Title of Invention	CATALYST AND PROCESS FOR HYDROCRACKING HYDROCARBON CONTAINING FRACTION
Abstract	The invention relates to a hydrocracking catalyst that contains at least one metal of group VIB, and/or at least one metal of group VIII of the periodic table, an alumina matrix, phosphorus, optionally at least one element from group VIlA (fluorine), and a zeolite Y that is not fully dealuminificated, with a crystalline parameter that is -greater than 2,438 nm, an overall SiO<sub>2</sub>/A1<sub>2</sub>O<sub>3</sub> ratio that is less than 8, and a framework SiO<sub>2</sub>/A1<sub>2</sub>O<sub>3</sub> ratio that is less than 21 and greater than the overall SiO<sub>2</sub>/A1<sub>2</sub>O<sub>3</sub> ratio. The invention also relates to a process for hydrocracking with this catalyst, in particular at low pressures of 7.5 to 11 MPa.

Title of Invention

CATALYST AND PROCESS FOR HYDROCRACKING HYDROCARBON CONTAINING FRACTION

Abstract

The invention relates to a hydrocracking catalyst that contains at least one metal of group VIB, and/or at least one metal of group VIII of the periodic table, an alumina matrix, phosphorus, optionally at least one element from group VIlA (fluorine), and a zeolite Y that is not fully dealuminificated, with a crystalline parameter that is -greater than 2,438 nm, an overall SiO2/A12O3 ratio that is less than 8, and a framework SiO2/A12O3 ratio that is less than 21 and greater than the overall SiO2/A12O3 ratio. The invention also relates to a process for hydrocracking with this catalyst, in particular at low pressures of 7.5 to 11 MPa.

Full Text	This invention relates to a catalyst for hydrocracking feedstocks that contain hydrocarbon, whereby said calalyst comprises al least one metal from group VIB (group 6 according to the new notation of the periodic table: Handbook of Chemistry and Physics, 76th P.dition, 1095-1996), preferably molybdenum and tungsten, and optionally a( least one metal from group VIII (groups 8, 0 and 10) of said classification, preferably cobalt, nickel and iron, combined with a substrate that comprises an amorphous or pooily crystallized porous alumina matrix and a non-dealuminafed zeolite Y that has a crystalline parameter that is greater than 2A~W nm. The alumina matrix of the catalyst contains phosphorus and optionally at least one element from group VMA (group 17 of halogens) and in particular fluorine. This invention ulso relates to the processes for preparation of said catalyst, as well as its use for hydrocracking of feedstocks that contain hydrocarbon, such as petroleum fractions and carbon-derived fractions that contain sulfur and nitrogen in the form of organic compounds, whereby said feedstocks optionally contain metals and/or oxygen. The conventional hydrocracking of petroleum fractions is a very important refining process that makes it possible to produce, from excess heavy feedstocks that contain hydiocarbon, fractions that are lighler than gasolines, jet fuels, and light gas-oils that the refiner seeks in order \o adapt production to demand, Compared lo catalytic cracking, the advantage of catalytic hydrocracking is lo provide middle distillates, jet fuels, and gas-oils of very good quality. The catalysts that are used in conventional hydrocracking arc all of the bifunclional type that combine an acid function with a hydrogenating function. The acid function is provided by substrates with large surface areas (generally 150 lo 800 m^g"1) that have a surface acidity, such as the halogenaled aluminas (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 VIIT of the periodic table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium, and platinum, or by a contbina(ion of at least one metal from group VI of the periodic table, such as chromium, molybdenum, and tungsten and at least one metal from group VIII that is preferably not a noble metal. The balance between Ihe acid function and the hydrogenating function is the main parameter that controls the activity and scleclivily of the catalyst. A weak acid function and a strong hydrogenating function provide low-activity catalysts thai work at a generally high temperature (greater than or equal to 390"C) and at a volumetric flow rate at low feed rate (VVH expressed hy volume of feedstock to be treated per unit of volume of catalys( and per hour is generally less than or equal to 2) but (hat have very good selectivity for middle distillates. Conversely, a strong acid function and a weak hydrogenating function provide catalysts that are very active but have poor selectivity for middle distillates. Furthermore, a weak acid function is less sensitive to deactivation, in particular by nitrogenous compounds, than a strong acid function. The challenge therefore is to select judiciously each of the functions in order to adjust the activity/selectivity pair of the catalyst. The low-acidity substrates generally consist of amorphous or poorly crystallized oxides, The low-acidity substrates include the family of amorphous silica-aluminas. Some of the catalysts on the hydrocracking market consist of silica-alumina combined with a combination of sulfides of the metals of groups V1B and VITI. These catalysts make it possible to treat feedstocks that have high contents of heleroatomic poisons, sulfur, and nitrogen. These catalysts have very good selectivity for middle distillates; (hey are- very resistant to the strong nitrogen content, and the products that are formed are of good quality. The drawback of these catalytic systems with an amorphous substrate base is their low activity. The substrates that have strong acidity generally contain a dcaluminated zeolite, for example of the dealnminaled Y type or USY (Ultra Stable Y zeolite), combined with a binder, for example alumina. Some catalysts on the hydrocracking market consist of dealuminated zeolite Y and alumina, which is combined cither with a mc(al from group VIII or with a combination of sulfides of the metals of groups V1B and VIII. These catalysts are preferably used for treating feedstocks whose contents of heleroatomic poisons, sulfur, and nitrogen are less than 0.01% by weight. These systems are very active, and the products that are formed arc of good quality. The drawback to these catalytic systems with a zeolite substrate base is their selectivity for middle distillates, which is not quite as good as that of catalysts with an amorphous substrate base and very high sensitivity to nitrogen content. These catalysis can tolerate only low nitrogen contents in the feedstock, generally less than 100 ppm by weight. The applicant has discovered that, to obtain a hydrocracking catalyst that has a good level of activity and good stability based on feedstocks with high nitrogen content, it is advantageous to combine an acidic amorphous oxide matrix of the alumina type and doped with phosphorus nnd optionally at least one element from group VIIA and in particular fluorine with a very acidic zeolite Y that is not fully dealuminated. Zeolite that is not fully dealuminated is defined as a zeolite Y with a faujasite structure (Zeolite Molecular Sieves Structure, Chemistry and Uses, D. W, BRl:CK, J. WILLF,Y and Sons 1973). The crystalline parameter of this zeolite may have decreased in value clue to the extraction of aluminum from the structure or framework (luring preparation, but the overall SiO/Al,03 ratio has not changed since the aluminum has not been extracted chemically. Such a zeolite that is not fully dealuminated therefore has a silicon and aluminum composition that is expressed by the overall SiO2/Al20, ratio that is equivalent to the starting non-dcaluminatcd zeolite Y. This zeolite Y that is not fully dealuminated may be in hydrogen form or may be at least partially exchanged with metallic callous, for example with cations of alkaline-earth metals and/or cations of rare earth metals of atomic number 57 to 71 inclusive. A zeolite that is lacking in rare earths and alkaline--ear(hs will be preferred, likewise for the catalyst. The zeolite that is not fully dealuminated may be obtained by any treatment that does not extract the aluminum from the sample, such as, for example, treatment with water vapor, treatment by SiCl4,... The catalyst of this invention generally contains, in % by weight relative to the total mass of the catalyst, at least one metal that is selected from the following groups and with the following contents: - 1 lo 40%, preferably 3 to 45% and even more preferably 5 to 30% of at least one metal from group VIB, and/or, - 0.1 to 30%, preferably 0.1 to 25% and even more preferably 0.1 to 20% of at least one metal from group VIII, whereby the catalyst also contains: - 1 to 09%, preferably 10 to 98% and even more preferably 15 to 95% and at least one amorphous or poorly crystallized alumina matrix, - 0.1 to 80%, or else 0.1 to 60% and preferably 0.1-30%, indeed 0.1-20% and even 0.1- 12%, of at least one zeolite Y (hat is not fully dealuminatcd with a crystalline parameter that is greater than 2,438 nm, an overall SiO/Al,O, molar ratio thai is less than 8, a framework SiO,/AI,O, molar ratio that is calculated according to the so-called Pichtner-Schmittlcr correlation (in Crysl. Res. Tech. 1984, 19, Kl) that is less than 21 and greater than vSiO,/AI,O, overall, - 0.1 to 20%, preferably 0.1 to 15% and even more preferably 0,1 to 10% of phosphorus, and optionally, - 0 to 20%;, preferably 0.1 to 15%, and even more preferably 0,1 to 10% of at least one element that is selected from group VIIA, preferably fluorine. The catalysts that are obtained by this invention are produced in the form of grains of various shapes and sizes. They are generally used in the form of cylindrical or polylobed eximdates such as bilobed, trilobed, or polylobed cxtrudates of straight or twisted shape, but may optionally be manufactured and used in the form of crushed powder, tablets, rings, balls, or wheels. They have a specific surface area, measured by nitrogen adsorption according to the HBT method (Brunauer, Emmeti, Teller, J. Am. Chcm. Soc., Vol. 60, 309-316 (1938)), of greater than 140 m3/g, a total pore volume (VPT), measured by mercury porosimctry, of between 0.2 and 1.5 cm7g, and a size distribution of pores (hat can be monomodal, bimodal, or polymodal. Preferably the catalysts of this invention have a monomodal pore distribution. Advantageously, the catalyst according to the invention has few macropore;› (‹IO% of the VPT is located in the pores with a diameter that is greater than 250 A and preferably 7% of the VPT). the pores with a diameter that is greater than 160 A represent 1-14% of the VPT, and preferably 17%, whereas at least 60% of the PVT (preferably 65%, or bctlcr 70%) conesponds to pore diameters of 100-160 A, whereby the remainder corresponds to pores of ‹ 100 A (1 A -10,wm). Thus, in this catalyst the majority of the pores have diameters of 100-160 A. vSaid catalyst has a hydrocracking activity for gas-oil type fractions under vacuum that is superior to that of the catalytic formulas that are known in the prior art. Wi(hout being tied to any theory, it seems thai this particularly high activity of (he catalysts of this invention is due, on the one hand, to the reinforcement of the acidity of the catalyst by the presence of an acidified alumina matrix by the addition of P, which also brings an improvement in the hydrodenitrifying properties of the active phase, which comprises at least one metal from group VIB and optionally al least one metal from group VIII and, on The other hand, by the presence of the very acidic zeolite Y, a good portion of whose acidity will be neutralized by the nitrogenous compounds, but whose acid sites thai are left under operating conditions will impart adequate hydrocracking activity to the catalyst. The catalyr/.. of {hi¾; invc-mion Ciu› l»v i-u^aicd \ty miy v\ IIIU methods mm arc weii known to one skilled in the art. Advantageously, said catalyst is obtained by mixing an alumina source that is optionally doped with phosphorus and a starting zeolite Y source, whereby said mixture is then shaped. The elements of groups VIII and/or VIB, group VIIA and phosphorus are introduced completely or partially during mixing, or else completely after shaping (preferred). Shaping is followed by calcination at a temperature of 250 to ‹SOO°C. One of the preferred shaping methods in this invention consists in mixing (he starting zeolite Y in a moist alumina gel for several tons of minutes, and in then passing (he paste that is thus obtained through a die to form cxtruda(es thai have a diameter of preferably between 0.4 and 4 mm. The alumina source is usually selected from the group that is formed by the alumina gels and alumina powders that are obtained by calcination of aluminum hydroxides and oxyhydioxides. Tt is preferred to use matrices that contain alumina, in any of these forms that arc known to one skilled in the art* for example gamma-alumina. The preferred zeolite Y source is a zeolite Y powder that is characterized by various specifications: a crystalline parameter of greater than 2,451 inn; an overall SiO/A'ip, molar ratio of less than 8, a framework Si(¾/AI,Oj, molar ratio, calculated according to the so-called Fichtncr Schmittlcr correlation (in Cryst. Res. Tech. 1984, 19, Kl), of less than 11; a sodium content of less than 0.2% by weight that is determined on the zeolite that is calcined at 1 lOO"C; a CNti capacity for recovery of sodium ions, expressed in one gram of Na per 100 grams of modified, neutralized, and then caleined zeolite, of greater than about 0.95; a specific surface area, determined by the B.E,T. method, of greater than about 400 m2/g, and preferably greater than 600 mVg; a water vapor adsorption capacity at 25nC for a partial pressure of 2.6 torr (or 34.6 MPa) of greater than about 6%, a pore distribution, determined by nitrogen physisorption, that comprises between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite (hat is contained in pores with a diameter of between 20 x 10'"' m and 80 x JO10 m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite that is contained in pores with a diameter that is greater than 80 x 10",n m and generally less than 1000 x 10""' m, whereby the remainder of the pore volume is contained in the pores with a diameter of less than 20 x 1010 m. The catalyst also contains a hydrogenating function. The hydrogenating function is assured by at least one metal or metal compound of group VI, such as molybdenum and tungsten in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one preferably non-noble metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic: table. The hydrogenating function as defined above can be introduced into (he catalyst at various levels of preparation and in various ways. It can be. introduced only partially (the case, for example, of combinations of metal oxides of groups VI and VIII) or completely at the time of mixing of the alumina source, whereby the remainder of the hydrogenating clemenl(s) is (are) then introduced after mixing and more generally after calcination. Preferably, the metal from group VIII is introduced at the same time as or after the metal from group VI, regardless of the method of introduction, It can be introduced by one or more ion-exchange operations on the calcined substrate that consists of the zeolite that is dispersed in the alumina matrix, with solutions that contain (he precursor salts of (he metals that are selected when the latter belong to group VIII. Jt can be introduced by one or more operations for impregnating the substrate that is shaped and calcined by a solution of the precursors of the oxides of the metals of groups VIII (in particular cobalt and nickel) when (he precursors of the oxides of metals of group VI (in particular molybdenum or tungsten) have been previously introduced at the time of the mixing of the substrate. Finally, it can be introduced by one or more operations for impregnating the calcined substrate that consists of the zeolite and the alumina matrix that is optionally doped with P and/or F, with solutions that contain the precursors of the oxides of metals of groups VI and/or VIII, whereby the precursors of the oxides of metals of group V11I are preferably introduced after those of group VI or at the same time as the latter. In the case where the elements are introduced in several impregnations of the corresponding precursor salts, an intermediate calcination stage of the catalyst should be. carried out at a temperature of between 250 and 6OO"C. The element sources of group VIB that can be used are well known to one skilled in the art. For example, among the sources of molybdenum and tungsten, preferably ammonium oxides and salts, such as ammonium molybdate, ammonium hcptamolybdate, and ammonium tungstatc are used. The sources of the element from group V11I that can be used arc well known to one skilled in the art. For example, nitrates, sulfates. and IIHHHP,R \VU] be used. The introduction of phosphorus into (he catalyst can be carried out at various levels of preparation and in various ways. A preferred method according to the invention consists in preparing an aqueous solution of «t least one element from group VI and optionally at least one element from group VIII and a compound of phosphorus and in carrying out so-called dry impregnation, in which the volumes of the pores of the precursor are filled by the solution that contains the metal from group VI, optionally the metal from group VIII, phosphorus, and optionally the clement from group V11A. The impregnation of molybdenum and/or tungsten can be facilitated by adding phosphoric acid to the solutions, which also makes it possible to introduce phosphorus to promote the catalytic activity. Other phosphorus compounds can be used, as is well known to one skilled in the an. Phosphorus and the element that is selected from among the halide ions of group V11A can be introduced by one or more impregnation operations with excess solution in the calcined precursor. The preferred phosphorus source is orthophosphoric acid H,PO,, but its salts md esters, such as ammonium phosphates, are also suitable. Phosphomolybdic acid and its salts and introduced in the form of, for example, a mixture of phosphoric acid and a basic organic compound thai contains nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine family and chinolcincs and the compounds of (he pyrrole family. The sources of the element from group VIIA that can be used are well known to one skilled in the art. For example, fluoride onions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkaline metals, ammonium, or an organic compound. In this 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 hydroly7,able compounds flint can release fluoride anions in water, such as ammonium fluorosilicate (NH^SiF,,, silicon tetrafluoride Sil74, or sodium te(rafluoridc Na2SiFft, Fluorine can be introduced by, for example, impregnation of an aqueous solution of hydrofluoric acid or ammonium fluoride. The catalysts that are thus obtained are used for hydrocracking of, in particular, distillate-type heavy fractions that contain hydrocarbon and arc under vacuum, deasphaltcd or hydrotreated residues, or the equivalent. The heavy fractions preferably consist of at least 80% by volume of compounds whose boiling points arc at least 35O"C and preferably between 350 and 58O°C (i.e., corresponding to compounds that contain at least 15 to 20 carbon atoms), They generally contain heteroatoms such as sulfur and nitrogen. The nitrogen content is usually between 1 and 5000 ppm by weight, and the sulfur content is between 0.01 and 5% by weight, These feedstocks are lacking in metals or at most they contain only traces of metal without any effect on the catalyst; the optional metals have been removed by hydrotrca£menl, The hydrocracking conditions, such as temperature, pressure, hydrogen recycling rate, and hourly volume rate, can be highly variable depending on the nature of the feedstock, the quality of the products desired, and the facilities that the refiner uses. The temperature is generally greater than 2OO"C and often between 25O'C and 48O"C. The pressure is greater than 0,1 MPa and often greater than 1 MPa. The hydrogen recycling rate is a( leas! 50 and often between 80 and 5000 normal liters of hydrogen per liter of fccdslock. The hourly volume rale is generally between 0,1 and 20 volumes of feedstock per volume of catalyst and per hour. The catalysis of this invention preferably undergo a sulfurization treatment that makes i( possible lo transform, at leas( partially, metal sulfidc radicals before (hey are brought into contact with the fccdslock that is lo be treated. This activation treatment by sulfuri/ation is well known to one skilled in the art and can be carried out by any method that is already described in the literature. A standard sulfurization method thai is well known to one skilled in the art consists in heating, in (he presence of hydrogen sulfide, to a temperature of between 150 and 8OO"C, preferably between 250 and 6OO"C, generally in a continuous flow reader. Finally, owing to the composition of (he catalyst, the latter can be readily reproduced. The catalyst can be used under variable hydrocracking conditions with pressures of al least 2 MPa, a reaction temperature of al least 23O"C, an H2/feedstock ratio of at least 100 Nl H2/l of feedstock and an hourly volume rate of 0.1 -10 h"The treated feedstocks that contain hydrocarbon have initial boiling points of al least I5O"C and preferably at least 35O"C, and more advantageously, i( is a boiling fraction between 35O-58‹rc. The catalyst of this invention can be used for hydrocracking of various fractions thai contain hydrocarbon, for example, distillate-type fractions, under a vacuum that are strongly loaded with sulfur and nitrogen. In a first partial hydrocracking method, the conversion level is less than 55%. The catalyst according to the inveniion is then used at a temperature that is generally greater than or equal lo 23O°C or to 3OO°C, generally at most 4K()"C, and often between 35O"C and 45O"C. The pressure is generally greater than 2 MPa and less than or equal to 12 MPa. A moderate pressure range, which is 7.5-11 MPa, preferably 7.5-10 MPa or else 8-11 MPa and advantageously 8.5-10 MPa, is particularly advantageous, The quantity of hydrogen is al least 100 normal liters of hydrogen per liter of fccdslock and often between 200 and 3000 normal liters of hydrogen per liter of fccdslock. The hourly volume rate is generally between 0.1 and 10 If1. Under these conditions, the catalysis of this invention exhibit belter activity in man me commercial catalysis. In this embodiment, the catalyst of this invention can be used lor partial hydrocraeking, advantageously under conditions of moderate hydrogen pressure, of fractions such as, for example, distillates under vacuum that are strongly loaded with sulfur and nitrogen and that have been previously hydrotreatcd. In this hydrocraeking method, the conversion leve? is less (han 55%. In (his case, the petroleum fraction conversion process takes place in two stages, whereby the catalysts according to the invention are used in the second stage, Catalyst 1 of the first stage has a hydrofrcatment function and comprises a matrix that preferably has an alumina base and preferably does not contain zeolite, and at least one metal that has a hydrogenating function. Said matrix can also consist of, or contain, silica, silica-alumina, boron oxide, magnesia, zirconia, titanium oxide, or a combination of these oxides. The hydrotreatment function is assured by at least one metal or metal compound of group Vlll, such as nickel and cobalt in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic table. The total concentration of metal oxides of groups VI and VITT is between 5 and 40% by weight and preferably between 7 and 30% by weight, and the ratio by weight, expressed in metallic oxide of metal (or metals) of group VI to metal (or metals) of group VIII, is between J.25 and 20 and preferably between 2 and 10, Moreover, this catalyst can contain phosphorus. The phosphorus content, expressed in diphosphorus pentaoxide concentration, will generally be at most 15%, preferably between 0.1 and 15% by weight, and preferably between 0.15 and 10% by weight. It may also contain boron in a(n) (atomic) ratio of B/P = 1,05-2, whereby the sum of the contents in B and P, expressed in oxides, is 5-15% by weight. The first stage generally takes place at a temperature of 35O-46O"C and preferably 360-45O"C, a total pressure of 2 to 12 MPa; and preferably 7.5-11 MPa, 7,5- ]0 MPa or 8-11 MPa or 8.5-10 MPa, an hourly volume rate of 0.1-5 \i\ and preferably 0,2-2 h' and with a quantity of hydrogen of at least 100 NI/NI of feedstock, and preferably 260-3000 NJ/N1 of feedstock. For the conversion stage with the catalyst according to the invention (or second stage), the temperatures arc generally greater than or equal to 23O°C and often between 3OO°C and 43O°C. The pressure is generally between 2 and 12 MPa, preferably 7.5-11 MPa or 7,5-10 MPa or 8 11 MPa or 8.5-10 MPa. The quantity of hydrogen is at least 100 1/1 of feedstock and often between 200 and 3000 1/i of hydrogen per liter of feedstock. The hourly volume rale is generally between 0.15 and 10 h1. Under these conditions, the catalysis of this invention have belter activity in terms of conversion, bydrodcsulfurization, hydrodenitrificalion and better selectivity for middle distillates than the commercial catalysts. The life time of the catalysts is improved in the moderate pressure range. In a second embodiment, the catalyst of this invention can be used for hydrocracking under high hydrogen pressure conditions of at least 8.5 MPa, preferably at least 9 MPa or al least 10 MPa. The treated fractions are* for example, of the distillate type under vacuum and strongly loaded with sulfur and nitrogen that have been previously hyclrolreated. In this hydrocracking method, the conversion level is greater than 55%. In this case, the petroleum fraction conversion process takes place in two stages, whereby the catalyst according to the invention is used in the second stage. Catalyst 1 of the first stage has a hydrotreatment function and comprises a matrix that preferably has an alumina base and preferably does not contain zeolite, and at least one metal that has a hydrogenating function. Said matrix can also consist of, or contain, silica, silica-alumina, boron oxide, magnesia, zirconia, litanium oxide or a combination of these oxides. The hydro-dchydrogena(ing function is assured by at least one metal or metal compound of group VIII, such as nickel and cobalt in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic table. The lotal concentration of oxides of metals of groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% by weight, and the ratio by weight, expressed in metallic oxide of meial (or metals) of group VI to metal (or nielals) of group VIII, is between 1,25 and 20 and preferably between 2 and 10. Furthermore, this catalyst can contain phosphorus. The phosphorus content, expressed by concentration of diphosphorus pentaoxide will generally be at most 15%, preferably between 0,1 and 15% by weight and preferably between 0.15 and 10% by weight. It can also contain boron in a B/P = 1.02-2 (atomic) ratio, whereby the sum of (he contents of B and P that are expressed in oxides is 5-15% by weight. The first stage takes place generally al a temperature of 35O-46O°C and preferably 360-45O°C a pressure greater than 8.5 MPa and preferably greater than JO MPa, an hourly volume rate of 0.1-5 IV1 and preferably 0,2-2 h'\ and with a quantity of hydrogen of at least 100 Nl/Nl of feedstock and preferably 260-3000 Nl/Nl of feedstock. For the conversion stage with the catalyst according to the invention (or second stage), the temperatures are generally greater than or equal to 23O°C and often between %i)lTr. ›md •TM;"i.:. The pj-cssiiic i› £cnciiiiiy gicuicr man 6.5 Ivipa and prcierably greater than 10 MPa. The tiiM•imij- vt iijrimigc;ji i› tti JCWM JUW in or icecisk›cK and o)ten between 200 and 3000 1/1 of hydrogen per liter of feedstock. The hourly volume rate is generally heiwppn O ! 5 that are considerably lower than those of the commercial catalysts. The following examples illustrate this invention without, however, iimitina its acono,. Example 1: Production of a Catalyst CP1 not according to the invention Catalyst CP1 is produced in the following way: SB3-lypc alumina that is supplied by the Cond‹5a Company is extruded through a die with a diameter of 1.4 mm, The cxlrudales are then dried for one night at I2O°C under air and then calcined at 55O"C under air. The exlrudaies are impregnated in the dry state with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orthophosphoric acid, dried for one night at I2O"C under air, and finally calcined under air at 55O"C• The contents by weight of oxides are as follows (relative to (he catalyst): 2.9% by weight of nickel oxide NiO 12.6% by weight of molybdenum oxide MoO, 4.9% by weight of phosphorus oxide P20 Example 2; Production of a Catalyst CP2 not according to the invention Catalyst CP2 is produced in the following way: a Siralox 3(Mype silica-alumina thai is supplied by the Condea Company is extruded through a die with a diameter of 1.4 nun. This silica-alumina contains about 30% by weight of SiOr The extrudaies arc ihen dried for one night at I2(TC under air and (hen calcined at 55O"C under air. The extrudates arc impregnated in the dry state with a solution of a mixture of ammonium heplamolybda(e, nickel nitrate, and orthophosphoric acid, dried for one night at l?O"C under air. and finally calcined under air at 55O"C. The oxide contents by weight are as follows (relative to the catalyst); 2.7% by weight of nickel oxide NiO 12.4% by weight of molybdenum oxide Mo(¾ 4,1 % by weight of phosphorus oxide P205 This type of catalyst is representative of the industrial catalysts for partial hydrocracking of distillates under vacuum. Example 3: Production of a Catalyst CP3 not according to the Invention Catalyst CP3 is produced in the following way: 20% by weight of a zeolite Y with a crystalline parameter (hat is equal to 2.428 nm and an overall SiO2/Al2O3 ratio of 15.2 and a framework SiO2/Al2O3 ratio of 60 that is mixed with 80% by weight of SB3-lype alumina that is supplied by the Cond6a Company is used. The mixed paste is then extruded through a die with a diameter of 1.4 mm. The extrudates are then dried for one night at l2()"C under air and (hen calcined at 55O"C under air. The extrudates are impregnated hi the dry state with an aqueous solution of a mixture of ammonium hcptamoJybdatc, nickel nitrate, and orthophosphoric acid, dried for one night at I2()°C under air, and finally calcined under air at 55(TC. The oxide contents by weight are as follows (relative to the catalyst): 3.0% by weight of nickel oxide NiO 13.0% by weight of molybdenum oxide MoOa 4,4% by weight of phosphorus oxide P205 The final catalyst contains 16.3% by weight of zeolite Y with a mesh parameter of 2.428 nm, an overall SiO2/Al2O3 ratio of 15,2, and a framework SiO2/AI2O3 ratio of 60. Example 4; Production of a Catalyst (T4 According to the invention Catalyst CP4 is produced in (he following way: 20% by weight of a zeoli(e Y with a crystalline parameter that is equal to 2,453 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SiO2/AI2O3 ratio of 8.6 that is mixed with 80% by weight of SB3-lype alumina that is supplied by the Cond6a Company is used. The mixed paste is then extruded through a die with a diameter of 1.4 mm. The extrudales arc then dried for one night at I2()"C under air and then calcined at 55O°C under air. The extrudales are impregnated in the dry state with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orlhophosphoric acid, dried for one night a( I2O"C under air, and finally calcined under air at 55O°C. The contents by weight of active oxides are as follows (relative lo (he catalyst): 2.6% by weight of nickel oxide NiO 12.0% by weight of molybdenum oxide MoO, 4.4% by weight of phosphorus oxide P205 The final catalyst contains 16.5% by weight of zeolite Y with a mesh parameter of 2.444 nm, an overall SiO2/AI2O3 ratio of 6.6, and a framework SiO2/AI2O3 ratio of 14.2. Example 5t Production of a Catalyst CP5 According to the invention Catalyst CP5 is produced in the following way: R% by weight of a zeolite Y with a crystalline parameter of 2.453 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SiO2/AI2O3 ratio of 8.6 that is mixed with 92% by weight of SB3-typc alumina thai is supplied by the Cond6a Company is used. The mixed paste is (hen extruded through a die with a diameter of 1.4 mm. The extrudates are then dried for one night at 12CTC under air and then calcined at 55O"C under air. The extrudales arc impregnated in (he dry slate with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orlhophosphoric acid, dried for one night at 120C under air, and finally calcined under air at 55O°C. The active oxide-contents by weight are as follows (relative to the catalyst): 2.8% by weight of nickel oxide NiO 14.5% by weight of molybdenum oxide MoO, 4.6% by weight of phosphorus oxide P,O‹ • The final catalyst contains 6.1% by weight of zeolite Y with a mesh parameter of 2.443 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SJO2/AI2O3 ratio of 14.8. Kxample 6: Comparison of Catalysts in Hyclrocracking of a Gas-Oil Under Vacuum ai Low Pressure* The catalysts, the steps for whose preparation are described in the examples above, are used under hyclrocracking conditions at moderate pressure on a petroleum feedstock whose main characteristics arc as follows: starting point 365°C 10% point 43O°C 50% point 472°C 90% point 5O4°C end point 539°C pour point + 39°C density (20/4) 0.92°C sulfur (% by weight) 2,46 nitrogen (ppm by weight) 1130 The catalytic test unit comprises two fixed bed reactors, with upward circulation of the feedstock ("up-flow"). 40 ml of catalyst is introduced into each of the reactors. First hydrotreatmen( stage catalyst HTH548, which is sold by the Procatalysc Company and comprises an element from group VJ and an element from group VIII that arc deposited on alumina, is introduced into the first reaclor, the one into which the feedstock passes first. Hydrocraoking catalyst (CP1, CP2t CP3 or CP4) is introduced into the second reactor, the one into which the feedstock passes last. The two catalysts undergo an in-situ sulfurization stage before reaction. Any in-situ or ex situ sulfurization method is suitable. Once the sulfurization is carried out, the feedstock that is described above can be transformed. The total pressure is 8,5 MPa, the hydrogen flow rale is 500 liters of gaseous hydrogen per liter of injected feedstock, and fhe hourly volume rote is O.X h '. The two reactors operate at the same temperature. The. catalytic performance levels aie expressed by coarse conversion at 4OO°C (CB), by ronrse selectivity (SB), and by hydrodesulfuriyafion conversions (HDS) and hydrodcniirification conversions fHDN). These catalytic performance levels are measured on the catalyst after a stabilization period, generally at least 48 hours, has been met. Coarse conversion CB is set equal to: CB rr % by weight of 38OV1"" of the effluent Coarse selectivity SB is set equal to: SB =r 100% by weight of fraction (I5O°C-38O°C)/wcighl of fraction 380"C,rw of the effluent Hydrodcsulfurizing conversion HDS is set equal to: HDS^‹S, l( -S,m ,)/S , 100 = (24600 -S„, f)/24600100 Hydro‹lenitrifying conversion HND is set equal to: HDN = (N . -N„,^/N , 100 = (1130-N m , t)/l 130100 v Mutiny oifruMH' timing c•(m›int- In the following table, we recorded coarse conversion CB at 4OO°C, coarse selectivity SB, hydro(lesulfurizing conversion HDS and hydrodenitrifying conversion HDN for the four catalysts. The use of amorphous catalysis CPl ami (T? shows, that (he catalyst thai has a silica alumina malm provides a better conversion level of fraction 3RO"Cp5"1 than catalyst CPl with an alumina base. In contrast, catalyst CPl. which has an alumina substrate, has the advantage of providing belter performance levels in hydrotreatment (hydrodesulfuwation and hydrodenitiifieation), The use of a catalyst with a zeolite base Y (CP3 or CP4) makes it possible to achieve a Iiiphev conversion level of fraction 3R0Tp,,h than the one that is obtained with amorphous catalysts (CPl and CP2). Depending on die zeolite Y type used and compared to catalyst CP2, this conversion pain varies from 6.5% by weight {catalyst CP3 that has a strongly dcaluminated zeolite} to 10.1% by weight (catalyst CVA (hat has a non-dealuminaled zeolite). Coarse selectivity doerr:i‹:r›Q ‹]?ghtiy when the conversion increases but remains satisfactory, even for the most active catalyst CP4, Furthermore, the use of an alumina matrix that is combined with these zeolites makes it possible to obtain significantly belter catalyst hydrotreatment performance levels (hydrodesulfurization and hydrodenitiifieation). Catalysts CP3 and CP4, which contain zeolite and an alumina substrate, have higher hyclrodesulfuri/ing and hyclrodenitrifying conversion levels than those thai are obtained with catalyst CP2, which contains a silica-alumina matrix, does not contain zeolite, and represents a commercial catalyst. Overall, the use of a non-dealuminaled zcoli(e makes it possible to obtain a catalyst CP4 that is significantly more convertible at isotempcrature than amorphous catalyst CPl with a moderate reduction of selectivity and a catalyst that is more desnlfuri/Jng and more denitrifying than catalyst CP2, which contains an amorphous acid phase and catalyst CP3, which contains u strongly dcaluminated zeolite. The catalysts that contain an alumina (hat is acidified by phosphorus and a zeolite thai is not fully dcaluminated are therefore particularly advantageous for hydrocracking distillate-type feedstock under a vacuum that contains nitrogen at a moderate hydrogen pressure. Example 7; Comparison of Catalysts for Hydrocracking a Gas-Oil Under a Vacuum at a Higher Pressure The catalysts, the steps for whose preparation are described in the examples above, are used under the hydrocraeking conditions at high pressure (12 MPa) on a petroleum feedstock whose main characteristics are as follows; starling point 2'77°C 10% point 381°C 50% point 482°C 00% point 53l°C end point 545°C j›our point +39°C density (20/4) 0.919 sulfur (% by weight) 2.46 nitrogen (ppm by weight) 930 The catalytic test unit comprises two fixed bed reactors, with upward circulation of the feedstock ("up-flow"). 40 ml of catalyst is iniroduccd into each of the reactors, Catalyst 1 of firs! hydrotreatment stage HR360, which is sold by the Procatatyse Company and comprises an element from group VI and an element from group VIII that are deposited on alumina, is introduced into the first reactor, the one into which the feedstock passes first. Second-stage catalyst 2, i.e., the hydroconvcrsion catalyst, is introduced into the second rcaclor, the one into which the feedstock passes last. The two catalysts undergo an in-siui sulfurizing stage before reaction. Any hvsitu or cx-situ sulfurizing method is suitable, Once sulfurizalion is carried out, the feedstock thai is described above can be transformed, The total pressure is 12 MPa, the hydrogen flow is 1000 liters of gaseous hydrogen per liter of injected feedstock, and the hourly volume rate is 0.9 h'1. The catalytic performance levels are expressed by the temperature that makes it possible to achieve a coarse conversion level of 70% and by the coarse selectivity. These catalytic performance levels are measured on the catalyst after a stabilization period, generally at least 48 hours, has elapsed. Coarse conversion CB is set equal to: CB = % by weight of 3K0"CW> of (he effluent Coarse selectivity SB is set equal lo; SB - 100% by weight of fmction CI5or-^8OT)/weighi of fraction 380"CW, of the effluent The reaction temperature is set so as lo achieve a coarse conversion CB thai is ecjual lo 70% by weight. In the following table, we recorded the reaction temperatures and the coarse selec(ivitics for two catalysts CP3 and (VS. The use of the catalyst that contains the zeolite that is not fully dealuminated with the alumina matrix thai is doped with phosphorus CP5 makes it possible to reach a very high selectivity, higher than that of catalyst CP3, while having a lower reaction temperature since a temperature rise of 3"C is observed relative lo catalyst CP3. Jt can be noted that these improvements are obtained with a catalyst that has a zeolite content that is mud) lower than that of the comparison catalyst since a decrease of 16,3% by weight of zeolite to 6.1% has taken place. CLAIMS f. Catalyst that comprises: ) 99% by weight ol al leas( one alumina matrix, 0.1-80% by weight of at least one zeolite Y with a crystalline parameter (hat is greater than 2/138 nm, wi(h an overall SiO/Al,O, molar ratio thai is less than 8 and a framework SiO,/Al/), molar ratio that is less than 21 and greater than overall SiO/Al,O, molar ratio, 0.1-30% by weight of at least one metal from group VIII and/or 1-40% by weight of a( least one metal from group VIB, 0.1 -20% by weight of phosphorus, 0-20% by weight of at least one element from group VIIA. 2. Catalyst according to claim ], whose element from group VIIA is fluorine. 3. Catalyst according (o one of the preceding claims, in which the pores with a diameter › 25 nm occupy a volume that is less than 10% of the total pore volume (VPT), the pores with a diameter greater than 16 nm occupy 1 to 14% of the VPT; and the pores with a diameter of JO-16 nm occupy at least 60% of the VPT, whereby the remainder corresponds to pores with a diameter that is less than 10 nm. 4. Catalyst according to one of the preceding claims that is obtained by mixing zeolite Y with a moist alumina gel, followed by extrusion and calcination at 250-600"C. 5. Process for hydrocracking, with a catalyst according to one of the preceding claims, at a pressure of al least ?. MPa, and a temperature of at least 23O"C, a quantity of hydrogen of at least 100 Nl H2/l of feedstock and an hourly volume rate of 0.1-10 h'1. 6. Process according to claim 5, in which the pressure is 2-12 MPa, the temperature is 3O(M8OV, and the conversion is less than 55%. 7. Process according to claim (\ in which the pressure is 7.5 11 MPa. 8. Process according to claim 6, in which the pressure is R- II MPa. 0. Process according to claim 5. in which the pressure is at least 8.5 MPa, the temperature is 300-43O"C, and the conversion is at least 55%. 10. Process according (o one of claims 5 to 8, in which the feedstock is hydrotreatcd prior lo hydrocracking. 11. Process according to claim 9, in which the hydrolrealmenl catalyst contains a( least one niclal from group VJIT, al least one metal from group VIB and phosphorus, and optionally boron. 12. Catalyst substantially as herelnabove described and exemplified. 13# Catalyst and process for hydrocracking substantially as herelnabove described and exemplified, t t Dated this the 16th day of October 1998

Full Text

This invention relates to a catalyst for hydrocracking feedstocks that contain hydrocarbon, whereby said calalyst comprises al least one metal from group VIB (group 6 according to the new notation of the periodic table: Handbook of Chemistry and Physics, 76th P.dition, 1095-1996), preferably molybdenum and tungsten, and optionally a( least one metal from group VIII (groups 8, 0 and 10) of said classification, preferably cobalt, nickel and iron, combined with a substrate that comprises an amorphous or pooily crystallized porous alumina matrix and a non-dealuminafed zeolite Y that has a crystalline parameter that is greater than 2A~W nm. The alumina matrix of the catalyst contains phosphorus and optionally at least one element from group VMA (group 17 of halogens) and in particular fluorine.
This invention ulso relates to the processes for preparation of said catalyst, as well as its use for hydrocracking of feedstocks that contain hydrocarbon, such as petroleum fractions and carbon-derived fractions that contain sulfur and nitrogen in the form of organic compounds, whereby said feedstocks optionally contain metals and/or oxygen.
The conventional hydrocracking of petroleum fractions is a very important refining process that makes it possible to produce, from excess heavy feedstocks that contain hydiocarbon, fractions that are lighler than gasolines, jet fuels, and light gas-oils that the refiner seeks in order \o adapt production to demand, Compared lo catalytic cracking, the advantage of catalytic hydrocracking is lo provide middle distillates, jet fuels, and gas-oils of very good quality.
The catalysts that are used in conventional hydrocracking arc all of the bifunclional type that combine an acid function with a hydrogenating function. The acid function is provided by substrates with large surface areas (generally 150 lo 800 m^g"1) that have a surface acidity, such as the halogenaled aluminas (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 VIIT of the periodic table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium, and platinum, or by a contbina(ion of at least one metal from group VI of the periodic table, such as chromium, molybdenum, and tungsten and at least one metal from group VIII that is preferably not a noble metal.

The balance between Ihe acid function and the hydrogenating function is the main parameter that controls the activity and scleclivily of the catalyst. A weak acid function and a strong hydrogenating function provide low-activity catalysts thai work at a generally high temperature (greater than or equal to 390"C) and at a volumetric flow rate at low feed rate (VVH expressed hy volume of feedstock to be treated per unit of volume of catalys( and per hour is generally less than or equal to 2) but (hat have very good selectivity for middle distillates. Conversely, a strong acid function and a weak hydrogenating function provide catalysts that are very active but have poor selectivity for middle distillates. Furthermore, a weak acid function is less sensitive to deactivation, in particular by nitrogenous compounds, than a strong acid function. The challenge therefore is to select judiciously each of the functions in order to adjust the activity/selectivity pair of the catalyst.
The low-acidity substrates generally consist of amorphous or poorly crystallized oxides, The low-acidity substrates include the family of amorphous silica-aluminas. Some of the catalysts on the hydrocracking market consist of silica-alumina combined with a combination of sulfides of the metals of groups V1B and VITI. These catalysts make it possible to treat feedstocks that have high contents of heleroatomic poisons, sulfur, and nitrogen. These catalysts have very good selectivity for middle distillates; (hey are- very resistant to the strong nitrogen content, and the products that are formed are of good quality. The drawback of these catalytic systems with an amorphous substrate base is their low activity.
The substrates that have strong acidity generally contain a dcaluminated zeolite, for example of the dealnminaled Y type or USY (Ultra Stable Y zeolite), combined with a binder, for example alumina. Some catalysts on the hydrocracking market consist of dealuminated zeolite Y and alumina, which is combined cither with a mc(al from group VIII or with a combination of sulfides of the metals of groups V1B and VIII. These catalysts are preferably used for treating feedstocks whose contents of heleroatomic poisons, sulfur, and nitrogen are less than 0.01% by weight. These systems are very active, and the products that are formed arc of good quality. The drawback to these catalytic systems with a zeolite substrate base is their selectivity for middle distillates, which is not quite as good as that of catalysts with an

amorphous substrate base and very high sensitivity to nitrogen content. These catalysis can tolerate only low nitrogen contents in the feedstock, generally less than 100 ppm by weight.
The applicant has discovered that, to obtain a hydrocracking catalyst that has a good level of activity and good stability based on feedstocks with high nitrogen content, it is advantageous to combine an acidic amorphous oxide matrix of the alumina type and doped with phosphorus nnd optionally at least one element from group VIIA and in particular fluorine with a very acidic zeolite Y that is not fully dealuminated.
Zeolite that is not fully dealuminated is defined as a zeolite Y with a faujasite structure (Zeolite Molecular Sieves Structure, Chemistry and Uses, D. W, BRl:CK, J. WILLF,Y and Sons 1973). The crystalline parameter of this zeolite may have decreased in value clue to the extraction of aluminum from the structure or framework (luring preparation, but the overall SiO/Al,03 ratio has not changed since the aluminum has not been extracted chemically. Such a zeolite that is not fully dealuminated therefore has a silicon and aluminum composition that is expressed by the overall SiO2/Al20, ratio that is equivalent to the starting non-dcaluminatcd zeolite Y. This zeolite Y that is not fully dealuminated may be in hydrogen form or may be at least partially exchanged with metallic callous, for example with cations of alkaline-earth metals and/or cations of rare earth metals of atomic number 57 to 71 inclusive. A zeolite that is lacking in rare earths and alkaline--ear(hs will be preferred, likewise for the catalyst.
The zeolite that is not fully dealuminated may be obtained by any treatment that does not extract the aluminum from the sample, such as, for example, treatment with water vapor, treatment by SiCl4,...
The catalyst of this invention generally contains, in % by weight relative to the total mass of the catalyst, at least one metal that is selected from the following groups and with the following contents:
- 1 lo 40%, preferably 3 to 45% and even more preferably 5 to 30% of at least one metal
from group VIB,
and/or,
- 0.1 to 30%, preferably 0.1 to 25% and even more preferably 0.1 to 20% of at least one
metal from group VIII,

whereby the catalyst also contains:
- 1 to 09%, preferably 10 to 98% and even more preferably 15 to 95% and at least one amorphous or poorly crystallized alumina matrix,
- 0.1 to 80%, or else 0.1 to 60% and preferably 0.1-30%, indeed 0.1-20% and even 0.1-
12%, of at least one zeolite Y (hat is not fully dealuminatcd with a crystalline parameter that is
greater than 2,438 nm, an overall SiO/Al,O, molar ratio thai is less than 8, a framework
SiO,/AI,O, molar ratio that is calculated according to the so-called Pichtner-Schmittlcr
correlation (in Crysl. Res. Tech. 1984, 19, Kl) that is less than 21 and greater than vSiO,/AI,O,
overall,
- 0.1 to 20%, preferably 0.1 to 15% and even more preferably 0,1 to 10% of
phosphorus,
and optionally,
- 0 to 20%;, preferably 0.1 to 15%, and even more preferably 0,1 to 10% of at least one
element that is selected from group VIIA, preferably fluorine.
The catalysts that are obtained by this invention are produced in the form of grains of various shapes and sizes. They are generally used in the form of cylindrical or polylobed eximdates such as bilobed, trilobed, or polylobed cxtrudates of straight or twisted shape, but may optionally be manufactured and used in the form of crushed powder, tablets, rings, balls, or wheels. They have a specific surface area, measured by nitrogen adsorption according to the HBT method (Brunauer, Emmeti, Teller, J. Am. Chcm. Soc., Vol. 60, 309-316 (1938)), of greater than 140 m3/g, a total pore volume (VPT), measured by mercury porosimctry, of between 0.2 and 1.5 cm7g, and a size distribution of pores (hat can be monomodal, bimodal, or polymodal. Preferably the catalysts of this invention have a monomodal pore distribution.
Advantageously, the catalyst according to the invention has few macropore;› (‹IO% of the VPT is located in the pores with a diameter that is greater than 250 A and preferably 7% of the VPT). the pores with a diameter that is greater than 160 A represent 1-14% of the VPT, and preferably 17%, whereas at least 60% of the PVT (preferably 65%, or bctlcr 70%) conesponds to pore diameters of 100-160 A, whereby the remainder corresponds to pores of ‹ 100 A (1 A -10,wm).

Thus, in this catalyst the majority of the pores have diameters of 100-160 A.
vSaid catalyst has a hydrocracking activity for gas-oil type fractions under vacuum that is superior to that of the catalytic formulas that are known in the prior art. Wi(hout being tied to any theory, it seems thai this particularly high activity of (he catalysts of this invention is due, on the one hand, to the reinforcement of the acidity of the catalyst by the presence of an acidified alumina matrix by the addition of P, which also brings an improvement in the hydrodenitrifying properties of the active phase, which comprises at least one metal from group VIB and optionally al least one metal from group VIII and, on The other hand, by the presence of the very acidic zeolite Y, a good portion of whose acidity will be neutralized by the nitrogenous compounds, but whose acid sites thai are left under operating conditions will impart adequate hydrocracking activity to the catalyst.
The catalyr/.. of {hi¾; invc-mion Ciu› l»v i-u^aicd \ty miy v\ IIIU methods mm arc weii known to one skilled in the art.
Advantageously, said catalyst is obtained by mixing an alumina source that is optionally doped with phosphorus and a starting zeolite Y source, whereby said mixture is then shaped. The elements of groups VIII and/or VIB, group VIIA and phosphorus are introduced completely or partially during mixing, or else completely after shaping (preferred). Shaping is followed by calcination at a temperature of 250 to ‹SOO°C. One of the preferred shaping methods in this invention consists in mixing (he starting zeolite Y in a moist alumina gel for several tons of minutes, and in then passing (he paste that is thus obtained through a die to form cxtruda(es thai have a diameter of preferably between 0.4 and 4 mm.
The alumina source is usually selected from the group that is formed by the alumina gels and alumina powders that are obtained by calcination of aluminum hydroxides and oxyhydioxides. Tt is preferred to use matrices that contain alumina, in any of these forms that arc known to one skilled in the art* for example gamma-alumina.
The preferred zeolite Y source is a zeolite Y powder that is characterized by various specifications: a crystalline parameter of greater than 2,451 inn; an overall SiO/A'ip, molar ratio of less than 8, a framework Si(¾/AI,Oj, molar ratio, calculated according to the so-called Fichtncr Schmittlcr correlation (in Cryst. Res. Tech. 1984, 19, Kl), of less than 11; a sodium

content of less than 0.2% by weight that is determined on the zeolite that is calcined at 1 lOO"C; a CNti capacity for recovery of sodium ions, expressed in one gram of Na per 100 grams of modified, neutralized, and then caleined zeolite, of greater than about 0.95; a specific surface area, determined by the B.E,T. method, of greater than about 400 m2/g, and preferably greater than 600 mVg; a water vapor adsorption capacity at 25nC for a partial pressure of 2.6 torr (or 34.6 MPa) of greater than about 6%, a pore distribution, determined by nitrogen physisorption, that comprises between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite (hat is contained in pores with a diameter of between 20 x 10'"' m and 80 x JO*10 m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite that is contained in pores with a diameter that is greater than 80 x 10",n m and generally less than 1000 x 10""' m, whereby the remainder of the pore volume is contained in the pores with a diameter of less than 20 x 1010 m.
The catalyst also contains a hydrogenating function. The hydrogenating function is assured by at least one metal or metal compound of group VI, such as molybdenum and tungsten in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one preferably non-noble metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic: table.
The hydrogenating function as defined above can be introduced into (he catalyst at various levels of preparation and in various ways. It can be. introduced only partially (the case, for example, of combinations of metal oxides of groups VI and VIII) or completely at the time of mixing of the alumina source, whereby the remainder of the hydrogenating clemenl(s) is (are) then introduced after mixing and more generally after calcination. Preferably, the metal from group VIII is introduced at the same time as or after the metal from group VI, regardless of the method of introduction, It can be introduced by one or more ion-exchange operations on the calcined substrate that consists of the zeolite that is dispersed in the alumina matrix, with solutions that contain (he precursor salts of (he metals that are selected when the latter belong to group VIII. Jt can be introduced by one or more operations for impregnating the substrate that is shaped and calcined by a solution of the precursors of the oxides of the metals of groups VIII (in particular cobalt and nickel) when (he precursors of the oxides of metals of group VI (in

particular molybdenum or tungsten) have been previously introduced at the time of the mixing of the substrate. Finally, it can be introduced by one or more operations for impregnating the calcined substrate that consists of the zeolite and the alumina matrix that is optionally doped with P and/or F, with solutions that contain the precursors of the oxides of metals of groups VI and/or VIII, whereby the precursors of the oxides of metals of group V11I are preferably introduced after those of group VI or at the same time as the latter.
In the case where the elements are introduced in several impregnations of the corresponding precursor salts, an intermediate calcination stage of the catalyst should be. carried out at a temperature of between 250 and 6OO"C.
The element sources of group VIB that can be used are well known to one skilled in the art. For example, among the sources of molybdenum and tungsten, preferably ammonium oxides and salts, such as ammonium molybdate, ammonium hcptamolybdate, and ammonium tungstatc are used.
The sources of the element from group V11I that can be used arc well known to one skilled in the art. For example, nitrates, sulfates. and IIHHHP,R \VU] be used.
The introduction of phosphorus into (he catalyst can be carried out at various levels of preparation and in various ways. A preferred method according to the invention consists in preparing an aqueous solution of «t least one element from group VI and optionally at least one element from group VIII and a compound of phosphorus and in carrying out so-called dry impregnation, in which the volumes of the pores of the precursor are filled by the solution that contains the metal from group VI, optionally the metal from group VIII, phosphorus, and optionally the clement from group V11A.
The impregnation of molybdenum and/or tungsten can be facilitated by adding phosphoric acid to the solutions, which also makes it possible to introduce phosphorus to promote the catalytic activity. Other phosphorus compounds can be used, as is well known to one skilled in the an.
Phosphorus and the element that is selected from among the halide ions of group V11A can be introduced by one or more impregnation operations with excess solution in the calcined precursor.

The preferred phosphorus source is orthophosphoric acid H,PO,, but its salts md esters, such as ammonium phosphates, are also suitable. Phosphomolybdic acid and its salts and
introduced in the form of, for example, a mixture of phosphoric acid and a basic organic compound thai contains nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine family and chinolcincs and the compounds of (he pyrrole
family.
The sources of the element from group VIIA that can be used are well known to one skilled in the art. For example, fluoride onions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkaline metals, ammonium, or an organic compound. In this 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 hydroly7,able compounds flint can release fluoride anions in water, such as ammonium fluorosilicate (NH^SiF,,, silicon tetrafluoride Sil74, or sodium te(rafluoridc Na2SiFft, Fluorine can be introduced by, for example, impregnation of an aqueous solution of hydrofluoric acid or ammonium fluoride.
The catalysts that are thus obtained are used for hydrocracking of, in particular, distillate-type heavy fractions that contain hydrocarbon and arc under vacuum, deasphaltcd or hydrotreated residues, or the equivalent. The heavy fractions preferably consist of at least 80% by volume of compounds whose boiling points arc at least 35O"C and preferably between 350 and 58O°C (i.e., corresponding to compounds that contain at least 15 to 20 carbon atoms), They generally contain heteroatoms such as sulfur and nitrogen. The nitrogen content is usually between 1 and 5000 ppm by weight, and the sulfur content is between 0.01 and 5% by weight, These feedstocks are lacking in metals* or at most they contain only traces of metal without any effect on the catalyst; the optional metals have been removed by hydrotrca£menl,
The hydrocracking conditions, such as temperature, pressure, hydrogen recycling rate, and hourly volume rate, can be highly variable depending on the nature of the feedstock, the quality of the products desired, and the facilities that the refiner uses. The temperature is generally greater than 2OO"C and often between 25O'C and 48O"C. The pressure is greater than

0,1 MPa and often greater than 1 MPa. The hydrogen recycling rate is a( leas! 50 and often between 80 and 5000 normal liters of hydrogen per liter of fccdslock. The hourly volume rale is generally between 0,1 and 20 volumes of feedstock per volume of catalyst and per hour.
The catalysis of this invention preferably undergo a sulfurization treatment that makes i( possible lo transform, at leas( partially, metal sulfidc radicals before (hey are brought into contact with the fccdslock that is lo be treated. This activation treatment by sulfuri/ation is well known to one skilled in the art and can be carried out by any method that is already described in the literature.
A standard sulfurization method thai is well known to one skilled in the art consists in heating, in (he presence of hydrogen sulfide, to a temperature of between 150 and 8OO"C, preferably between 250 and 6OO"C, generally in a continuous flow reader.
Finally, owing to the composition of (he catalyst, the latter can be readily reproduced.
The catalyst can be used under variable hydrocracking conditions with pressures of al least 2 MPa, a reaction temperature of al least 23O"C, an H2/feedstock ratio of at least 100 Nl H2/l of feedstock and an hourly volume rate of 0.1 -10 h"The treated feedstocks that contain hydrocarbon have initial boiling points of al least I5O"C and preferably at least 35O"C, and more advantageously, i( is a boiling fraction between 35O-58‹rc.
The catalyst of this invention can be used for hydrocracking of various fractions thai contain hydrocarbon, for example, distillate-type fractions, under a vacuum that are strongly loaded with sulfur and nitrogen. In a first partial hydrocracking method, the conversion level is less than 55%. The catalyst according to the inveniion is then used at a temperature that is generally greater than or equal lo 23O°C or to 3OO°C, generally at most 4K()"C, and often between 35O"C and 45O"C. The pressure is generally greater than 2 MPa and less than or equal to 12 MPa. A moderate pressure range, which is 7.5-11 MPa, preferably 7.5-10 MPa or else 8-11 MPa and advantageously 8.5-10 MPa, is particularly advantageous, The quantity of hydrogen is al least 100 normal liters of hydrogen per liter of fccdslock and often between 200 and 3000 normal liters of hydrogen per liter of fccdslock. The hourly volume rate is generally between 0.1 and 10 If1. Under these conditions, the catalysis of this invention exhibit belter activity in

man me commercial catalysis.
In this embodiment, the catalyst of this invention can be used lor partial hydrocraeking, advantageously under conditions of moderate hydrogen pressure, of fractions such as, for example, distillates under vacuum that are strongly loaded with sulfur and nitrogen and that have been previously hydrotreatcd. In this hydrocraeking method, the conversion leve? is less (han 55%. In (his case, the petroleum fraction conversion process takes place in two stages, whereby the catalysts according to the invention are used in the second stage, Catalyst 1 of the first stage has a hydrofrcatment function and comprises a matrix that preferably has an alumina base and preferably does not contain zeolite, and at least one metal that has a hydrogenating function. Said matrix can also consist of, or contain, silica, silica-alumina, boron oxide, magnesia, zirconia, titanium oxide, or a combination of these oxides. The hydrotreatment function is assured by at least one metal or metal compound of group Vlll, such as nickel and cobalt in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic table. The total concentration of metal oxides of groups VI and VITT is between 5 and 40% by weight and preferably between 7 and 30% by weight, and the ratio by weight, expressed in metallic oxide of metal (or metals) of group VI to metal (or metals) of group VIII, is between J.25 and 20 and preferably between 2 and 10, Moreover, this catalyst can contain phosphorus. The phosphorus content, expressed in diphosphorus pentaoxide concentration, will generally be at most 15%, preferably between 0.1 and 15% by weight, and preferably between 0.15 and 10% by weight. It may also contain boron in a(n) (atomic) ratio of B/P = 1,05-2, whereby the sum of the contents in B and P, expressed in oxides, is 5-15% by weight.
The first stage generally takes place at a temperature of 35O-46O"C and preferably 360-45O"C, a total pressure of 2 to 12 MPa; and preferably 7.5-11 MPa, 7,5- ]0 MPa or 8-11 MPa or 8.5-10 MPa, an hourly volume rate of 0.1-5 \i\ and preferably 0,2-2 h' and with a quantity of hydrogen of at least 100 NI/NI of feedstock, and preferably 260-3000 NJ/N1 of feedstock.

For the conversion stage with the catalyst according to the invention (or second stage), the temperatures arc generally greater than or equal to 23O°C and often between 3OO°C and 43O°C. The pressure is generally between 2 and 12 MPa, preferably 7.5-11 MPa or 7,5-10 MPa or 8 11 MPa or 8.5-10 MPa. The quantity of hydrogen is at least 100 1/1 of feedstock and often between 200 and 3000 1/i of hydrogen per liter of feedstock. The hourly volume rale is generally between 0.15 and 10 h1.
Under these conditions, the catalysis of this invention have belter activity in terms of conversion, bydrodcsulfurization, hydrodenitrificalion and better selectivity for middle distillates than the commercial catalysts. The life time of the catalysts is improved in the moderate pressure range.
In a second embodiment, the catalyst of this invention can be used for hydrocracking under high hydrogen pressure conditions of at least 8.5 MPa, preferably at least 9 MPa or al least 10 MPa. The treated fractions are* for example, of the distillate type under vacuum and strongly loaded with sulfur and nitrogen that have been previously hyclrolreated. In this hydrocracking method, the conversion level is greater than 55%. In this case, the petroleum fraction conversion process takes place in two stages, whereby the catalyst according to the invention is used in the
second stage.
Catalyst 1 of the first stage has a hydrotreatment function and comprises a matrix that preferably has an alumina base and preferably does not contain zeolite, and at least one metal that has a hydrogenating function. Said matrix can also consist of, or contain, silica, silica-alumina, boron oxide, magnesia, zirconia, litanium oxide or a combination of these oxides. The hydro-dchydrogena(ing function is assured by at least one metal or metal compound of group VIII, such as nickel and cobalt in particular. It is possible to use a combination of at least one metal or metal compound of group VI (in particular molybdenum or tungsten) and at least one metal or metal compound of group VIII (in particular cobalt or nickel) of the periodic table. The lotal concentration of oxides of metals of groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% by weight, and the ratio by weight, expressed in metallic oxide of meial (or metals) of group VI to metal (or nielals) of group VIII, is between 1,25 and 20 and preferably between 2 and 10. Furthermore, this catalyst can contain phosphorus. The

phosphorus content, expressed by concentration of diphosphorus pentaoxide will generally be at most 15%, preferably between 0,1 and 15% by weight and preferably between 0.15 and 10% by weight. It can also contain boron in a B/P = 1.02-2 (atomic) ratio, whereby the sum of (he contents of B and P that are expressed in oxides is 5-15% by weight.
The first stage takes place generally al a temperature of 35O-46O°C and preferably 360-45O°C a pressure greater than 8.5 MPa and preferably greater than JO MPa, an hourly volume rate of 0.1-5 IV1 and preferably 0,2-2 h'\ and with a quantity of hydrogen of at least 100 Nl/Nl of feedstock and preferably 260-3000 Nl/Nl of feedstock.
For the conversion stage with the catalyst according to the invention (or second stage), the temperatures are generally greater than or equal to 23O°C and often between %i)lTr. ›md
•TM;"i.:. The pj-cssiiic i› £cnciiiiiy gicuicr man 6.5 Ivipa and prcierably greater than 10 MPa. The tiiM•imij- vt iijrimigc;ji i› tti JCWM JUW in or icecisk›cK and o)ten between 200 and 3000 1/1 of
hydrogen per liter of feedstock. The hourly volume rate is generally heiwppn O ! 5 that are considerably lower than those of the commercial catalysts.
The following examples illustrate this invention without, however, iimitina its acono,.
Example 1: Production of a Catalyst CP1 not according to the invention
Catalyst CP1 is produced in the following way: SB3-lypc alumina that is supplied by the Cond‹5a Company is extruded through a die with a diameter of 1.4 mm, The cxlrudales are then dried for one night at I2O°C under air and then calcined at 55O"C under air. The exlrudaies are impregnated in the dry state with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orthophosphoric acid, dried for one night at I2O"C under air, and finally calcined under air at 55O"C• The contents by weight of oxides are as follows (relative to (he catalyst):
2.9% by weight of nickel oxide NiO
12.6% by weight of molybdenum oxide MoO,
4.9% by weight of phosphorus oxide P20
Example 2; Production of a Catalyst CP2 not according to the invention
Catalyst CP2 is produced in the following way: a Siralox 3(Mype silica-alumina thai is supplied by the Condea Company is extruded through a die with a diameter of 1.4 nun. This silica-alumina contains about 30% by weight of SiOr The extrudaies arc ihen dried for one night at I2(TC under air and (hen calcined at 55O"C under air. The extrudates arc impregnated in the dry state with a solution of a mixture of ammonium heplamolybda(e, nickel nitrate, and orthophosphoric acid, dried for one night at l?O"C under air. and finally calcined under air at 55O"C. The oxide contents by weight are as follows (relative to the catalyst);
2.7% by weight of nickel oxide NiO
12.4% by weight of molybdenum oxide Mo(¾
4,1 % by weight of phosphorus oxide P205
This type of catalyst is representative of the industrial catalysts for partial hydrocracking of distillates under vacuum.
Example 3: Production of a Catalyst CP3 not according to the Invention
Catalyst CP3 is produced in the following way: 20% by weight of a zeolite Y with a crystalline parameter (hat is equal to 2.428 nm and an overall SiO2/Al2O3 ratio of 15.2 and a framework SiO2/Al2O3 ratio of 60 that is mixed with 80% by weight of SB3-lype alumina that is supplied by the Cond6a Company is used. The mixed paste is then extruded through a die with a diameter of 1.4 mm. The extrudates are then dried for one night at l2()"C under air and (hen calcined at 55O"C under air. The extrudates are impregnated hi the dry state with an aqueous solution of a mixture of ammonium hcptamoJybdatc, nickel nitrate, and orthophosphoric acid, dried for one night at I2()°C under air, and finally calcined under air at 55(TC. The oxide contents by weight are as follows (relative to the catalyst):
3.0% by weight of nickel oxide NiO
13.0% by weight of molybdenum oxide MoOa
4,4% by weight of phosphorus oxide P205

The final catalyst contains 16.3% by weight of zeolite Y with a mesh parameter of 2.428 nm, an overall SiO2/Al2O3 ratio of 15,2, and a framework SiO2/AI2O3 ratio of 60.
Example 4; Production of a Catalyst (T4 According to the invention
Catalyst CP4 is produced in (he following way: 20% by weight of a zeoli(e Y with a crystalline parameter that is equal to 2,453 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SiO2/AI2O3 ratio of 8.6 that is mixed with 80% by weight of SB3-lype alumina that is supplied by the Cond6a Company is used. The mixed paste is then extruded through a die with a diameter of 1.4 mm. The extrudales arc then dried for one night at I2()"C under air and then calcined at 55O°C under air. The extrudales are impregnated in the dry state with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orlhophosphoric acid, dried for one night a( I2O"C under air, and finally calcined under air at 55O°C. The contents by weight of active oxides are as follows (relative lo (he catalyst):
2.6% by weight of nickel oxide NiO
12.0% by weight of molybdenum oxide MoO,
4.4% by weight of phosphorus oxide P205
The final catalyst contains 16.5% by weight of zeolite Y with a mesh parameter of 2.444 nm, an overall SiO2/AI2O3 ratio of 6.6, and a framework SiO2/AI2O3 ratio of 14.2.
Example 5t Production of a Catalyst CP5 According to the invention
Catalyst CP5 is produced in the following way: R% by weight of a zeolite Y with a crystalline parameter of 2.453 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SiO2/AI2O3 ratio of 8.6 that is mixed with 92% by weight of SB3-typc alumina thai is supplied by the Cond6a Company is used. The mixed paste is (hen extruded through a die with a diameter of 1.4 mm. The extrudates are then dried for one night at 12CTC under air and then calcined at 55O"C under air. The extrudales arc impregnated in (he dry slate with an aqueous solution of a mixture of ammonium heptamolybdatc, nickel nitrate, and orlhophosphoric acid, dried for one night at 120C under air, and finally calcined under air at 55O°C. The active oxide-contents by weight are as follows (relative to the catalyst):

2.8% by weight of nickel oxide NiO 14.5% by weight of molybdenum oxide MoO, 4.6% by weight of phosphorus oxide P,O‹ •
The final catalyst contains 6.1% by weight of zeolite Y with a mesh parameter of 2.443 nm and an overall SiO2/AI2O3 ratio of 6.6 and a framework SJO2/AI2O3 ratio of 14.8.
Kxample 6: Comparison of Catalysts in Hyclrocracking of a Gas-Oil Under Vacuum ai Low Pressure*
The catalysts, the steps for whose preparation are described in the examples above, are used under hyclrocracking conditions at moderate pressure on a petroleum feedstock whose main characteristics arc as follows:
starting point 365°C
10% point 43O°C
50% point 472°C
90% point 5O4°C
end point 539°C
pour point + 39°C
density (20/4) 0.92°C
sulfur (% by weight) 2,46
nitrogen (ppm by weight) 1130
The catalytic test unit comprises two fixed bed reactors, with upward circulation of the feedstock ("up-flow"). 40 ml of catalyst is introduced into each of the reactors. First hydrotreatmen( stage catalyst HTH548, which is sold by the Procatalysc Company and comprises an element from group VJ and an element from group VIII that arc deposited on alumina, is introduced into the first reaclor, the one into which the feedstock passes first. Hydrocraoking catalyst (CP1, CP2t CP3 or CP4) is introduced into the second reactor, the one into which the feedstock passes last. The two catalysts undergo an in-situ sulfurization stage before reaction. Any in-situ or ex situ sulfurization method is suitable. Once the sulfurization is carried out, the feedstock that is described above can be transformed. The total pressure is 8,5

MPa, the hydrogen flow rale is 500 liters of gaseous hydrogen per liter of injected feedstock, and fhe hourly volume rote is O.X h '. The two reactors operate at the same temperature.
The. catalytic performance levels aie expressed by coarse conversion at 4OO°C (CB), by ronrse selectivity (SB), and by hydrodesulfuriyafion conversions (HDS) and hydrodcniirification conversions fHDN). These catalytic performance levels are measured on the catalyst after a stabilization period, generally at least 48 hours, has been met.
Coarse conversion CB is set equal to:
CB rr % by weight of 38OV1"" of the effluent
Coarse selectivity SB is set equal to:
SB =r 100% by weight of fraction (I5O°C-38O°C)/wcighl of fraction 380"C,rw of the effluent
Hydrodcsulfurizing conversion HDS is set equal to:
HDS^‹S, l( -S,m ,)/S , *100 = (24600 -S„, f)/24600*100
Hydro‹lenitrifying conversion HND is set equal to:
HDN = (N . -N„,^/N , *100 = (1130-N m , t)/l 130*100
v Mutiny oifruMH' timing c•(m›int-
In the following table, we recorded coarse conversion CB at 4OO°C, coarse selectivity SB, hydro(lesulfurizing conversion HDS and hydrodenitrifying conversion HDN for the four catalysts.

The use of amorphous catalysis CPl ami (T? shows, that (he catalyst thai has a silica alumina malm provides a better conversion level of fraction 3RO"Cp5"1 than catalyst CPl with an alumina base. In contrast, catalyst CPl. which has an alumina substrate, has the advantage of providing belter performance levels in hydrotreatment (hydrodesulfuwation and hydrodenitiifieation),
The use of a catalyst with a zeolite base Y (CP3 or CP4) makes it possible to achieve a Iiiphev conversion level of fraction 3R0Tp,,h than the one that is obtained with amorphous catalysts (CPl and CP2). Depending on die zeolite Y type used and compared to catalyst CP2, this conversion pain varies from 6.5% by weight {catalyst CP3 that has a strongly dcaluminated zeolite} to 10.1% by weight (catalyst CVA (hat has a non-dealuminaled zeolite). Coarse selectivity doerr:i‹:r›Q ‹]?ghtiy when the conversion increases but remains satisfactory, even for the most active catalyst CP4, Furthermore, the use of an alumina matrix that is combined with these zeolites makes it possible to obtain significantly belter catalyst hydrotreatment performance levels (hydrodesulfurization and hydrodenitiifieation). Catalysts CP3 and CP4, which contain zeolite and an alumina substrate, have higher hyclrodesulfuri/ing and hyclrodenitrifying conversion levels than those thai are obtained with catalyst CP2, which contains a silica-alumina matrix, does not contain zeolite, and represents a commercial catalyst. Overall, the use of a non-dealuminaled zcoli(e makes it possible to obtain a catalyst CP4 that is significantly more convertible at isotempcrature than amorphous catalyst CPl with a moderate reduction of selectivity and a catalyst that is more desnlfuri/Jng and more denitrifying than catalyst CP2, which contains an amorphous acid phase and catalyst CP3, which contains u strongly dcaluminated zeolite.
The catalysts that contain an alumina (hat is acidified by phosphorus and a zeolite thai is not fully dcaluminated are therefore particularly advantageous for hydrocracking distillate-type feedstock under a vacuum that contains nitrogen at a moderate hydrogen pressure.
Example 7; Comparison of Catalysts for Hydrocracking a Gas-Oil Under a Vacuum at a Higher Pressure

The catalysts, the steps for whose preparation are described in the examples above, are used under the hydrocraeking conditions at high pressure (12 MPa) on a petroleum feedstock whose main characteristics are as follows;
starling point 2'77°C
10% point 381°C
50% point 482°C
00% point 53l°C
end point 545°C
j›our point +39°C
density (20/4) 0.919
sulfur (% by weight) 2.46
nitrogen (ppm by weight) 930
The catalytic test unit comprises two fixed bed reactors, with upward circulation of the feedstock ("up-flow"). 40 ml of catalyst is iniroduccd into each of the reactors, Catalyst 1 of firs! hydrotreatment stage HR360, which is sold by the Procatatyse Company and comprises an element from group VI and an element from group VIII that are deposited on alumina, is introduced into the first reactor, the one into which the feedstock passes first. Second-stage catalyst 2, i.e., the hydroconvcrsion catalyst, is introduced into the second rcaclor, the one into which the feedstock passes last. The two catalysts undergo an in-siui sulfurizing stage before reaction. Any hvsitu or cx-situ sulfurizing method is suitable, Once sulfurizalion is carried out, the feedstock thai is described above can be transformed, The total pressure is 12 MPa, the hydrogen flow is 1000 liters of gaseous hydrogen per liter of injected feedstock, and the hourly volume rate is 0.9 h'1.
The catalytic performance levels are expressed by the temperature that makes it possible to achieve a coarse conversion level of 70% and by the coarse selectivity. These catalytic performance levels are measured on the catalyst after a stabilization period, generally at least 48 hours, has elapsed.
Coarse conversion CB is set equal to:

CB = % by weight of 3K0"CW> of (he effluent
Coarse selectivity SB is set equal lo;
SB - 100% by weight of fmction CI5or-^8OT)/weighi of fraction 380"CW, of the effluent
The reaction temperature is set so as lo achieve a coarse conversion CB thai is ecjual lo 70% by weight. In the following table, we recorded the reaction temperatures and the coarse selec(ivitics for two catalysts CP3 and (VS.

The use of the catalyst that contains the zeolite that is not fully dealuminated with the alumina matrix thai is doped with phosphorus CP5 makes it possible to reach a very high selectivity, higher than that of catalyst CP3, while having a lower reaction temperature since a temperature rise of 3"C is observed relative lo catalyst CP3. Jt can be noted that these improvements are obtained with a catalyst that has a zeolite content that is mud) lower than that of the comparison catalyst since a decrease of 16,3% by weight of zeolite to 6.1% has taken place.

CLAIMS
f. Catalyst that comprises:
) 99% by weight ol al leas( one alumina matrix,
0.1-80% by weight of at least one zeolite Y with a crystalline parameter (hat is greater than 2/138 nm, wi(h an overall SiO/Al,O, molar ratio thai is less than 8 and a framework SiO,/Al/), molar ratio that is less than 21 and greater than overall SiO/Al,O, molar ratio,
0.1-30% by weight of at least one metal from group VIII and/or 1-40% by weight of a( least one metal from group VIB,
0.1 -20% by weight of phosphorus,
0-20% by weight of at least one element from group VIIA.
2. Catalyst according to claim ], whose element from group VIIA is fluorine.
3. Catalyst according (o one of the preceding claims, in which the pores with a diameter › 25 nm occupy a volume that is less than 10% of the total pore volume (VPT), the pores with a diameter greater than 16 nm occupy 1 to 14% of the VPT; and the pores with a diameter of JO-16 nm occupy at least 60% of the VPT, whereby the remainder corresponds to pores with a diameter that is less than 10 nm.
4. Catalyst according to one of the preceding claims that is obtained by mixing zeolite Y with a moist alumina gel, followed by extrusion and calcination at 250-600"C.
5. Process for hydrocracking, with a catalyst according to one of the preceding claims, at a pressure of al least ?. MPa, and a temperature of at least 23O"C, a quantity of hydrogen of at least 100 Nl H2/l of feedstock and an hourly volume rate of 0.1-10 h'1.
6. Process according to claim 5, in which the pressure is 2-12 MPa, the temperature is 3O(M8OV, and the conversion is less than 55%.
7. Process according to claim (\ in which the pressure is 7.5 11 MPa.
8. Process according to claim 6, in which the pressure is R- II MPa.
0. Process according to claim 5. in which the pressure is at least 8.5 MPa, the temperature is 300-43O"C, and the conversion is at least 55%.

10. Process according (o one of claims 5 to 8, in which the feedstock is hydrotreatcd
prior lo hydrocracking.
11. Process according to claim 9, in which the hydrolrealmenl catalyst contains a( least
one niclal from group VJIT, al least one metal from group VIB and phosphorus, and optionally
boron.
12. Catalyst substantially as herelnabove described and
exemplified.
13# Catalyst and process for hydrocracking substantially
as herelnabove described and exemplified,
t t
Dated this the 16th day of October 1998

Documents:

2340-mas-1998-abstract.pdf

2340-mas-1998-claims filed.pdf

2340-mas-1998-claims granted.pdf

2340-mas-1998-correspondnece-others.pdf

2340-mas-1998-correspondnece-po.pdf

2340-mas-1998-description(complete)filed.pdf

2340-mas-1998-description(complete)granted.pdf

2340-mas-1998-form 1.pdf

2340-mas-1998-form 26.pdf

2340-mas-1998-form 3.pdf

2340-mas-1998-form 4.pdf

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Patent Number

212451

Indian Patent Application Number

2340/MAS/1998

PG Journal Number

07/2008

Publication Date

15-Feb-2008

Grant Date

03-Dec-2007

Date of Filing

16-Oct-1998

Name of Patentee

INSTITUT FRANCAIS DU PETROLE

Applicant Address

1 ET 4, AVENUE DE BOIS-PREAU 92852 RUESIL-MALMAISON CEDEX,

Inventors:

#	Inventor's Name	Inventor's Address
1	GEROGE-MARCHAL NATHALIE	8, RUE GEOFFREY SAINT HILAIRE 75005 PARIS,
2	MIGNARD SAMUEL	22, AVENUE GUY DE MAUPASSANT, 78400 CHATOU,
3	KASZTELAN SLAVIK	27, RUE RAYMOND QUENEAU 92500 RUEIL MALMAISON,

PCT International Classification Number

C 10 G 11/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	97/13.128	1997-10-20	France