination can be carried out under partial pressure of ammonia.

Post synthesis synthesis treatments

Post-synthesis treatments can be performed to improve the properties of the support.

Said support can thus optionally be subjected to a hydrothermal treatment in a confined atmosphere or under a stream of steam. Hydrothermal treatment in a confined atmosphere means treatment by autoclaving in the presence of water at a temperature above room temperature.

In the event that said hydrothermal treatment is carried out ^■ confined atmosphere, said support comprising porous mineral matrix and Y zeolite and NU-86, shaped may be treated different ways. Thus, said support may advantageously be impregnated with acid, prior to its passage through the autoclave, the autoclaving being carried out either in the vapor phase or in the liquid phase, this vapor or liquid phase of the autoclave possibly being acidic or not . This impregnation, prior to autoclaving, may be acidic or not. This impregnation, prior to autoclaving can be carried out dry or by immersion of said support in an acidic aqueous solution. Preferably, the impregnation is carried out dry.

The autoclave is preferably a rotary basket autoclave such as that defined in patent application EP-A-0 387 109.

The temperature during autoclaving is advantageously between 100 and 250 ° C for a period of time between 30 minutes and 3 hours.

Catalyst preparation

The hydrogenating function can be introduced in part only (for example, combinations of metal oxides of groups VIB and VIII) or in full at the time of mixing the zeolite, with the oxide gel chosen as a matrix. Part of the metals may be deposited prior to shaping on the zeolite mixture.

The hydrogenating function can be introduced by one or more ion exchange operations on the calcined support consisting of a zeolite as previously described, 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 catalyst contains 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. It is possible to impregnate Molybdenum precursors or tungsten precursors which contain phosphorus, such as Keggin or Strandberg type polyoxometalates, which also makes it possible to introduce phosphorus so as to promote the catalytic activity. The impregnation of the matrix is preferably carried out by the "dry" impregnation method well known to those skilled in the art. The impregnation may be carried out in a single step by a solution containing all the constitutive elements of the final catalyst or in several stages by means of several successive impregnations interspersed with intermediate drying steps, with solutions containing one or more metals.

Phosphorus, boron, silicon as a doping element 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 oxygenated water and to carry out a so-called dry impregnation, in which the pore volume of the precursor is filled with the solution containing 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 the precursor is a nickel-molybdenum catalyst supported on a support containing zeolite and alumina, it is possible to impregnate this precursor with aqueous ammonium biborate solution. and of Rhodorsil E1P 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 drying, for example at 80 ° C., and 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 group VIIA element, preferably fluorine, it is for example possible to impregnate the catalyst with a solution of ammonium fluoride, 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 implemented 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 and 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 group VIIA, at least one element of group VIIB, 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 the case where the catalyst contains an organic additive, said organic additive may advantageously be introduced alone or in mixture after shaping and calcining the support. Said organic additive may be introduced by impregnation before impregnation of the metal precursors, co-impregnation with the metal precursors or post-impregnation after impregnation of the metal precursors and optionally drying of the catalyst thus formed. In order to complete the catalyst preparation, the wet solid is allowed to stand under a humid atmosphere at a temperature of preferably between 10 and 80 ° C. Said moist solid obtained is advantageously dried at a temperature between 60 and 150 ° C. Then the solid obtained is optionally calcined at a temperature advantageously between 150 and 800 ° C.

The sources of group VIII elements that can be used are well known to those skilled in the art. The precursors of the non-noble group VIII metal (s) are preferably chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates. Nickel hydroxycarbonate, nickel nitrate, cobalt nitrate, nickel carbonate or nickel hydroxide, cobalt carbonate or cobalt hydroxide are preferably used.

The precursors of the noble (e) metal (s) of group VIII are / are advantageously chosen from halides, for example chlorides, nitrates, acids such as chloroplatinic acid, oxychlorides such as ammoniacal oxychloride of ruthenium.

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, it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( H ₃ PMo ₁₂ 04O) and salts thereof, and optionally silicomolybdic acid (H ₄ SiMo ₁₂ 0 o) and the corresponding salts. Molybdenum sources may also be any polyoxometalate of Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example. Molybdenum trioxide and heteropolyanions of the Strandberg (P2M05O23 ^{6 "} ), Keggin (M012O40 ^3" ), lacunated Keggin or substituted Keggin type known to those skilled in the art are preferably used.

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 (H ₃ W ₁₂ 0 ₄ o) and their salts, and optionally silicotungstic acid (H ₄ SiW ₁₂ 0 ₄ o) and its salts. Tungsten sources can also be any polyoxometalate of Keggin type, Keggin lacunary, substituted Keggin, Dawson, for example. Oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of the Keggin, Keggin lacunary or substituted Keggin type known to those skilled in the art are preferably used.

The phosphorus source may advantageously be orthophosphoric acid H ₃ PO ₄ , the corresponding salts and esters or ammonium phosphates. Phosphorus can also advantageously be introduced together with the group VIB element (s) in the form of heteropolyanions of Keggin, Keggin lacunary, substituted Keggin or Strandberg type such as, for example, in the form of acid. phosphomolybdic acid and its salts, phosphotungstic acid and its salts, during the synthesis of said matrix. Phosphorus, when not introduced during the synthesis of said matrix but in post-impregnation, may advantageously 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, pyridine and quinoline family compounds and pyrrole family compounds.

Many sources of silicon can be used. Thus, it is possible to use ethyl orthosilicate Si (OEt) _4i siloxanes, polysiloxanes, halide silicates such as ammonium fluorosilicate (NH ₄ ) ₂ SiF ₆ or sodium fluorosilicate Na ₂ SiF ₆ . 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 boron source may advantageously be boric acid, preferably orthoboric acid H ₃ B0 ₃ , ammonium biborate or pentaborate, boron oxide, boric esters. Boron may also be introduced together with the group VIB element (s) in the form of heteropolyanions of Keggin, Keggin lacunary, substituted Keggin such as for example in the form of boromolybdic acid and its salts, or borotungstic acid and its salts during the synthesis of said matrix. Boron, when it is not introduced during the synthesis of said matrix but in post-impregnation, can advantageously be introduced for example by a boric acid solution in a water / alcohol mixture or in a mixture of water / ethanolamine. Boron may also advantageously 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.

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 of 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 that can release fluoride anions in water, such as ammonium fluorosilicate (NH ₄ ) ₂ SiF ₆ , silicon tetrafluoride SiF ₄ or sodium tetrafluoride Na ₂ SiF ₆ . The fluorine may be introduced for example by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.

The organic compounds used as promoting elements for the hydrogenating function are preferably chosen from chelating agents, non-chelating agents, reducing agents and additives known to those skilled in the art. Said organic compounds are advantageously chosen from optionally etherified mono-, di- or polyalcohols, carboxylic acids, sugars, non-cyclic mono, di or polysaccharides such as glucose, fructose, maltose, lactose or sucrose, esters, ethers, crown ethers, cyclodextrins and compounds containing sulfur or nitrogen such as nitriloacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine alone or as a mixture.

The catalysts thus obtained, in oxide 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. , a pore 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.

Preferably, the catalysts according to the invention are in the form of spheres or extrusions. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm. The shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings. The trilobal form is preferably used, but any other form can be used.

The packed packing density of the catalysts is greater than 0.65 g / cm ³ and preferably greater than 0.75 g / cm ³ The shaping can be carried out using the catalyst shaping techniques known to those skilled in the art, such as, for example: extrusion, coating, spray drying or tabletting.

Water can be added or removed to adjust the viscosity of the extrusion paste. This step can be performed at any stage of the kneading step.

To adjust the solid content of the extrusion paste to make it extrudable, a predominantly solid compound and preferably an oxide or hydrate may also be added. A hydrate and, more preferably, an aluminum hydrate are preferably used. The loss on ignition of this hydrate will be greater than 15%.

The acid content added to the kneading before shaping is less than 30%, preferably between 0.5 and 20% by weight of the anhydrous mass of silica or alumina involved in the synthesis.

Extrusion can be performed by any conventional tool, commercially available. The paste resulting from the mixing is extruded through a die, for example using a piston or a single screw or twin extrusion screw. This extrusion step can be performed by any method known to those skilled in the art.

The catalysts thus obtained are used for the conversion of hydrocarbon feeds and in particular by hydrocracking.

Hydrocracking process

The present invention also relates to a process for hydrocracking hydrocarbon feeds using the catalyst according to the present invention, said process operating, in the presence of hydrogen, at a temperature above 200 ° C., at a pressure greater than 1 MPa, at a space velocity of between 0.1 and 20 h -1 and a quantity of hydrogen introduced is such that the volume ratio by volume of hydrogen / liter of hydrocarbon is between 80 and 5000 L / L.

Preferably, the hydrocracking process according to the invention operates at a temperature of between 250 and 480 ° C., preferably between 320 and 450 ° C., very preferably between 330 and 435 ° C., under a pressure of between 2 and 25 MPa, preferably between 3 and 20 MPa, at a space velocity of between 0.1 and 6 h -1, preferably between 0.2 and 3 h -1, and with a quantity of hydrogen introduced. such that the volume ratio of hydrogen liter / liter of hydrocarbon is between 100 and 2000 L / L.

These operating conditions used in the process according to the invention generally make it possible to achieve pass conversions, products having boiling points below 340 ° C., and better below 370 ° C, greater than 15% by weight and even more preferably between 20 and 95% by weight.

A wide variety of fillers can be processed in the process according to the invention. They advantageously contain at least 20% by volume and preferably at least 80% by volume of compounds boiling above 340 ° C.

The hydrocarbon feedstock used in the process according to the present invention is advantageously chosen from LCOs (Light Cycle Oil = light gas oils from a catalytic cracking unit), atmospheric distillates, vacuum distillates such as, for example, gas oils derived from the direct distillation of crude or conversion units such as FCC, coker or visbreaking, feeds from aromatic extraction units of lubricating oil bases or from solvent dewaxing of oil bases lubricant, distillates from processes for desulphurization or hydroconversion in fixed bed or bubbling bed of RAT (atmospheric residues) and / or RSV (vacuum residues) and / or deasphalted oils, paraffins from the Fischer process -Tropsch and deasphalted oils, taken alone or mixed. The list above is not exhaustive. Said fillers preferably have a boiling point T5 greater than 340 ° C., preferably greater than 370 ° C., that is to say that 95% of the compounds present in the feed have a boiling point greater than 340 ° C. and preferably greater than 370 ° C.

The nitrogen content of the feedstocks treated in the processes according to the invention is advantageously greater than 500 ppm by weight, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4000 ppm by weight and even more preferably between 1000 and 1000 ppm by weight. and 4000 ppm weight. The sulfur content of the fillers treated in the processes according to the invention is advantageously between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.5 and 3%. % weight

The charge may optionally contain metals. The cumulative nickel and vanadium content of the feeds treated in the processes according to the invention is preferably less than 1 ppm by weight.

The charge may optionally contain asphaltenes. The asphaltene content is generally less than 3000 ppm by weight, preferably less than 1000 ppm by weight, more preferably less than 200 ppm by weight.

Said hydrocarbon feed may optionally advantageously contain metals, in particular nickel and vanadium. The cumulative nickel and vanadium content of said hydrocarbon feedstock treated according to the hydrocracking method according to the invention is preferably less than 1 ppm by weight. The asphaltene content of said hydrocarbon feedstock is generally less than 3000 ppm, preferably less than 1000 ppm, even more preferably less than 200 ppm. Sulphidation of catalysts

Prior to the injection of the feedstock and in the case where said catalyst comprises non-noble metals, the catalysts used in the process according to the present invention are subjected to a sulphurization treatment making it possible to transform, at least in part, the metallic species in sulphide before they come into contact with the charge to be treated. This activation treatment by sulfurization is well known to those skilled in the art and can be performed by any method already described in the literature either in-situ, that is to say in the reactor, or ex-situ.

A conventional sulphurization method well known to those skilled in the art consists in heating the catalyst in the presence of hydrogen sulphide (pure or for example under a stream of a hydrogen / hydrogen sulphide mixture) at a temperature of between 150 and 800 ° C. preferably between 250 and 600 ° C, usually in a crossed-bed reaction zone.

Cribs

In the case where the feedstock contains resins and / or asphaltenes-type compounds, it is advantageous to first pass the feedstock over a bed of catalyst or adsorbent other than the hydrocracking or hydrotreatment catalyst. The catalysts or guard beds used according to the invention are in the form of spheres or extrudates. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm. The shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings. The cylindrical shape is preferably used, but any other shape may be used.

In order to remedy the presence of contaminants and / or poisons in the feed, the guard catalysts may, in another preferred embodiment, have more particular geometric shapes in order to increase their void fraction. The void fraction of these catalysts is between 0.2 and 0.75. Their outer diameter can vary between 1 and 35 mm. Among the particular forms possible without this list being exhaustive, we cite: hollow cylinders, hollow rings, Raschig rings, serrated hollow cylinders, crenellated hollow cylinders, pentaring carts, multi-hole cylinders, etc ..

These catalysts or guard beds may have been impregnated with an active phase or not. Preferably, the catalysts are impregnated with a hydro-dehydrogenation phase. Very preferably, the CoMo or NiMo phase is used.

These catalysts or guard beds may have macroporosity. The guard beds can be marketed by Norton-Saint-Gobain, for example the MacroTrap® guard beds. Guard beds can be marketed by Axens in the ACT family: ACT077, ACT645, ACT961 or HMC841, HMC845, HMC868 or HMC945. It may be particularly advantageous to superimpose these catalysts in at least two different beds of varying heights. The catalysts having the highest void content are preferably used in the first catalytic bed or first catalytic reactor inlet. It may also be advantageous to use at least two different reactors for these catalysts.

Modes of realization

The hydrocracking process according to the invention using the catalyst described above, covers the pressure and conversion ranges from mild hydrocracking to high pressure hydrocracking. Mild hydrocracking means hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 Pa.

The hydrocracking process according to the invention is carried out in the presence of at least one hydrocracking catalyst according to the invention. The hydrocracking process according to the invention may advantageously be carried out in one or two stages, independently of the pressure at which said process is carried out. It is carried out in the presence of one or more hydrocracking catalyst (s) obtained according to the invention, in one or more reaction unit (s) equipped with one or more reactor (s). .

The hydrocracking process according to the invention can advantageously use said catalyst described above alone, in one or more fixed bed catalytic beds, in one or more reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the unconverted fraction, optionally in combination with a conventional hydrotreating catalyst located upstream of the catalyst used in the process according to the present invention.

The hydrocracking process according to the invention can advantageously also use said catalyst described above alone, in one or more bubbling bed reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the reactor. unconverted fraction, optionally in combination with a conventional hydrotreating catalyst located in a fixed bed or bubbling bed reactor upstream of the catalyst used in the process according to the present invention.

The bubbling bed operates with removal of spent catalyst and daily addition of new catalyst to maintain stable catalyst activity.

The catalyst described according to the invention can also advantageously be used in the first hydrotreatment reaction zone, in pretreatment converting, alone or in combination with another conventional hydrorefining catalyst, situated upstream of the catalyst described according to the invention, in one or more catalytic bed (s), in one or more reactor (s), in fixed bed or bubbling bed. One-step process

The hydrocracking process according to the invention can advantageously be carried out in a so-called one-step process.

The so-called hydrocracking in one step, comprises firstly and in a general manner advanced hydrorefining which aims to carry out a hydrodenitrogenation and a desulphurization of the charge before it is sent on the hydrocracking catalyst proper , especially in the case where it comprises a zeolite. This extensive hydrorefining of the feed causes only a limited conversion of the feedstock into lighter fractions, which remains insufficient and must therefore be completed on the more active hydrocracking catalyst described above. However, it should be noted that no separation occurs between the two types of catalysts. All of the effluent at the outlet of the reactor is injected onto said hydrocracking catalyst proper and only after that a separation of the products formed is carried out. This version of the hydrocracking, also called "Once Through", has a variant that has a recycling of the unconverted fraction to the reactor for further conversion of the charge.

The catalyst described according to the invention is therefore advantageously used in a so-called hydrocracking process in a step, in a hydrocracking zone placed downstream of a hydrorefining zone, no intermediate separation being implemented. between the two areas.

Preferably, the hydrorefining catalyst used in the first hydrorefining reaction zone, alone or in combination with another conventional hydrorefining catalyst, located upstream of the catalyst described according to the invention, is a catalyst optionally comprising a doping element. selected from phosphorus, boron and silicon, said catalyst being based on non-noble group VIII elements and optionally in combination with group VIB elements on alumina or silica alumina support and even more preferably said catalyst comprises nickel and tungsten.

The catalyst described according to the invention can also advantageously be used in the first hydrorefining reaction zone, in pretreatment converting, alone or in combination with another conventional hydrorefining catalyst, situated upstream of the catalyst described according to the invention, in one or more catalytic bed (s), in one or more reactor (s).

One-step process in fixed bed with intermediate separation

The hydrocracking process according to the invention can advantageously be implemented in a so-called fixed-bed process with intermediate separation.

Said method advantageously comprises a hydrorefining zone, an area allowing partial removal of the ammonia, for example by a hot flash, and a zone comprising said hydrocracking catalyst according to the invention. This process for hydrocracking fillers in one step for the production of middle distillates and optionally of oil bases advantageously comprises at least a first hydrorefining reaction zone, and at least a second reaction zone, in which the hydrocracking of at least part of the hydrocracking is carried out; effluent from the first reaction zone. This process also advantageously comprises an incomplete separation of the ammonia from the effluent leaving the first zone. This separation is advantageously carried out by means of an intermediate hot flash. The hydrocracking performed in the second reaction zone is advantageously carried out in the presence of ammonia in an amount less than the amount present in the feed, preferably less than 1500 ppm by weight, more preferably less than 1000 ppm by weight and even more preferably less than 800 ppm nitrogen weight.

The catalyst described according to the invention is therefore advantageously used in a hydrocracking process called a fixed-bed intermediate separation step, in a hydrocracking zone placed downstream of a hydrorefining zone, an intermediate separation. partial elimination of ammonia being carried out between the two zones.

Two-step process

The hydrocracking process according to the invention can advantageously be implemented in a so-called two-step process.

The two-stage hydrocracking comprises a first step whose objective, as in the "one-step" process, is to perform the hydrorefining of the feedstock, but also to achieve a conversion of the latter of the order in general. from 40 to 60%. The effluent from the first step then undergoes separation (distillation), which is often called intermediate separation, which aims to separate the conversion products from the unconverted fraction. In the second step of a process two step hydrocracking step, only the fraction of the unconverted feedstock in the first step is treated. This separation allows a two-stage hydrocracking process to be more selective in middle distillates (kerosene + diesel) than a one-step process. Indeed, the intermediate separation of the conversion products avoids their "over-cracking" in naphtha and gas in the second step on the hydrocracking catalyst. Furthermore, it should be noted that the unconverted fraction of the feedstock treated in the second step generally contains very low levels of NH 3 as well as organic nitrogen compounds, generally less than 20 ppm by weight or even less than 10 ppm by weight. .

The configurations of fixed-bed or ebullated-bed catalytic beds described in the case of a so-called one-step process may advantageously be used in the first step of a so-called two-step scheme, that the catalyst according to the invention is used. alone or in combination with a conventional hydrorefining catalyst.

The catalyst described according to the invention is therefore advantageously used in a so-called two-stage hydrocracking process in the second hydrocracking stage placed downstream of the first hydrorefining stage, an intermediate separation being carried out between both areas.

For the so-called one-step processes and for the first hydrorefining stage of two-stage hydrocracking processes, the conventional hydrorefining catalysts that may advantageously be used are the catalysts optionally comprising a doping element chosen from phosphorus, boron and silicon, said catalyst being based on non-noble group VIII elements and optionally in combination with group VIB elements on alumina or silica alumina support and even more preferably said catalyst comprises nickel and tungsten.

According to a first embodiment of the hydrocracking process according to the invention, the hydrocracking catalyst (s) positioned in the hydrocracking process obtained is (are) advantageously used. singly or in sequence, in one or more catalytic beds, in a fixed bed or in a bubbling bed, in one or more reactors, in a so-called "one-step" hydrocracking scheme, with or without liquid recycling of the unconverted fraction, optionally in combination with a hydrorefining catalyst located upstream of the hydrocracking catalyst (s). The bubbling bed operates with removal of spent catalyst and daily addition of new catalyst to maintain stable catalyst activity.

According to a second embodiment of the hydrocracking process according to the invention, the hydrocracking catalyst (s) of the hydrocracking process according to the invention is (are) advantageously used, alone (s) or in a sequence, in one or more catalytic beds, in one and / or the other step of a "two-step" hydrocracking scheme. The "two-stage" scheme is a scheme for which there is an intermediate separation of the effluents between the two reaction zones. This scheme can take place with or without liquid recycling of the non converted from the first reaction zone or the second reaction zone. The first reaction zone operates in fixed bed or bubbling bed. In the particular case where the hydrocracking catalyst (s) obtained according to the invention would be placed in the first reaction zone, they would preferably be placed in association with a hydrorefining catalyst situated upstream of said catalysts.

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

EXAMPLE 1 Preparation of a Support S1 Containing a NU-86 Zeolite, a Y-Zeolite and a Silica-Alumina-type Porous Matrix and the Corresponding Catalyst C1 (in Accordance with the Invention)

One of the raw materials used is a NU-86 zeolite, which is prepared according to example 2 of patent EP 0 463768 A2 and has an overall Si / Al atomic ratio equal to 11 and an atomic ratio Na / Al equal to 0 25. Another raw material used is zeolite Y in protonated form (H +) CBV 720 from zeolyst (Table 1).

The NU-86 zeolite, synthetic crude, first undergoes so-called dry calcination at 550 ° C. under a stream of dry air for 9 hours. Then the solid obtained is subjected to four ion exchanges in a solution of NH ₄ N0 ₃ 10N, at about 100 ° C for 4 hours for each exchange. The solid thus obtained is referenced NH ₄ -NU-86/1 and has a Si / Al = 11 ratio and a Na / Al ratio = 0.0012. Its other physicochemical characteristics are summarized in Table 2.

The crystallites of zeolite NU-86 are in the form of crystals whose size varies from 0.4 μπι to 2 μιτι.

To prepare the support for the hydrocracking catalyst, 2% by weight of the aforementioned NU-86 zeolite is used which is mixed with 5.6% by weight of a above mentioned YZV 720 zeolite Y and with , 4% by weight of a silica alumina which contains 30% by weight of SiO ₂ and 70% by weight of Al ₂ O ₃ . The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air. The extrudates are then treated with steam at 750 ° C. for 2 hours.

The carrier extrudates containing NU-86 zeolite and Y zeolite previously described are dry-impregnated with an aqueous solution containing ammonium metatungstate and nickel nitrate. They are dried overnight at 120 ° C. under air and finally calcined under air at 450 ° C. for 2 hours. The oxide weight contents of catalyst C1 are 3% by weight for Ni (expressed as NiO) and 28% by weight for W (expressed as W0 ₃ ).

EXAMPLE 2 Preparation of a Support S2 Containing a NU-86 Zeolite and a Porous Matrix of Silica-Alumina Type and the Corresponding Catalyst C2 (Not in Accordance with the Invention)

The same NU-86 zeolite as in Example 1 was used for the preparation of support S2 and catalyst C2.

To prepare the support of the hydrocracking catalyst, 7.6% by weight of the aforementioned NU-86 zeolite is used which is mixed with 92.4% by weight of a silica alumina which contains 30% by weight of SiO 2. ₂ and 70% by weight of Al ₂ O ₃ . The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air. The extrudates are then treated with steam at 750 ° C. for 2 hours.

The carrier extrudates containing zeolite NU-86 are dry impregnated with an aqueous solution containing ammonium metatungstate and nickel nitrate. They are dried overnight at 120 ° C. under air and finally calcined under air at 450 ° C. for 2 hours. The oxide weight contents of catalyst C2 are 2.9% by weight for Ni (expressed as NiO) and 28.5% by weight for W (expressed as W0 ₃ ).

Example 3 Preparation of a Support S3 Containing a Zeolite Y and a Porous Matrix of Silica-Alumina Type and the Corresponding Catalyst C3 (Not in Accordance with the Invention)

The same zeolite Y as in Example 1 was used for the preparation of support S3 and catalyst C3.

To prepare the support of the hydrocracking catalyst, 7.6% by weight of the zeolite Y mentioned above is used which is mixed with 92.4% by weight of a silica alumina which contains 30% by weight of SiO ₂ and 70% by weight of AI ₂ 0 ₃ . The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air. The extrudates are then treated with steam at 750 ° C. for 2 hours.

The support extrudates containing zeolite Y are dry-impregnated with an aqueous solution containing ammonium metatungstate and nickel nitrate. They are dried overnight at 120 ° C. under air and finally calcined under air at 450 ° C. for 2 hours. The weight contents in oxides of the C3 catalyst are 3.1% by weight for Ni (expressed as NiO) and 28.3% by weight for W (expressed as W0 ₃ ).

EXAMPLE 4 Preparation of an S4 Support Containing a Y Zeolite A beta zeolite and a porous silica-alumina matrix and the corresponding C4 catalyst (not in accordance with the invention).

The same zeolite Y as in Example 1 was used for the preparation of support S4 and catalyst C4.

The zeolite beta used for the preparation of support S4 and catalyst C4 is described in Table 3.

Table 3: Describing the beta zeolite

To prepare the support for the hydrocracking catalyst, 5.6% by weight of the zeolite Y mentioned above is used, which is mixed with 2% by weight of the beta zeolite mentioned above and with 92.4% by weight. an alumina silica which contains 30% by weight of SiO ₂ and 70% by weight of Al ₂ O ₃ . The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air. The extrudates are then treated with steam at 750 ° C. for 2 hours.

The support extrudates containing zeolite Y and zeolite beta are dry impregnated with an aqueous solution containing ammonium metatungstate and nickel nitrate. They are dried overnight at 120 ° C. under air and finally calcined under air at 450 ° C. for 2 hours. The oxide weight contents of catalyst C4 are 3.1% by weight for Ni (expressed as NiO) and 28.7% by weight for W (expressed as W0 ₃ ).

EXAMPLE 5 Preparation of a Support S5 Containing a NU-86 Zeolite, a Y Zeolite and a Porous Alumina-type Matrix and the Corresponding Catalyst C5 (in Accordance with the Invention)

The same protonated NU-86 zeolite as in Example 1 was used for the preparation of support S5 and catalyst C5.

Another raw material used for the preparation of the support S5 is zeolite Y in the protonated form (H +) described in Table 4. Table 4: Description of zeolite Y

To prepare the support for the hydrocracking catalyst, 5% by weight of the aforementioned NU-86 zeolite is used which is mixed with 18% by weight of a zeolite Y mentioned above and with 77% by weight of an alumina gel. The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air.

The support extrudates containing the NU-86 zeolite, the Y zeolite and the aluminum matrix are impregnated dry with an aqueous solution in which Ni (OH) ₂ , MoO ₃ and H ₃ PO 4 have previously been solubilized. They are dried overnight at 120 ° C under air and calcined at 350 ° C. The NiMoP formulation of catalyst C5 is 2.7-23-4.9% by weight, based on the dry mass of catalyst respectively for Ni (expressed as NiO), for Mo (expressed as MoO 3) and for P (expressed as P2O5).

Example 6 Preparation of a Support S6 Containing a NU-86 Zeolite and a Porous Alumina-type Matrix and the Corresponding Catalyst C6 (Not in Accordance with the Invention)

The same NU-86 zeolite in protonated form as in Example 1 was used for the preparation of support S6 and catalyst C6.

To prepare the support for the hydrocracking catalyst, 23% by weight of the NU-86 zeolite mentioned above is used which is mixed with 77% by weight of an alumina gel. The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air.

The support extrudates containing the NU-86 zeolite and the alumina are dry-impregnated with an aqueous solution in which Ni (OH) ₂ , M0O ₃ and H ₃ PO ₄ have been solubilized beforehand. They are dried overnight at 120 ° C under air and calcined at 350 ° C. The NiMoP formulation of catalyst C6 is 2.6-23.2-4.7% by weight relative to the catalyst dry mass respectively for Ni (expressed as NiO), for Mo (expressed as MoO ₃ ) and for P (expressed as P ₂ 0 ₅ ).

Example 7 Preparation of a Support S7 Containing a Zeolite Y and a Porous Alumina-type Matrix and the Corresponding Catalyst C7 (Not in Accordance with the Invention)

The zeolite Y of Example 7 is the same as that used in Example 5.

To prepare the support for the hydrocracking catalyst, 23% by weight of the zeolite Y mentioned above is used which is mixed with 77% by weight of an alumina gel. The kneaded dough is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air.

The support extrusions are impregnated dry with an aqueous solution in which Ni (OH) ₂ , MoO ₃ and H ₃ PO ₄ have previously been solubilized. They are dried overnight at 120 ° C under air and calcined at 350 ° C. The NiMoP formulation of catalyst C7 is 2.6-23.1-4.8% by weight, based on the dry mass of catalyst respectively for Ni (expressed as NiO), for Mo (expressed as MoO ₃ ) and for P (expressed as P ₂ 0 ₅ ).

EXAMPLE 8 Preparation of an S8 Support Containing a Y Zeolite A beta zeolite and a porous alumina matrix and the corresponding C8 catalyst (not in accordance with the invention).

The zeolite Y used in Example 8 is the same as that used in Example 5. The beta zeolite used in Example 8 is the same as that used in Example 4.

To prepare the support for the hydrocracking catalyst, 18% by weight of the zeolite Y is used which is mixed with 5% by weight of the zeolite beta and with 77% by weight of an alumina gel. The kneaded paste is then extruded through a 1.8 mm diameter die. The extrudates are then dried overnight at 120 ° C. under air and then calcined at 550 ° C. under air.

The support extrudates thus prepared are impregnated dry with an aqueous solution in which Ni (OH) ₂ , MoO ₃ and H ₃ PO ₃ have been solubilized beforehand. They are dried overnight at 120 ° C under air and calcined at 350 ° C. The NiMoP formulation of the C8 catalyst is 2.7-23.2-5% by weight relative to the catalyst dry mass respectively for Ni (expressed as NiO), for Mo (expressed as MoO ₃ ) and for P (expressed as P ₂ O ₅ ).

Example 9: High-pressure hydrocracking evaluation of a vacuum distillate of catalysts C1, C2. C3 and C4

Catalysts C1, C2, C3 and C4, the preparation of which is described in Examples 1, 2, 3 and 4, are used to carry out the hydrocracking of a partially hydrotreated vacuum distillate, the main characteristics of which are given in Table 5.

Table 5: Characteristics of partially hydrotreated vacuum distillate.

The catalysts C1, C2, C3 and C4 were implemented according to the method of the invention using a pilot unit comprising 1 fixed bed reactor traversed, the fluids flow from top to bottom (down-flow). Prior to the hydrocracking test, the catalysts are sulfurized at 14 Pa, at 350 ° C. using a straight-run gas oil supplemented with 2% by weight of DMDS (dimethyl disulfide).

After sulphurisation, the catalytic tests were carried out under the following conditions:

Total pressure: 14 MPa,

Hydrogen flow rate: 1000 liters of gaseous hydrogen per liter of injected charge,

Space velocity (WH) equals 0.66 h ^-1 ,

The applied temperature is that for which 80% of gross conversion is obtained.

The feedstock is additivated with DMDS and aniline in order to maintain during the test the partial H ₂ S and NH ₃ pressures that would have been generated by the prior hydrotreatment of the unhydrotreated raw feedstock.

The catalytic performances are expressed in terms of the crude conversion of the 370+ fraction (molecules whose boiling point is greater than 370 ° C.) in the 370- fraction (molecules whose boiling point is less than 370 ° C.) and crude selectivity to middle distillates (150-370 ° C cut). The conversion and selectivity are expressed from simulated distillation results and gas analyzes by gas chromatography.

The gross conversion to products having a boiling point of less than 370 ° C, denoted CB 370 ° C, is taken to be equal to the mass percentage of molecules whose boiling point is less than 370 ° C in the effluents CB 370 ° C =% of 370 ° C ^" _emuents

The crude selectivity of middle distillates (a cut whose boiling points are between 150 and

370 ° C is denoted SB DM and is taken equal to:

SB DM = [(fraction 150-370 _ef fiuents)] / [(% of 370 ° C ^"emuents)].

The catalytic performances obtained are given in Table 6 below.

Table 6: Catalytic Results in High-Pressure Hydrocracking of Catalysts C1, C2,

C3 and C4.

Composition of the support Temperature for

SB DM

Catalyst maintain CB 370 ° C =

in% 80%

C1 (compliant) (SiAI + 5.6% Y + 2% NU-86) 396 ° C 72

C2 (non-compliant) (SiAI + 7.6% NU-86) 395 ° C 64

C3 (non-compliant) (SiAI + 7.6% Y) 401 ° C 68

C4 (non-compliant) (SiAI + 5.6% Y + 2% beta) 397.5 ° C 70 The results show that the particular combination of zeolite NU-86 with zeolite Y in catalyst C1 makes it possible to generate a very active catalyst that is highly selective for middle distillates. The presence alone of NU-86 zeolite (in the case of the non-compliant catalyst C2) makes it possible to obtain a very active catalyst that is extremely seldom selective in middle distillates. The addition of NU-86 in a catalyst containing zeolite Y makes it possible to significantly increase the conversion (comparison of catalysts C1 (compliant) and C3 (non-compliant)) and the particular combination of the two zeolites makes it possible surprisingly to significantly increase the selectivity of middle distillates, compared to other systems containing only one type of zeolite or a mixture of zeolite Y and beta zeolite (comparison of catalysts C1 (compliant) and C4 (non-compliant)).

Example 10: High-pressure hydrocracking evaluation of a vacuum distillate of catalysts C5, C6. C7 and C8

Catalysts C5, C6, C7 and C8, the preparation of which is described in Examples 5, 6, 7 and 8, are used to carry out hydrocracking of a hydrotreated vacuum distillate, the main characteristics of which are given in Table 7.

Table 7: Characteristics of the hydrotreated vacuum distillate.

The catalysts C5, C6, C7 and C8 were implemented according to the method of the invention using a pilot unit comprising 1 fixed bed reactor through which the fluids flow from top to bottom (down-flow). Prior to the hydrocracking test, the catalysts are sulfurized at 14 MPa at 350 ° C. using a straight-run gas oil supplemented with 2% by weight of DMDS (dimethyl disulphide).

Total pressure: 14 MPa,

Hydrogen flow rate: 000 liters of hydrogen gas per liter of injected charge,

Space velocity (WH) is equal to 1 h ^"1 ,

The applied temperature is that for which 70% of gross conversion is obtained.

The catalytic performances are expressed in terms of the crude conversion of the 370+ fraction (molecules whose boiling point is greater than 370 ° C.) in the 370- fraction (molecules whose boiling point is less than 370 ° C.) and yield of middle distillates (DM, cut 150-370 ° C). The Conversion and DM yield are expressed from simulated distillation results and gas analyzes by gas chromatography.

The gross conversion into products with a boiling point less than 370 ° C, denoted CB 370 ° C, is taken as equal to the weight percent of molecules having a boiling point lower than 370 ^C C Effluent CB 370 ° C % = 370 ° C ^_"é tants

The yield of middle distillates (a cut whose boiling points are between 150 and 370 ° C.) is taken as:

Yield in DM =% in molecules whose boiling points are included in 150 ° C and 370 ° C in the effluents.

The catalytic performances obtained are given in Table 8 below.

Table 8: Catalytic Results in High-Pressure Hydrocracking of C5, C6, C7 and C8

The results show that the particular combination of the zeolite NU-86 with the zeolite Y in the catalyst C5 makes it possible to generate a very active catalyst that is highly selective for middle distillates. The presence alone of NU-86 zeolite (in the case of the non-compliant C6 catalyst) makes it possible to obtain a very active catalyst that is extremely seldom selective in middle distillates. The addition of NU-86 in a catalyst containing zeolite Y makes it possible to significantly increase the conversion (comparison of catalysts C5 (compliant) and C7 (non-compliant)) and the particular combination of the two zeolites makes it possible surprisingly to significantly increase the selectivity of middle distillates, compared to other systems containing only one type of zeolite or a mixture of zeolite Y and beta zeolite (comparison of catalysts C5 (compliant) and C8 (non-compliant)).

Claims

A catalyst comprising at least one metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table, taken alone or as a mixture and a support comprising at least one NU-86 zeolite, at least one Y zeolite and at least one porous mineral matrix containing at least aluminum and / or at least silicon.

2. Catalyst according to claim 1 wherein said zeolite Y is a dealuminated zeolite called USY.

3. Catalyst according to one of claims 1 or 2 wherein said porous mineral matrix is selected from transition aluminas, doped alumina, silicalite and silicas, aluminosilicates, non-zeolitic crystallized molecular sieves alone or in admixture.

4. Catalyst according to claim 3 wherein said porous mineral matrix is selected from alumina and silica alumina.

5. Catalyst according to one of claims 1 to 4 wherein said catalyst comprises at least one Group VIB hydro-dehydrogenating metal in combination with at least one non-noble group VIII metal.

The catalyst according to claim 5 wherein the group VIB metal content is between 5 and 40% by weight based on the total weight of said catalyst, in oxide equivalent, and the non-noble metal content of group VIII is in oxide equivalent, between 0.5 and 10% by weight relative to the total weight of said catalyst.

7. Catalyst according to one of claims 1 to 6 wherein said catalyst comprises in% by weight relative to the total mass of the catalyst:

0.2 to 10%, of at least one NU-86 zeolite,

0.4 to 40%, of at least one zeolite Y,

from 0.5 to 50% of at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB and Group VIII metals,

1 to 99% of at least one porous mineral matrix comprising at least aluminum and / or at least silicon.

8. Process for hydrocracking hydrocarbon feeds using the catalyst according to one of claims 1 to 7, said process operating, in the presence of hydrogen, at a temperature greater than 200 ° C, at a pressure greater than 1 MPa, at a space velocity of between 0.1 and 20 -1 and at a quantity of hydrogen introduced is such that the ratio by volume of hydrogen liter / liter of hydrocarbon is between 80 and 5000 L / L.

9. The method of claim 8 wherein said method operates at a temperature between 250 and 480 ° C, at a pressure between 2 and 25 MPa, at a space velocity of between 0.1 and 6 h-1, and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 2000 L / L.

10. Method according to one of claims 8 or 9 wherein said hydrocarbon feedstock is selected from light gas oils from a catalytic cracking unit, atmospheric distillates, vacuum distillates, feeds from oil extraction units. of lubricating oil bases or derived from solvent dewaxing of lubricating oil bases, distillates from processes for desulphurization or hydroconversion to fixed bed or ebullated bed of atmospheric residues and / or residues under vacuum and and / or deasphalted oils, paraffins from the Fischer-Tropsch process and deasphalted oils, taken alone or as a mixture.

11. Method according to one of claims 8 to 10 wherein said method is implemented in a so-called one-step process.

12. The method of claim 11 wherein said catalyst is implemented in a hydrocracking zone placed downstream of a hydrorefining zone, no intermediate separation being implemented between the two zones.

13. Method according to one of claims 8 to 10 wherein said method is implemented in a so-called two-step process.

14. The method of claim 13 wherein said catalyst is implemented in the second hydrocracking step placed downstream of the first hydrorefining step, an intermediate separation being implemented between the two zones.