FR2790001A1 - Hydrocracking a hydrocarbon charge uses a catalyst containing an amorphous or poorly crystallized matrix of the oxide type and an IM-5 zeolite, a hydrogenating-dehydrogenating element, and boron or silicon as promoter - Google Patents

Abstract

Process for hydrocracking a hydrocarbon charge comprises contacting the charge with a catalyst containing an amorphous or poorly crystallized matrix of the oxide type and an IM-5 zeolite, a hydrogenating-dehydrogenating element consisting of a group VIII or group VIB metal, and boron or silicon as promoter. Independent claims are also included for: (1) a catalyst for hydrocracking a hydrocarbon charge comprising 0.1-99.7 (wt.%) IM-5 zeolite, 0.1-60 hydrogenating-dehydrogenating metal, 0.1-99 matrix, 0.1-20 boron or silicon, 0-20 phosphorus, 0-20 group VIIA metal, 0-20 group VIIB metal, and 0-60 group VB; and (2) a process for the production of the catalyst comprising: (a) forming a precursor by molding a matrix, IM-5 zeolite, a group VIB metal, a group VIII metal, boron or silicon as promoter, phosphorus, and a group VIIA metal; (b) calcining at at least 150O C; (c) impregnating the precursor obtained in (b) with a solution containing an element selected from a group VIIB, VB, VIII, VIB and VIIA element; (d) leaving the solid in a damp atmosphere at 10-120o C; and (e) drying at 60-150o C.

Description

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The present invention relates to a hydrocracking catalyst containing at least one matrix, an IM-5 zeolite, at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table, optionally at least one promoter 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 a catalyst based on IM-5 zeolite in hydrocracking hydrocarbon feeds.

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.

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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 a generally high temperature (greater than or equal to 390 ° C.), and at a low feed space velocity (the VVH expressed as the volume of charge to be treated per unit catalyst volume and per hour is generally less than or equal to 2 h -1) but having 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.

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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.

The research work carried out by the applicant on numerous zeolites and crystallized microporous solids has led him to discover that, surprisingly, a catalyst containing at least one IM-5 zeolite makes it possible to reach a catalytic activity and kerosene selectivities. and in essence significantly improved over the zeolite-containing catalysts known in the art.

More specifically, the subject of the invention is a process for hydrocracking hydrocarbon feedstocks, in which the feedstock to be treated is brought into contact with a catalyst comprising at least one amorphous or poorly crystallized oxide-type matrix and at least one IM-zeolite. 5.

The IM-5 zeolite used in the present invention is described in patent FR 2754 809. The invention also includes any zeolite of the same structural type as that of the IM-5 zeolite.

The zeolite structure, named IM-5, has a chemical composition, expressed on an anhydrous basis, in terms of molar ratios of oxides, by the formula: 100 XO2, m Y203, p R2 / nO, where m is equal to or lower at 10, p is between 0 (excluded) and 20, R represents one or more cations of valency n, X is silicon and / or germanium, preferably silicon, Y is selected from the group consisting of the following elements : aluminum, iron, gallium, boron, titanium, preferably Y is aluminum, and characterized in that it has, in raw synthesis form, an X-ray diffraction diagram comprising the lines presented in table 1.

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Table 1: X-ray diffraction table of the synthetic crude IM-5 zeolite

<Tb>
<tb> dhkl <SEP> () <SEP> I / Imax
<tb> 11,80,35 <SEP> FàTF (1)
<tb> 11,50,30 <SEP> FàTF (1)
<tb> 11,250,30 <SEP> FàTF (1)
<tb> 9,950,20 <SEP> m <SEP> to <SEP> F
<tb> 9,500.15 <SEP> m <SEP> to <SEP> F
<tb> 7,080,12 <SEP> f <SEP> to <SEP> m <SEP>
<tb> 6,040.10 <SEP> tf <SEP> to <SEP> f
<tb> 5,750.10 <SEP> f
<tb> 5,650.10 <SEP> f
<tb> 5,500.10 <SEP> tf
<tb> 5,350.10 <SEP> tf
<tb> 5,030.09 <SEP> tf
<tb> 4,720.08 <SEP> f <SEP> to <SEP> m
<tb> 4,550.07 <SEP> f
<tb> 4,260.07 <SEP> tf
<tb> 3,920.07 <SEP> F <SEP> to <SEP> TF (2)
<tb> 3,940.07 <SEP> TF <SEP> (2)
<tb> 3,850.05 <SEP> TF <SEP> (2)
<tb> 3,780.04 <SEP> F <SEP> to <SEP> TF (2)
<tb> 3,670.04 <SEP> m <SEP> to <SEP> F
<tb> 3,550.03 <SEP> m <SEP> to <SEP> F
<tb> 3,370,02 <SEP> f
<tb> 3,300,015 <SEP> f
<tb> 3,0990,012 <SEP> f <SEP> to <SEP> m <SEP>
<tb> 2,9700,007 <SEP> tf <SEP> to <SEP> f
<tb> 2,8150,005 <SEP> tf
<tb> 2,7200,005 <SEP> tf
<Tb>
(1) Rays forming part of the same massif, (2) Rays forming part of the same massif.

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 The zeolite IM-5 in its hydrogen form, designated H-IM-5, obtained by calcination (s) and / or ion exchange (s), as explained below, has an X-ray diffraction pattern comprising the lines presented in Table 2.

Table 2: X-ray diffraction table of IM-5 zeolite in form H,
H-IM-5 obtained by calcination

<Tb>
<tb> dhkl <SEP> () <SEP> I / Imax
<tb> 11,80,30 <SEP> FàTF (1)
<tb> 11,450,25 <SEP> TF (1)
<tb> 11,200,20 <SEP> FàTF (1)
<tb> 9,900.15 <SEP> m <SEP> to <SEP> F <SEP>
<tb> 9,500.15 <SEP> m <SEP> to <SEP> F
<tb> 7,060.12 <SEP> f <SEP> to <SEP> m <SEP>
<tb> 6,010.10 <SEP> tf <SEP> to <SEP> f
<tb> 5,700.10 <SEP> f
<tb> 5,300.10 <SEP> tf
<tb> 5,030.09 <SEP> tf
<tb> 4,710,08 <SEP> f
<tb> 4,250.07 <SEP> tf
<tb> 3,870.07 <SEP> m <SEP> to <SEP> F <SEP> (2)
<tb> 3,810.05 <SEP> m <SEP> to <SEP> F <SEP> (2)
<tb> 3,760.04 <SEP> m <SEP> to <SEP> F <SEP> (2)
<tb> 3,670.04 <SEP> f <SEP> to <SEP> m
<tb> 3,540.04 <SEP> m <SEP> to <SEP> F
<tb> 3,370,03 <SEP> f
<tb> 3,3160,015 <SEP> f
<tb> 3,1030,012 <SEP> f
<tb> 3,0800,010 <SEP> f <SEP> to <SEP> m <SEP>
<tb> 2,9500,010 <SEP> tf <SEP> to <SEP> f
<tb> 2,8800,007 <SEP> tf
<tb> 2,7900,005 <SEP> tf
<tb> 2,5900,005 <SEP> tf
<Tb>
(1) Rays forming part of the same massif, (2) Rays forming part of the same massif.

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These diagrams are obtained using a diffractometer using the conventional powder method with copper Ka radiation. From the position of the diffraction peaks represented by the angle 2 #, we calculate, by the Bragg relation, the characteristic lattice spacings dhkl characteristic of the sample. The intensity is calculated on the basis of a relative intensity scale on which a value of 100 is assigned to the line with the highest intensity on the diffraction pattern X: very low (tf) means less than 10, low (f) means less than 20, mean (m) means between 20 and 40, strong (F) means between 40 and 60, very strong (TF) means greater than 60.

The IM-5 zeolite can therefore be used in its "raw synthesis form", as well as forms obtained by dehydration and / or calcination and / or ion exchange.

The expression "in its crude synthetic form" refers to the product obtained by synthesis and washing with or without drying or dehydration. In its "crude synthesis form", the IM-5 zeolite may comprise a metal cation M, which is an alkaline, in particular sodium, and / or ammonium, and may comprise nitrogen-containing organic cations such as those described below or their decomposition products, or their precursors. These nitrogenous organic cations are designated herein by the letter Q, which also includes decomposition products and precursors of said nitrogenous organic cations.

The calcined forms of the IM-5 zeolite do not contain any nitrogenous organic compound, or in a quantity less than the "synthetic form of synthesis", insofar as the organic substance is eliminated for the most part, generally by a heat treatment consisting in burn the organic substance in the presence of air, the hydrogen ion (H +) then forming the other cation.

Among the ion exchange forms of IM-5 zeolite, the ammonium form (NH4 +) is important because it can easily be converted to hydrogen form by calcination. The hydrogen form and ion-containing metal-containing forms are described below.

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In some cases, subjecting the zeolite according to the invention to the action of an acid may give rise to the partial or total elimination of a base element such as aluminum, as well as the generation of form hydrogen. This may be a means of modifying the composition of the substance of the zeolite after it has been synthesized.

The IM-5 zeolite in hydrogen form (acid form), called H-IM-5, is produced by calcination and ion exchange as described below.

The IM-5 zeolite is at least partly in H + form (as defined above) or NH4 + or metal, said metal being selected from the group consisting of groups IA, IB, IIA, IIB, IIIA, IIIB (including the rare earths), VIII, Sn, Pb and Si, preferably at least partly in H + form or at least partly in metallic form, can also be used.

The IM-5 zeolite will preferably be used at least partly in acidic form (and preferably entirely in H form) or partially exchanged with metal cations, for example cations of alkaline earth metals.

The IM-5 zeolites that come into the composition according to the invention are then used with the silicon and aluminum contents obtained in the synthesis.

It is also possible to use the dealuminated IM-5 zeolite, which is described in patent application FR-2,758,810, and which has an overall Si / Al atomic ratio greater than 5, preferably greater than 10, more preferably higher at 15, and even more preferably between 20 and 400.

The IM-5 zeolite is advantageously at least partly and preferably substantially completely in acid form.

The atomic ratio Na / Al is generally less than 0.45 and preferably less than 0.30 and even more preferably less than 0.15.

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To prepare the dealuminated IM-5 zeolite, at least two dealumination methods may be employed, starting from the synthetic raw IM-5 zeolite comprising organic structurant. They are described below. But any other method known to those skilled in the art can also be used.

The first so-called direct acid etching method comprises a first calcination step under dry air flow, at a temperature generally of between approximately 450 and 550 ° C., which aims to eliminate the organic structuring agent present in the microporosity of the zeolite, followed by a treatment step with an aqueous solution of a mineral acid such as HNO 3 or HCl or organic such as CH 3 CO 2 H.

This last step can be repeated as many times as necessary in order to obtain the desired level of dealumination. Between these two steps it is possible to carry out one or more ionic exchanges with at least one NH 4 NO 3 solution, so as to eliminate at least partly, preferably almost completely, the alkaline cation, in particular sodium. Similarly, at the end of the dealumination treatment by direct acid etching, it is possible to carry out one or more ionic exchanges with at least one NH 4 NO 3 solution, so as to eliminate the residual alkaline cations and in particular sodium.

To reach the desired Si / Al ratio, it is necessary to choose the operating conditions; from this point of view the most critical parameters are the treatment temperature of the aqueous acid solution, the concentration of said acid, the nature of said acid, the ratio between the amount of acidic solution and the mass of zeolite treated, the duration treatment and the number of treatments performed.

The second so-called heat treatment method (in particular with water vapor or "steaming") + etching, comprises, initially, the calcination under a flow of dry air, at a temperature generally of between approximately 450 and 550 C, which aims to eliminate the organic template occluded in the microporosity of the zeolite. Then the solid thus obtained is subjected to one or more ionic exchanges with at least one NH 4 NO 3 solution, so as to eliminate at least partly, preferably almost completely, the alkaline cation, in particular sodium, present in the cationic position in the zeolite. .

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The zeolite thus obtained is subjected to at least one framework dealumination cycle, comprising at least one heat treatment carried out, optionally and preferably in the presence of steam, at a temperature generally of between 550 and 900 ° C., and optionally followed at least one acid attack by an aqueous solution of a mineral or organic acid. The calcination conditions in the presence of water vapor (temperature, water vapor pressure and treatment time) as well as the conditions of acid attack after calcination (duration of the attack, concentration of the acid, nature the acid used and the ratio between the volume of acid and the mass of zeolite) are adapted to obtain the desired level of dealumination. For the same purpose we can also play on the number of heat treatment cycles-acid attack that are performed.

The dealumination cycle of the framework, comprising at least one heat treatment step carried out, optionally and preferably in the presence of steam and at least one acid attack step of the IM-5 zeolite, may be carried out repeated as many times as necessary to obtain the dealuminated IM-5 zeolite having the desired characteristics. Similarly, following the heat treatment carried out, optionally and preferably in the presence of water vapor, several successive acid attacks, with acid solutions of different concentrations, can be operated.

A variant of this second calcination method may consist in carrying out the heat treatment of the IM-5 zeolite containing the organic template, at a temperature generally of between 550 and 850 ° C., optionally and preferably in the presence of water vapor. In this case, the steps of calcination of the organic structurant and dealumination of the framework are carried out simultaneously. Then, the zeolite is optionally treated with at least one aqueous solution of a mineral acid (for example HNO 3 or HCl) or an organic acid (CH 3 CO 2 H for example). Finally, the solid thus obtained may optionally be subjected to at least one ionic exchange with at least one NH 4 NO 3 solution, so as to eliminate substantially any alkaline cation, in particular sodium, present in the cationic position in the zeolite.

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The zeolite is then used with the Si / Al ratio obtained after dealumination.

The catalyst also contains a hydrogenating function provided by 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 include a 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 a group VIB element, preferably tungsten and molybdenum. Advantageously, the combinations of at least one non-noble metal of group VIII and at least one metal of group VIB are used. The following combinations of metals are preferred: 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. By way of nonlimiting example, mention may be made of alumina, silica and silica-alumina. Clays (for example, natural clays such as kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, phosphates of zirconium, coal. 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 contains at least one promoter element chosen 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.

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 When the catalyst contains silicon, silicon is introduced as a promoter on the support according to the invention. Silicon is mainly located on the support matrix and 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 catalyst components, or even by establishing a distribution map of the elements present in the catalyst by electron microprobe.

Another subject of the invention is a catalyst comprising at least one amorphous or poorly crystallized oxide-type matrix, an IM-5 zeolite, and at least one hydro-dehydrogenating element chosen from the group consisting of Group VIII metals and metals. Group VI B, and at least one promoter element selected from the group consisting of boron and silicon. Advantageously, the catalyst comprises, in addition, phosphorus. These catalysts are advantageously used in hydrocracking.

The catalyst of the present invention generally contains, in% by weight with respect to the total mass of the catalyst: 0 to 60%, or 0.1 to 60%, preferably 0.1 to 50% and even more preferably from 0.1 to 40% of at least one hydro-dehydrogenating metal, advantageously chosen from the group consisting of Group VIB and Group VIII metals, 0.1 to 99%, preferably from 1 to 98%, at least one amorphous or poorly crystallized porous mineral matrix of oxide type, said catalyst also containing from 0.1 to 99.8%, preferably from 0.1 to 90%, preferably from 0.1 to 80%, and even more preferably from 0.1 to 60% of IM-5 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 chosen from the group formed by silicon, boron and phosphorus, excluding the silicon optionally contained in the IM-5 zeolite, 0 to 20%, preferably from 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 15%.
10% of at least one element selected from group VIIB.

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A preferred catalyst closes, in% by weight with respect to the total mass of catalyst: 0.1 to 99.7% of IM-5 zeolite; 0.1 to 60% of at least one hydro-dehydrogenating metal; 1 to 99% of at least one matrix, 0.1 to 20% of boron and / or silicon, 0 to 20% of phosphorus, with the sum of the amounts of boron and / or phosphorus and / or silicon of at most 20%, 0 to 20% of at least one element of group VII A, 0 to 20% of at least one element of group VII B.

This catalyst may also comprise all the characteristics described above: preferred ranges of values for the components, preferred components, optional groups VII A and VII B.

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.

The catalyst may 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.

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 IM-5 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 with a diameter of between 0.4 and 4 mm.

The hydrogenating function can be introduced only in part (for example, combinations of Group VIB and VIII metal oxides) or in full at the time of mixing the zeolite, ie the IM-5 zeolite, with the oxide gel chosen as the matrix.

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 The hydrogenating function can be introduced by one or more ion exchange operations on the calcined support consisting of an IM-5 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 IM-5 zeolite, at least one matrix, as defined above, and at least one metal selected from the group consisting of Group VIB metals and Group VIII metals. .

In the case where the catalyst contains boron and / or silicon and / or 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 can be introduced into the catalyst at various levels of the preparation and in various ways.

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 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 catalyst supported on a support containing IM-5 zeolite and alumina, it is possible to impregnate this precursor with aqueous solution. of Rhodorsil E1P ammonium biborate and silicone from the company Rhône Poulenc, to carry out a drying, for example at 80 ° C., and then to impregnate 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.

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.

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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.

A preparation process consists of the following operations: a) a solid known as the precursor is prepared, containing at least the following compounds: at least one matrix, at least one IM-5 zeolite, optionally at least one element selected from the elements group VI B and group VIII, at least one promoter element selected from the group consisting of boron and silicon, optionally phosphorus, optionally at least one element of group VII A, the whole being preferably shaped, b) the dry solid obtained in step a) is calcined at a temperature of at least 150 ° C., c) the solid precursor obtained at the end of step b) is impregnated with a solution containing at least one element of group VII B,

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 d) the wet solid is allowed to stand under a humid atmosphere at a temperature of between 10 and 120 ° C., e) the wet solid obtained in step d) is dried at a temperature of between 60 ° C. and 150 ° 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, 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.

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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.

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.

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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 obtained by the present invention are used for the hydrocracking of hydrocarbon feeds such as petroleum cuts. The feedstocks used in the process are gasolines, kerosenes, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, residues or deasphalted crudes, fillers derived 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. In these heavy cuts, preferably at least 80% by volume of compounds have boiling points of at least 350 ° C. and preferably between 350 ° and 580 ° C. (i.e. corresponding to minus 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 catalyst of the present invention can be advantageously used for the hydrocracking of vacuum distillate-type cuts heavily loaded with sulfur and nitrogen.

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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 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 of heating 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., generally in a crossed-bed reaction zone.

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 amount of hydrogen 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.

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.

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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, the catalyst may optionally contain phosphorus and optionally boron.

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 10h-1. 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.

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 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.

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.

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

EXAMPLE 1 Preparation of a Hydrocracking Catalyst Support Containing an IM-5 Zeolite The IM-5 zeolite used in this example is the one whose preparation is described in Example 1 of Patent FR 2 754 809.

The product obtained above is calcined under nitrogen for 24 hours at 550 ° C .; this step was immediately followed by a second calcination in air at 450 ° C. for 24 hours.

The resulting material was then contacted for 2 hours at room temperature with an aqueous solution of 1 mole of ammonium chloride using 50 ml of solution per gram of solid calcined product. The substance was then filtered, washed with deionized water and dried at 110 ° C. This treatment was repeated 3 times. The substance was then calcined under air for 24 hours at 550 ° C. The calcined product was analyzed by X-ray diffraction. The diffractogram obtained is in agreement with Table 2 reported previously.

Analysis of Si, Al and Na in the product, performed by atomic emission spectroscopy, gave the following molar composition:
SiO 2: 3.9 Al 2 O 3: 0.008 Na 2 O A hydrocracking catalyst support containing the IM-5 zeolite manufactured above was obtained in the following manner. 15.3 g of the IM-5 zeolite are mixed with 84.7 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.

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Example 2 Preparation of hydrocracking catalysts containing an IM-5 zeolite in accordance with the invention and with Molybolene (Table 3) IM-5 Mo catalyst The support extrudates containing an IM-5 zeolite of Example 1 are impregnated to dryness with an aqueous solution of ammonium heptamolybdate, dried overnight at 120 ° C. under air and finally calcined in air at 550 ° C. The weight contents of the oxides of the IM-5Mo catalyst obtained are given in Table 3.

IM-5 MoB Catalyst The IM-5Mo catalyst was then impregnated with an aqueous solution containing ammonium biborate to obtain a deposit of 1.6% 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 IM-5MoB is obtained.

IM-5 MoSi Catalyst In the same way, an IM-5MoSi catalyst was then prepared by impregnating the IM-5Mo catalyst with a Rhodorsil EP1 silicone emulsion (Rhone-Poulenc) so as to deposit about 2.0% of SiO 2. The impregnated extrudates are then dried overnight at 120 ° C. and then calcined at 550 ° C. for 2 hours under dry air.

Catalyst IM-5 MoBSi Finally, an IM-5MoBSi catalyst was obtained impregnating the IM-5Mo catalyst with 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.

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 Example 3: hydrocracking catalysts containing an IM-5 zeolite according to the invention, and with nickel and Molybolene (Table 4).

IM-5 NiMo Catalyst The support extrudates containing an IM-5 zeolite prepared in Example 1 are dry-impregnated with an aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate, dried overnight at 120.degree. C. under air and finally calcined under air at 550 ° C. The oxide weight contents of the catalyst IM-5NiMo obtained are given in Table 4.

IM-5 NiMoP Catalyst 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. under air and finally calcined in air at room temperature. 550 C.

IM-5 NiMoPB Catalyst We then impregnated the IM-5NiMoP catalyst sample 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 IM-5NiMoPB is obtained.

IM-5 NiMoPSi Catalyst A catalyst IM-5NiMoPSi was obtained by the same procedure as the catalyst IM-5NiMoPB above but replacing in the impregnation solution the boron precursor by the Rhodorsil EP1 silicone emulsion.

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IM-5 Catalyst NiMoPBSi Finally, an IM-5NiMoPBSi catalyst was obtained by the same procedure as the above catalysts but using an aqueous solution containing the ammonium biborate and the 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 calcining at 550 ° C. for 2 hours in dry air, the catalyst IM-5NiMoPBSiF is obtained.

Table 3: catalysts IM-5 + Mo + promoter

<Tb>
<tb> Catalyst <SEP> IM-5 <SEP> MB <SEP> IM-5 <SEP> MBB <SEP> IM-5 <SEP> MoSi <SEP> IM-5 <SEP> MoBSi
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 14.1 <SEP> 14.6 <SEP> 14.3 <SEP> 14.2
<tb> B2O3 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.45 <SEP> 0 <SEP> 1.4
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 12.2 <SEP> 11.9 <SEP> 13.6 <SEP> 13.7
<tb> Complement <SEP> to <SEP> 100% <SEP> 73.7 <SEP> 72.05 <SEP> 72.1 <SEP> 70.7
<tb> compound <SEP> mostly <SEP> of
<tb> Al2O3 <SEP> (% <SEP> wt)
<Tb>
Table 4: Characteristics of catalysts IM-5 + NiMo + promoter + possible G. VII A

<Tb>
<tb> Catalyst <SEP> IM-5 <SEP> IM-5 <SEP> IM-5 <SEP> IM-5 <SEP> IM-5 <SEP> IM-5
<tb> NiMo <SEP> NiMoP <SEP> NiMoPB <SEP> NiMoPSi <SEP> NiMoPBSi <SEP> NiMoPBSiF
<tb> MoO3 <SEP> (% <SEP> wt) <SEP> 13.6 <SEP> 13.5 <SEP> 12.9 <SEP> 13.1 <SEP> 12.9 <SEP> 12.9
<tb> NiO <SEP> (% <SEP> wt) <SEP> 2.95 <SEP> 2.1 <SEP> 3.0 <SEP> 3.05 <SEP> 2.9 <SEP> 2.85
<tb> P20s <SEP> (% <SEP> wt) <SEP> 0 <SEP> 4.55 <SEP> 4.5 <SEP> 4.4 <SEP> 4.6 <SEP> 4.5
<tb> B2O3 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 0 <SEP> 1.55 <SEW> 0 <SEP> 1.6 <SEW> 1.5
<tb> SiO2 <SEP> (% <SEP> wt) <SEP> 11.8 <SEP> 11.3 <SEP> 11.1 <SEP> 13.3 <SEP> 12.7 <SEP> 12.5
<tb> F <SEP> (% <SEP> pds) <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 1.1
<tb> Supplement <SEP> to
<tb> 100% <SEP> Compound <SEP> 71.65 <SEP> 68.55 <SEP> 66.95 <SEP> 66.15 <SEP> 65.3 <SEP> 64.65
<tb> mainly
<tb> of <SEP> Al2O3 <SEP> (% <SEP> wt)
<Tb>

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 Example 4 Preparation of catalysts according to the invention with G. VII B (Table 5).

IM-5 NiMoPMn Catalyst The IM-5NiMoP catalyst 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 IM-5NiMoPMn is obtained.

IM-5 catalyst NiMoPMnBSi 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 in dry air and the IM-5NiMoPMnBSi catalyst is obtained.

Catalyst IM-5 NiMoPMnBSiF 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 calcining at 550 ° C. for 2 hours in dry air, the catalyst IM-5NiMoPMnBSiF is obtained. The weight contents of these catalysts are shown in Table 5.

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Table 5: Characteristics of IM-5NiMo catalysts containing manganese

<Tb>
<tb> Catalyst <SEP> IM-5 <SEP> IM-5 <SEP> IM-5
<tb> NiMoPMn <SEP> NiMoPMnBSi <SEP> NiMoPMnBSiF
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 12.8 <SEP> 12.2 <SEP> 12.5
<tb> NiO <SEP> (% <SEP> wt) <SEP> 3.05 <SEP> 2.7 <SEP> 2.9
<tb> MnO2 <SEP> (% <SEP> wt) <SEP> 2.2 <SEP> 1.9 <SEP> 2.1
<tb> P2O5 <SEP> (% <SEP> wt) <SEP> 4.7 <SEP> 4.8 <SEP> 4.4
<tb> B203 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.4 <SEP> 1.3
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 11.0 <SEP> 12.6 <SEP> 12.4
<tb> F <SEP> (% wt) <SEP> 0 <SEP> 0 <SEP> 1.0
<tb> Complement <SEP> to <SEP>
<tb> 100% <SEP> Compound <SEP> 66.25 <SEP> 64.4 <SEP> 63.4
<tb> predominantly <SEP> of <SEP> 66.25 <SEP> 64.4 <SEP> 63.4
<tb> Al2O3 <SEP> (% <SEP> wt)
<Tb>
The electron microprobe analysis of the catalysts IM-5NiMoPSi, IM-5NiMoPBSi, IM-5NiMoPBSiF (Table 4) and catalysts IM-5NiMoPMnBSi, IM-5NiMoPMnBSiF (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 5 Preparation of a Support Containing an IM-5 Zeolite and Silicuminum We made a silica-alumina powder by coprecipitation having a composition of 2% SiO 2 and 98% Al 2 O 3. A hydrocracking catalyst support containing this silica-alumina and the IM-5 zeolite of Example 1 was then manufactured. For this purpose, 18.5% by weight of the IM-5 zeolite of Example 1 is used, which is mixed with 81.5% by weight of a matrix composed of the silica alumina prepared above.

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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.

EXAMPLE 6 Preparation of Hydrocracking Catalysts Containing an IM-5 Zeolite and a Silica-Alumina The support extrudates containing a silica-alumina and an IM-5 zeolite of Example 5 are impregnated dry with an aqueous solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, dried overnight at 120 ° C. under air and finally calcined in air at 550 ° C. The oxide weight contents of the catalyst IM-5-SiAl-NiMoP obtained are shown in Table 6.

We impregnated the IM-5-SiAl-NiMoP catalyst sample with an aqueous solution containing ammonium biborate so as to impregnate 1.5% B203 mass. 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 is obtained named IM-5-SiAI-NiMoPB which therefore contains silicon in the silica-alumina matrix.

The characteristics of the IM-5-SiAl-NiMo catalysts are summarized in Table 6.

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Table 6: IM-5-SiAl-NiMo catalysts

<Tb>
<tb> Catalyst <SEP> IM-5-SiAI-NiMoP <SEP> IM-5-SiAI-NiMo <SEP> PB
<tb> Mo03 <SEP> (% <SEP> wt) <SEP> 13.4 <SEP> 13.1
<tb> NiO <SEP> (% <SEP> wt) <SEP> 2.8 <SEP> 2.9
<tb> P2O5 <SEP> (% <SEP> wt) <SEP> 4.6 <SEP> 4.8
<tb> B203 <SEP> (% <SEP> wt) <SEP> 0 <SEP> 1.3
<tb> Si02 <SEP> (% <SEP> wt) <SEP> 14.9 <SEP> 14.6
<tb> Complement <SEP> to <SEP> 100%
<tb> compound <SEP> predominantly <SEP> of <SEP> 64.3 <SEP> 63.3
<tb> AI203 <SEP> (% <SEP> wt) <SEP> 64.3 <SEP> 63.3
<Tb>
Example 7 Preparation of a Zeolite-Y-Containing Medium (Comparative Example) A hydrocracking catalyst support containing a Y-zeolite was manufactured in large amounts so that different catalysts based on the same support could be prepared. For this purpose, 20.5% by weight of a dealuminated Y zeolite with a crystalline parameter equal to 2.429 nm and a SiO 2 / Al 2 O 3 ratio of 30.4 and a SiO 2 / Al 2 O 3 ratio of 58, which is mixed at 79, are used. 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 humid air containing 7.5% of water. 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. Matrix analysis by X-ray diffraction reveals that it is composed of low crystallinity cubic gamma alumina and dealuminated Y zeolite.

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Example 8 Preparation of hydrocracking catalysts containing a Y zeolite (not in accordance with the invention) The carrier extrudates containing a dealuminated Y zeolite of Example 7 are impregnated dry with an aqueous solution of a mixture of heptamolybdate ammonium nitrate and nickel nitrate, dried overnight at 120 C in air and finally calcined in air at 550 C. The oxide weight contents of the catalyst YNiMo obtained are shown in Table 7. The catalyst YNiMo final contains in particular 16.3% by weight of zeolite Y of 2,429 nm mesh parameter SiO2 / Al2O3 overall ratio of 30.4 and SiO2 / Al2O3 framework ratio of 58.

The extrudates of Example 7 are impregnated as above but in addition to orthophosphoric acid, and treated in the same manner as above to obtain the YNiMoP catalyst.

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 silicone emulsion (Rhône-Poulenc).

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 7.

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TABLE 7 Characteristics of YNiMo Catalysts (Comparative)

<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> P2O5 <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> Complement <SEP> to <SEP>
<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 7) 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 9 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
Starting point 365 C
Item 10% 430 C
Point 50% 472 C
Point 90% 504 C
End Point 539 C
Pour point + 39 C

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The catalytic test unit comprises two fixed-bed reactors, with up-flow of the charge.In the first reactor, the one in which the charge passes first, the first hydrotreatment stage catalyst is introduced. comprising a Group VI element and a Group VIII element deposited on alumina, In the second reactor, the one in which the feedstock passes last, a hydrocracking catalyst described above is introduced. ml of catalyst Both reactors operate at the same temperature and at the same pressure The operating conditions of the test unit are as follows:
Total pressure 5 MPa
Hydroprocessing catalyst 40 cm3
40 cc hydrocracking catalyst
400 C temperature
Hydrogen flow rate 20 I / 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.

The catalytic performances are expressed by the gross conversion at 400 C (CB), by the crude selectivity in middle distillates (SB) and by the 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 gross conversion CB is taken as equal to: minus CB =% wt of 380 C of the effluent minus 380 C represents the fraction distilled at a temperature of less than or equal to 380 C.

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The gross selectivity SB in middle distillates is taken as equal to: minus SB = 100 * weight of the fraction (150 C-380 C) / weight of the fraction 380 C of the effluent The conversion into hydrodesulfurization HDS is taken equal to: HDS = (Sinitial - Seff luent) / Sinitial * 100 = (24600 -Seffluent) / 24600 * 100 The conversion to hydrodenitrogenation HDN is taken as: HDN = (Ninitial - Neffluent) Ninitial * 100 = (1130 - Neffluent) / 1130 * In the following table, we have reported the gross conversion CB at 400 ° C., the crude selectivity SB, the conversion to HDS hydrodesulfurization and the conversion to hydrodenitrogenation HDN for the catalysts.

Table 8 Catalytic Activities of Catalysts in Partial Hydrocracking at 400 ° C.

<Tb>
<tb> CB <SEP> SB <SEP> HDS <SEP> HDN
<tb> (% wt) <SEP> (%) <SEP> (%) <SEP> (%)
<tb> NiMoP / Y <SEP> 48.7 <SEP> 80.3 <SEP> 99.43 <SEP> 96.6
<tb> NiMoPB / Y <SEP> 49.3 <SEP> 80.4 <SEP> 99.57 <SEP> 97.4
<tb> NiMoPSi / Y <SEP> 49.5 <SEP> 78.9 <SEP> 99.85 <SEP> 98.3
<tb> NiMoP / IM-5-SiAI <SEP> 50.2 <SEP> 60.3 <SEP> 98.6 <SEP> 96.5
<tb> NiMoPB / IM-5-SiAI <SEP> 50.6 <SEP> 59.7 <SEP> 98.5 <SEP> 97.4
<tb> NiMo / IM-5 <SEP> 50.1 <SEP> 60.2 <SEP> 98.6 <SEP> 94.9
<tb> NiMoP / IM-5 <SEP> 50.2 <SEP> 60.9 <SEP> 99.4 <SEP> 96.3
<tb> NiMoPB / IM-5 <SEP> 50.6 <SEP> 60.8 <SEP> 99.5 <SEP> 97.2
<tb> NiMoPSi / IM-5 <SEP> 50.9 <SEP> 60.5 <SEP> 99.5 <SEP> 98.1
<tb> NiMoPBSi / IM-5 <SEP> 51.4 <SEP> 60.6 <SEP> 99.6 <SEP> 98.5
<Tb>
The results in Table 8 show that the use of a catalyst according to the invention containing an IM-5 zeolite is more active than the catalysts of the prior art and that on the other hand the addition of at least one element chosen from the group formed by B, Si and P brings an improvement in the performance of the catalyst in conversion. The catalysts of the invention containing boron and silicon are therefore particularly useful for partial hydrocracking of vacuum distillate type feedstocks containing nitrogen at a moderate hydrogen pressure.

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In addition, the results in Table 8 show that it is advantageous to introduce the silicon on the already prepared catalyst (IM-5NiMo series) rather than in the form of a silicon-containing support obtained from a silica-silica. alumina (IM-5-SiAINiMo 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 10 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 petroleum feed 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 over a catalyst comprising a group VIB element (Mo) and a group VIII element (Ni) deposited on alumina.

0.6% by weight of aniline and 2% by weight of dimethyl disulfide are added to the feed 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. 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.

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Once the sulfurization is complete, 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 80 I / h
Charge rate 80 cm3 / h 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 equal to: SB ions = 100 * weight of the fraction (150 C-380 C) / weight of the fraction 380 C less than the effluent The yield of gasoline (27-150) (below Yield Ess) is equal to the weight% of compounds having a boiling point between 27 and 150 C in the effluents.

The yield of jet fuel (kerosene, 150-250) (below Yt Kero) is equal to the weight% of compounds having a boiling point of between 150 and 250 ° C. in the effluents. The yield of gas oil (250-380) is equal to the weight% of compounds having a boiling point between 250 and 380 C in the effluents.

The reaction temperature is set so as to reach a gross conversion CB equal to 70% by weight. In Table 9 we have reported the reaction temperature and crude selectivity for the catalysts described in Tables 3,4 and 5.

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Table 9: Catalytic Activities of High-conversion Hydrocracking Catalysts (70%)

<Tb>
<tb> Yard <SEP> Yard
<tb> T (C) <SEP> Gasoline <SEP> Kerosene
<tb> (% <SEP> pds) <SEP> (% <SEP> pds)
<tb> NiMo / Y <SEP> 375 <SEP> 20.5 <SEP> 24.1
<tb> NiMoP / Y <SEP> 374 <SEP> 21.2 <SEP> 24.7
<tb> NiMoPB / Y <SEP> 374 <SEP> 20.7 <SEP> 23.6
<tb> NiMoPSiN <SEP> 374 <SEP> 19.9 <SEP> 23.1
<tb> Mo / IM-5 <SEP> 372 <SEP> 37.3 <SEP> 12.2
<tb> MoB / IM-5 <SEP> 372 <SEP> 37.5 <SEP> 12.6
<tb> MoSi / IM-5 <SEP> 371 <SEP> 37.1 <SEP> 12.1
<tb> MoBSi / IM-5 <SEP> 370 <SEP> 36.9 <SEP> 12.0
<tb> NiMo / IM-5 <SEP> 372 <SEP> 38.3 <SEP> 12.0
<tb> NiMoP / IM-5 <SEP> 372 <SEP> 38.1 <SEP> 13.1
<tb> NiMoPB / IM-5 <SEP> 370 <SEP> 38.0 <SEP> 12.4
<tb> NiMoPSi / IM-5 <SEP> 370 <SEP> 38.5 <SEP> 12.8
<tb> NiMoPBSi / IM-5 <SEP> 369 <SEP> 37.8 <SEP> 12.6
<tb> NiMoPBSiF / IM-5 <SEP> 366 <SEP> 37.5 <SEP> 13.3
<tb> NiMoPMn / IM-5 <SEP> 370 <SEP> 37.4 <SEP> 12.8
<tb> NiMoPMnBSi / IM-5 <SEP> 369 <SEP> 37.0 <SEP> 12.5
<tb> NiMoPMnBSiF / IM-5 <SEP> 366 <SEP> 36.9 <SEP> 12.3
<Tb>
Table 9 shows that the use of a catalyst according to the invention containing IM-5 zeolite leads to higher conversion levels (i.e. lower conversion temperatures for a given conversion of 70% by weight) relative to the non-compliant 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. Furthermore, all the catalysts according to the invention leads to improved gasoline yields compared to those recorded in the case of catalysts of the prior art.

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In general, the addition of at least one element selected from the group P, B, Si, VIIB, VIIA to the catalyst containing the IM-5 zeolite and the group VIB element makes it possible to improve the activity. in conversion, which results in a reduction of the reaction temperature necessary to reach 70% of conversion but tends to decrease the crude selectivity in gasoline and kerosene and in particular the selectivity in gasoline, the latter still remaining substantially greater than that obtained with the catalysts based on zeolite Y of the prior art.

Claims (7)

 1. Hydrocracking process of hydrocarbon feeds, wherein the feedstock to be treated is contacted with a catalyst comprising at least one amorphous or poorly crystallized oxide type matrix and at least one IM-5 zeolite. 2. hydrocracking process according to claim 1 wherein the catalyst further comprises at least one hydro-dehydrogenating element selected from group VIB and group VIII. 3 hydrocracking process according to one of the preceding claims wherein the catalyst further comprises at least one promoter element selected from the group consisting of boron, phosphorus and silicon. 4. hydrocracking process according to one of the preceding claims wherein the catalyst further comprises at least one element selected from Group VII elements A. 5. Method according to one of the preceding claims wherein the catalyst further comprises at least one element of group VII B. 6. Method according to one of the preceding claims wherein the group VIB element is molybdenum or tungsten and the group VIII element is iron, cobalt or nickel. 7. Method according to one of the preceding claims wherein the catalyst contains in% by weight relative to the total mass of the catalyst: - 0.1 to 99.8% of at least one IM-5 zeolite, - 0 to 60 % of at least one element selected from group VII B; 0.1 to 99% of at least one amorphous or poorly crystallized porous mineral matrix of oxide type; 0 to 60% of at least one selected element among the elements of group VIB and group VIII, <Desc / Clms Page number 39>  from 0 to 20% of at least one promoter element chosen from the group consisting of silicon, boron and phosphorus, excluding the silicon optionally contained in IM-5 zeolite, from 0 to 20% of at least an element chosen from the group VIIA. 8. Method according to one of claims 1 to 7 wherein the catalyst matrix is selected from the group consisting of alumina, silica, silica-alumina, clays, magnesia, titanium oxide boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, coal, aluminates. 150 C, c) the solid precursor obtained at the end of step b) is impregnated with a solution containing at least one element of group VIIB, d) the wet solid is allowed to stand under a humid atmosphere at a temperature of between 10 and 120 ° C., e) the wet solid obtained in step d) is dried at a temperature of between 60 and 150 ° C. 10. The process according to claim 9, in which the catalyst is sulphurized before it is applied. contact with the load. 9. Method according to one of the preceding claims wherein the catalyst is prepared according to the following method: a) is prepared a solid called the precursor, containing at least the following compounds: minus one matrix, at least one IM-5 zeolite, optionally at least one element selected from Group VIB and Group VIII elements, optionally at least one promoter element selected from the group consisting of boron, silicon, and phosphorus, optionally at least one group VIIA element, all of which preferably being shaped, b) the dry solid obtained in step a) is calcined at a temperature of at least <Desc / Clms Page number 40> MPa a hydrogen quantity of at least 50 liters of hydrogen per liter of feedstock, and a hourly volumetric rate of between 0.1 and 20 volume of feedstock per volume of catalyst per hour. 11. Method according to one of the preceding claims wherein the load is treated at a temperature above 200 C, a pressure greater than 0.1. VI B, and at least one promoter element selected from the group consisting of boron and silicon. 12. Catalyst comprising at least one amorphous or poorly crystallized oxide-type matrix, an IM-5 zeolite, at least one hydro-dehydrogenating element chosen from the group consisting of Group VIII metals and the metals of the group The catalyst of claim 12 further comprising phosphorus. Catalyst according to one of claims 11 to 12, further comprising at least one element of group VII A. Catalyst according to one of claims 12 to 14, further comprising at least one element of group VII B. Catalyst according to one of claims 12 to 15 closing in% by weight relative to the total mass of catalyst: - 0.1 to 99.7% of IM-5 zeolite, - 0.1 to 60% of at least a hydro-dehydrogenating metal, - 0.1 to 99% of at least one matrix, - 0.1 to 20% of boron and / or silicon, - 0 to 20% of phosphorus, with the sum of the amounts of boron and / or phosphorus and / or silicon of at most 20%, 0 to 20% of at least one element of group VII A, 0 to 20% of at least one element of group VII B. <Desc / Clms Page number 41> 7. Process for preparing a catalyst according to one of claims 12 to 16 wherein: a) is prepared a solid called the precursor, containing at least the following compounds: at least one matrix, at least one IM-5 zeolite , optionally at least one element selected from group VI B and group VIII elements, at least one promoter element selected from the group consisting of boron and silicon, optionally, phosphorus, optionally at least one element of group VII A the whole being preferably shaped, b) the dry solid obtained in step a) is calcined at a temperature of at least 150 C, c) the solid precursor obtained at the end of step b) is impregnated with a solution containing at least one element of group VII B, d) the wet solid is allowed to stand under a humid atmosphere at a temperature between 10 and 120 ° C., e) the wet solid obtained in step d) is dried at a temperature of between 60 and 150 ° C.