MXPA97006566A - Catalytic compositions and their use in hydrocarbon conversion processes - Google Patents

Abstract

The present invention provides a catalytic composition, and a hydrocarbon conversion process that utilizes it. Comprising a molecular sieve having substantially the same structure as the zeolite and a constant of unitary cells or mesh (ao) less than or equal to 2.495 nm and a volume of mesoporous, contained in the mesopores having a diameter in the range from 2 to 60 nm, of at least 0.05 ml / g, and a binder substance, wherein the ratio between the unit cell constant (ao) and the mesoporous volume is defined as in the table (

Description

CATALYTIC COMPOSITIONS AND THEIR USE IN HYDROCARBON CONVERSION PROCESSES The present invention relates to catalytic compositions and hydrocarbon conversion processes that use them. Many hydrocarbon conversion processes in the petroleum industry are carried out using catalytic compositions based on zeolite Y. Zeolite Y has very frequently been subjected to certain steps of the stabilization and / or dealumination process during its preparation which results in the same, that has a constant of unitary cells or mesh, reduced (a0) and a molar ratio of silica to alumina, increased. These stabilized zeolites, as well as the zeolite Y as synthesized, possess relatively few pores that are larger than 2 nanometers (nm) in diameter and therefore have a limited mesoporum volume (a mesoporum typically has a diameter in the range). from 2 to 60 nm). U.S. Patent Application No. 5 354 452 describes a process in which the ultra-stable Y zeolites having a relation REF: 25548 mole of silica to alumina from 6 to 20, and super-stable Y zeolites having a mole ratio of silica to alumina of at least 18 and a unit cell or mesh (a0) constant of 2420 to 2448 nm (24.20 a 24.48 A) are subjected to a hydrothermal treatment with steam at 538 to 649 ° C (1000 to 1200 ° F) followed by an acid treatment at 60 to 93 ° C (140 to 200 ° F). The hydrothermally treated zeolite is characterized by a unit cell or mesh (a0) constant typically in the range of 2/427 to 2439 nm (24.27 to 24.39 A), a secondary pore volume contained in mesopores having a diameter in the range from 10 to 60 nm (100 to 600 Á) from 0.09 to 0.13 ml / g, and a total pore volume of 0.16 to 0.20 ml / g, while the hydrothermally treated, acidified zeolite is characterized by a unit cell constant ( a0) typically in the range of 2,405 to 2,418 nm (24.05 to 24.18 Á), a secondary pore volume contained in mesopores having a diameter in the range of 10 to 60 nm (100 to 600 Á) from 0.11 to 0.14 ml / g, and a total pore volume of 0.16 to 0.25 ml / g. Now, it has been found possible, surprisingly, to prepare catalytic compositions containing certain 'Y-type' molecular sieves with even higher mesoporous volumes which can be advantageously used in the conversion of hydrocarbon oils, for example, by catalytic thermo-disintegration or hydrodisintegration, to produce desirable products in greater yield and selectivity. According to the present invention, there is provided a catalytic composition comprising a molecular sieve having substantially the same structure as zeolite Y, a unit cell constant (a0) of less than or equal to 2485 nm and a volume of mesoporous, contained in mesopores having a diameter in the range of 2 to 60 nm, of at least 0.05 ml / g, and a binder substance, wherein the ratio between the unit cell constant (a0) and the mesoporous volume is defined as follows: Unitary cell constant (nm) Mesoporum volume (ml / g) 2.485 > aQ > 2.460 > 0.05 2.460 > a0 > 2,450 > 0.18 2.450 > a0 > 2.427 > 0.23 2.427 > a0 '> 0.26 The molecular sieve used in the catalytic compositions of the invention is defined as having substantially the same structure as zeolite Y. This definition is intended to encompass molecular sieves derived not only from zeolite Y per se but also from zeolites Y modified in which a proportion of the aluminum ions have been replaced by other metal ions such as iron, titanium, gallium, tin, chromium or scandium ions but whose structures are not significantly different from that of the zeolite Y, as can be determined by X-ray crystallography. Examples of Y zeolites modified with iron and / or titaniumsuitable are those described in U.S. Patent Nos. 5 176 817 and 5 271 761, and examples of suitable Y chromium and / or tin modified zeolites are those described in European Patent Application No. 321 177. However, , the molecular sieve used in the catalytic compositions of the invention are preferably derived from a Y zeolite per se, for example as described in Zeolite Molecular Sieves (Structure, Chemistry and Use) by Donald. Breck published by Robert E. Krieger Publishing Company Inc., 1984; and U.S. Patent Nos. 3,506,400, 3,671,191, 3,808,326, 3,929,672 and 5,242,677. The molecular sieve used in the present compositions has a unit cell or mesh (a0) constant less than or equal to (<) 2,485 nm (24.85 Á), preferably less than or equal to (<) 2,460 nm (24.60 Á), for example in the range of 2,427 to 2,485 nm (24.27 to 24.85 Á), preferably in the range of 2,427 to 2,460 nm (24.27 to 24.60 Á). Advantageously, the molecular sieve has a unit cell constant (a0) above 2440 nm (24.40 Á), for example in the range of 2,427 to 2,440 nm (24.27 to 24.40 Á), or a unit cell constant (a0). ) in the range of 2,450 to 2,460 nm (24.50 to 24.60 Á). The mesoporous volume of the molecular sieve, as contained in mesopores having a diameter in the range of 2 to 60 nm, will vary depending on the unit cell constant (a0) The relationship between the unit cell constant (a0) and the mesoporum volume is as follows: Cell Constant Unitary Mesoporum Volume (nm) (ml / g) 2.485 > aQ > 2.460 > 0.05 2.460 > aQ > 2.450 = 0.18 2.450 > as > 2.427 > 0.23 2.427 = a0 > 0.26 The molecular sieve can have a mesoporum volume of up to 0.8 ml / g, for example in the range of 0.05, preferably 0.18, more preferably 0.23, even more preferably 0.26, advantageously 0.3. and particularly 0.4 ml / g, up to 0.6 ml / g, especially up to 0.8 ml / g. Molecular sieves useful in the present invention can be conveniently prepared by a hydrothermal treatment in which the Y zeolite or the Y zeolite modified as described above is hydrothermally contacted with an aqueous solution having one or more dissolved therein. salts, acids, bases and / or organic compounds soluble in water at a temperature above the boiling point of the solution at an atmospheric temperature for a period of time sufficient to provide the zeolite with an increased mesoporum volume in mesopores having a diameter in the range of 2 to 60 nm. At the termination of the hydrothermal treatment, p. The product is separated, washed (using deionized water or an acid, for example nitric acid, solution) and recovered. The product obtained by this treatment will generally have a unit cell size (unit cell constant) and a molar ratio of silica to alumina similar to that of the starting zeolite. However, if desired, the product may be subjected to additional stabilization and / or dealumination treatments such as these are well known in the art in order to change the unit cell size and / or the molar ratio of silica to alumina. In the preparation of the hydrothermal, aqueous treatment solution, examples of salts that may be used include ammonium, alkali metal (for example sodium and potassium) and alkaline earth metal salts of organic and inorganic acids, strong and weak, (e.g. nitric and hydrochloric acids); examples of acids that can be used include strong organic acids such as nitric acid and hydrochloric acid as well as also weak organic acids such as acetic acid and formic acid; base examples that may be used include organic bases such as ammonium, alkali metal and alkaline earth metal hydroxides in conjunction with organic bases such as quaternary ammonium hydroxides, amine complexes and pyridinium salts; and salts of water-soluble organic compounds that can be used include alcohols of 1 to 6 carbon atoms and ethers. The concentration and amount of the aqueous solution in contact with the initial zeolite is adjusted to provide at least 0.1 parts by weight (pbw) of dissolved solute per part by weight of zeolite, on a dry weight basis. The pH of the hydrothermal, aqueous treatment solution may vary between 3 and 10 and depending on the zeolite, aqueous may vary between 3 and 10 and depending on the Y (modified) zeolite to be treated, a high pH or one may be preferred low. In this way, if the starting zeolite has a unit cell constant (a0) of 2,450 to 2,460 nm (2,460 nm >; aQ = 2450 nm), it is desirable to maintain or adjust the pH of the solution before contacting it with the zeolite at a value of 4.5 to 8; if the starting zeolite has a unit cell constant (a0) of > 2.427 a < 2450 nm (2450 nm> a0> 2.427 nm), then the pH of the solution should be maintained or adjusted desirably to a value of 3 to 8; and if the starting zeolite has a unit cell constant (a0) less than or equal to 2.427 nm (2.427 nm> a0), then the pH of the solution should be maintained or set desirably to a value of 3 to 7. The temperature of the hydrothermal treatment must be above the atmospheric boiling point of the aqueous solution. Although temperatures up to 400 ° C can be used, a temperature in the range of 110 or 115 to 250 ° C is usually satisfactory. Good results can be obtained by using a temperature in the range of 140 to 200 ° C. The treatment time is inversely related to the treatment temperature. In this way, at a higher temperature, a shorter time will be required to effect a given increase in the volume of the mesoporum. The treatment time can vary between 5 minutes and 24 hours but usually it is in the range of 2 to 12 hours. The duration of the hydrothermal treatment and the temperature at which it is applied must be such as to provide a volume of mesoporous in the final product which is at least 5%, preferably at least 10%, larger than the volume of the mesoporous start zeolite. A preferred molecular sieve for use in the catalytic composition of the present invention is one prepared by a process comprising contacting a Y (modified) zeolite as hereinabove defined hydrothermally with an aqueous solution having dissolved therein a or more salts, acids, bases and / or organic compounds soluble in water at a temperature above the atmospheric boiling point of the solution, followed by separation and washing with an acid solution. The acid solution can be an aqueous solution of one or more acids selected from organic and inorganic acids, for example nitric acid, hydrochloric acid, acetic acid, formic acid and citric acid. Compared to using water (deionized), washing with an acid solution has the advantage of further increasing the selectivity of the middle distillate of the increased mesoporous molecular sieve. As a binder in the catalyst compositions of the invention, it is convenient to use an organic oxide or a mixture of two or more such oxides. The binder substance can be amorphous or crystalline. Examples of suitable binder substances include alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria and mixture thereof. A preferred binder for use is alumina, or alumina in combination with a silica-alumina dispersion in an alumina matrix, particularly a gamma alumina matrix. The catalyst composition of the present invention preferably contains from 1 to 80% by weight (percent by weight) of the molecular sieve and from 20 to 99% by weight of binder, based on the total dry weight of the molecular sieve and the binder substance. More preferably, the catalyst composition contains from 10 to 70% by weight of the molecular sieve and from 30 to 90% by weight of binder, in particular from 20 to 50% by weight of the molecular sieve and from 50 to 80% by weight. weight of binder substance, based on the total dry weight of the molecular sieve and the binder substance. Depending on the application of the present catalytic compositions (for example in hydrodegradation), these may additionally comprise at least one hydrogenation component. Examples of hydrogenation components useful in the present invention include Group 6B (e.g., molybdenum and tungsten) and Group 8 metals (e.g., cobalt., nickel, iridium, platinum and palladium), their oxides and sulfides. The catalyst composition preferably contains at least two hydrogenation components, for example a molybdenum and / or tungsten component in combination with a cobalt and / or nickel component. Particularly preferred combinations are nickel / tungsten and nickel / molybdenum. Very advantageous results are obtained when metals are used in the sulfide form. The catalyst composition may contain up to 50 parts by weight of the hydrogenation component, catalyzed as a metal per 100 parts by weight of the total catalyst composition.

For example, the catalyst composition may contain from 2 to 40, more preferably from 5 to 25 and especially from 10 to 20, parts by weight of the metal (s) from group 6 and / or from 0.05 to 10, more preferably from 5 to 25 and especially from 10 to 20 parts by weight of the metal (s) of Group 6 and / or from 0.05 to 10, more preferably from 0.5 to 8 and advantageously from 2 to 5. to 6, parts by weight of the metal (s) of group 8, calculated as metal per 100 parts by weight of the total catalytic composition. The present catalyst compositions can be prepared according to techniques conventional in the art. A conventional method for preparing a catalyst composition for use in thermo-disintegration comprises mixing binder material with water to form a slurry or liquid colloid, adjusting the pH of the slurry or liquid colloid as appropriate and then adding a molecular sieve powder as defined above in conjunction with additional water to obtain a slurry or liquid colloid with a desired solids concentration. The slurry or liquid colloid is then spray dried. The spray-dried particles formed in this way can be used directly or can be calcined before use. A method for preparing a catalyst composition for use in hydrodisintegration comprises grinding or mixing a molecular sieve as defined above and a binder in the presence of water and optionally a peptizing agent, extruding the resulting mixture into pellets and calcining the pellets. The pellets thus obtained are then impregnated with one or more solutions of metal salts of group 6B and / or group 8 and calcined again. Alternatively, the molecular sieve and the binder can be co-milled in the presence of one or more solutions of the metal salts of group 6B and / or group 8 and optionally a peptizing agent. And the mixture thus formed is extruded into pellets. The pellets can then be calcined. The present invention further provides a process for converting a hydrocarbonaceous raw material into lower boiling materials comprising contacting the raw material at elevated temperature with a catalytic composition according to the invention. The hydrocarbonaceous raw materials useful in the present process can vary within a wide range of boiling point. These include lighter fractions such as kerosene fractions, as well as heavier fractions such as gas oils, coker gas oils, vacuum gas oils, deasphalted oils, long and short residues, catalytically thermo-disintegrated cycle oils, thermally or catalytically disintegrated gas oils and crude minerals combined, optionally originating from asphalt sands, oil from shale butiminoso, processes of improvement or enrichment of waste or biomass. It is also possible to use combinations of various hydrocarbon oils. The raw materials in general will comprise hydrocarbons having a boiling point of at least 330 ° C. In a preferred embodiment of the invention, at least 50% by weight of the raw material has a boiling point above 370 ° C. The raw material can have a nitrogen content of up to 5000 ppmw (parts per million by weight) and a sulfur content of up to 6% by weight. Typically, the nitrogen contents are in the range of 250 to 2000 ppmw and the sulfur contents are in the range of 0.2 to 5% by weight. It is possible and sometimes it may be desirable to subject part or all of the raw material to a pretreatment, for example, hydrodesnitrogenation, hydrodesulfurization or hydrodemetalization, methods for which they are known in the art. If the process is carried out under conditions of catalytic thermal disintegration (ie in the absence of hydrogen addition), the process is conveniently carried out in a catalytic bed that moves up or down, for example in the manner of the processes of the Termal Disintegration Catalytic Termoformación, conventional (TCC) or Fluidized Catalytic Termonodesintegración (FCC). The process conditions are preferably a reaction temperature in the range of 400 to 900 ° C, more preferably 450 to 800 ° C and especially 500 to 650 ° C.; a total pressure of 1 to 10 bar (1 x 105 to 1 x 106 Pa), in particular 1 to 7.5 bar (1 x 105 to 7.5 x 105 Pa); a weight ratio of catalyst composition / raw material (kg / kg) in the range of 5 to 150, especially 20 to 100; and a contact time between the catalytic composition and the raw material from 0.1 to 10 seconds, advantageously from 1 to 6 seconds. However, the process according to the present invention is preferably carried out under hydrogenation conditions, that is, under conditions of catalytic hydrodisintegration, for example conditions of hydrodisintegration of waste. In this way, the reaction temperature is preferably in the range of 250 to 500 ° C, more preferably 300 to 450 ° C and especially 350 to 450 ° C. The total pressure is preferably in the range of 50 to 300 bar (5 x 106 to 3 x 107 Pa), more preferably 75 to 250 bar (7.5 x 106 to 2.5 x 107 Pa) and even more preferably from 100 to 200 bars (1 x 107 to 2 x 107 to 2 x 107 Pa). The hydrogen partial pressure is preferably in the range of 25 to 250 bar (2.5 x 106 to 2.5 x 107 Pa), more preferably 50 to 200 bar (5 x 106 to 2 x 107 Pa) and even in more preferably from 60 to 180 bar (6 x 106 to 1.8 x 107 Pa). A space velocity in the range of 0.05 to 10 kg of raw material per liter of catalyst composition per hour (kg I "1 h" 1) is conventionally used. Preferably the space velocity is in the range of 0.1 to 8, particularly 0.1 to 5, kg, l-1.h-1. In addition, the total gas ratios (gas / feed ratios) in the range of 100 to 5000 Nl / kg are conveniently used. Preferably, the proportion of total gas used is in the range of 250 to 2500 Nl / kg. The present invention will be further understood from the following illustrative examples in which the constant of unit cells or mesh (ac) was determined according to the standard test method ASTM D 3942-80, the relative crystallinity (%) was determined at comparing the X-ray crystallography data for the mesoporous Y-zeolite Y with those for a corresponding normal Y-zeolite of the prior art, and the surface properties (ie surface area (m2 / g) and mesoporum volume ( ml / g)) were determined using nitrogen adsorption at -196 ° C (77 ° K).

Example 1 (i) Preparation of the molecular sieve with increased mesoporum volume A very ultrastable Y zeolite (VUSY) having a molar ratio of silica to alumina of 7.4, a unit cell constant (a0) of 2433 nm (24.33 A), a surface area of 691 m2 / g and a volume of mesopor 0.177 ml / g was added to an aqueous solution of 4N ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5. . The resulting slurry was placed in a stirred 2 liter autoclave and the slurry was heated at 150 ° C for 12 hours. After cooling, the contents of the autoclave were filtered to produce a molecular sieve having substantially the same structure as zeolite Y which, after 2 washes of three hours at 93 ° C with a solution of nitric acid (2 hydrogen ions (H +) milliequivalents (meq) per gram of zeolite) and drying at 110 ° C, it was found that there is a molar ratio of silica to alumina of 13.2, a unit cell constant (a0) of 2,429 nm (24.29 Á) , a relative crystallinity of 87%, a surface area of 756 m2 / g and a mesoporum volume of 0.322 ml / g. (ii) Preparation of a catalytic composition To a mixture consisting of a molecular sieve prepared as described in (i) above (5 g), silica-alumina 55/45, amorphous (104 g) and precipitated alumina of high microporosity (50 g) was added water (145 g). g) and acetic acid (96%, 4 g). The mixture was first milled and then extruded, after the addition of an extrusion aid, into pellets of cylindrical shape. The pellets were dried for 2 hours at 120 ° C and calcined subsequently for 2 hours at 530 ° C. The pellets thus obtained had a circular end surface diameter of 1.6 mm and a pore volume of water of 0.72 ml / g. The pellets comprised 4% by weight of the molecular sieve and 96% by weight of binder (66% by weight of silica-alumina and 30% by weight but of alumina), on a dry weight basis. 10.07 g of an aqueous solution of nickel nitrate (14% by weight of nickel) and 16.83 g of an aqueous solution of ammonium metatungstate (398.8% by weight of tungsten) were combined and the resulting nickel / tungsten solution was diluted with Water (18 g) and homogenized. 25.0 g of the pellets were impregnated with the homogenized nickel / tungsten solution, dried for 1 hour at 120 ° C and finally calcined for 2 hours at 500 ° C.

The pellets contained 3.9% by weight of nickel and 18. 9% by weight of tungsten, based on the total composition.

Example 2 (i) Preparation of a molecular sieve with increased mesoporum volume A highly ultrastable Y zeolite (VUSY) having a molar ratio of silica to alumina of 8.4, a unit cell constant (a0) of 2434 nm (24.34 A), a surface area of 727 m2 / g and a volume of mesoporium of 0.180 ml / g was added to an aqueous solution of 4N ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of the Y zeolite was 1.5. The resulting slurry was placed in a stirred 2 liter autoclave and the slurry was heated at 200 ° C for 6 hours. After cooling, the contents of the autoclave were filtered to produce a molecular sieve having substantially the same structure as zeolite Y which, after two 3 hour washes at 93 ° C, is a solution of nitric acid (two hydrogen ions (H +) milliequivalents (meq) per gram of zeolite) and drying at 110 ° C, it was found that there is a molar ratio of silica to alumina of 10.0, a constant of unit cells (as) of 2.427 nm (24.27 Á), a relative crystallinity of 71%, a surface area of 605 m2 / g and a mesoporum volume of 0.423 ml / g. (ii) Preparation of a catalytic composition In the manner described in Example 1 (ii), a molecular sieve prepared as described in (i) above (5 g) was combined with amorphous silica-alumina 55-45 (82 g) and high microporous precipitated alumina (40 g) to form pellets in cylindrical form which, after drying and calcination, had a circular end surface diameter of 1.2 mm and a pore volume of water of 0.717 ml / g. The pellets comprised 5% by weight of the molecular sieve and 95% by weight of the binder (65% by weight of silica-alumina and 30% by weight of alumina), on a dry weight basis. 8.34 g of an aqueous solution of nickel nitrate (14.1% by weight of nickel) and 8.29 g of an aqueous solution of ammonium metatungstate (67.3% by weight of tungsten) were combined and the resulting nickel / tungsten solution was diluted with water (7.2 g) and homogenized. 25.0 g of the pellets were impregnated with the homogenized nickel / tungsten solution, dried for 1 hour at 120 ° C and finally calcined for 2 hours at 500 ° C. The pellets contained 3.9% by weight of nickel and 18.9% by weight of tungsten, based on the total composition.

Example 3 (i) Preparation of a molecular sieve with increased mesoporum volume A very ultrastable Y zeolite (VUSY) having a molar ratio of silica to alumina of 7.4, a unit cell constant (a0) of 2433 nm (24.33 A), a surface area of 641 m2 / g and a volume of mesoporium of 0.177 ml / g was added to an aqueous solution of 4N ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5 . The resulting slurry was placed in a stirred two-liter autoclave and the slurry was heated at 180 ° C for 12 hours. After cooling, the contents of the autoclave were filtered to produce a molecular sieve having substantially the same structure as zeolite Y which, after two washes of three hours at 93 ° C with a solution of nitric acid (2 hydrogen ions (H +) milliequivalents (meq) per gram of zeolite) and drying at 110 ° C, it was found that there is a molar ratio of silica to alumina of 10.2, a unit cell constant (a0) of 2,428 nm (24.28 Á) , a relative crystallinity of 57%, a surface area of 519 m2 / g and a mesoporum volume of 0.458 ml / g. (ii) Preparation of a catalytic composition In the manner described in Example 1 (ii), a molecular sieve prepared as described in (i) above (7 g) was combined with amorphous silica-alumina 55/45 (125 g) and high-porous precipitated alumina. (60 g) to form cylindrical pellets which, after drying and calcination, had a circular end surface diameter of 1.6 mm and a water pore volume of 0.792 ml / g. The pellets comprised 4% by weight of the molecular sieve and 96% by weight of the binder (65% by weight of silica-alumina and 30% by weight of alumina), on a dry weight basis. 13.12 g of an aqueous solution of nickel nitrate (14.1% by weight of nickel) and 12.94 g of an aqueous solution of ammonium metatungstate (67.3% by weight of tungsten) were combined and the resulting nickel / tungsten solution was diluted with water (13.69 g) and homogenized. 32.53 g of the pellets were impregnated with the homogenized nickel / tungsten solution, dried for 1 hour at 120 ° C and finally calcined for 2 hours at 500 ° C. The pellets contained 3.9% by weight of nickel and 18.9% by weight of tungsten, based on the total composition.

Example 4 Hydro-Disintegration Experiment Each of the catalytic compositions of Examples 1 to 3 was evaluated by the selectivity of middle distillates in a hydrodisintegration performance test. The test involved contacting a hydrocarbonaceous raw material (a vacuum, heavy, hydrotreated gas oil) with the catalytic compositions (conventionally presulphized) in a single pass operation under the following operating conditions: a space velocity of 1.5 kg. of gas oil per liter of catalytic composition per hour (kq., l '1, h'1), a partial pressure of hydrogen sulfide of 5.5 bar (5.5 x 1Q5 Pa), an ammonium partial pressure of 0.075 bar (7.5 x 103 Pa), a pressure of 140 bar (14 x 106 Pa) and a gas ratio / feeding of 1500 Nl / kg. Vacuum, heavy, hydrotreated gas oil had the following properties: "Carbon content 86.5% by weight Hydrogen content 13.4% by weight Sulfur content 0.007% by weight Nitrogen content 16.1 ppmw Density (70/4) 0.8493 g / ml Kinematic viscosity at 100 ° C 8.81 mm2 / s (cS) Initial boiling point 345 ° C 10% by weight boiling point 402 ° C 20% by weight boiling point 423 ° C 30% by weight boiling point 441 ° C 40% by weight boiling point 456 ° C 50% by weight boiling point 472 ° C 60% by weight boiling point 490 ° C 70% by weight boiling point 508 ° C 80% by weight boiling point 532 ° C 90% by weight boiling point 564 ° C Final boiling point 741 ° C The performance of each catalyst composition was evaluated at 65% by weight of net conversion of the feed components with boiling point at 370 ° C. The selectivities for the middle distillates (ie, the boiling point of the fraction in the temperature range of 150 to 370 ° C) shown by the catalyst compositions of Examples 1 to 3 are given in the following Table 1.

Table 1 Catalytic composition Selectivity of Example medium distillates at 65% by weight of net conversion (% w / w) 1 70.5 2 72.5 3 72.5 As can be seen from the Table 1 above, the catalytic compositions of Examples 1 to 3 according to the invention show high selectivity of middle distillates.

Example 5 (i) Preparation of a molecular sieve with increased mesoporum volume A very ultra-stable Y-zeolite (VUSY) having a molar ratio of silica to alumina of 7.9, a unit cell constant (as) of 2431 nm (24.31 A) , a surface area of 550 m2 / g and a mesoporum volume of 0.141 ml / g was added to an aqueous solution of 4N ammonium nitrate (NH4N03) in an amount such that, on a dry weight basis, the ratio of the number grams of ammonium nitrate to the number of grams of zeolite Y was 1.5. The resulting slurry was placed in a stirred two-liter autoclave and the slurry was heated at 200 ° C for 6 hours. After cooling, the contents of the autoclave were filtered to produce a molecular sieve having substantially the same structure as zeolite Y which, after two washes of three hours at 93 ° C with demineralized water and drying at 100 ° C, it was found that there is a silica to alumina molar ratio of 8.5, a unit cell constant (a0) of 2,432 nm (24.32 Á), a relative crystallinity of 69%, a surface area of 481 m2 / g and a Mesoporum volume of 0.41 ml / g. (ii) Preparation of a catalytic composition In the manner described in Example 1 (ii), a molecular sieve prepared as described in (i) above (22.3 g) was combined with precipitated alumina of high microporosity (110.0 g) to form pellets in cylindrical form which, after drying and calcining, had a circular end surface diameter of 1.6 mm and a water pore volume of 0.642 ml / g. The pellets comprised 20% by weight of the molecular sieve and 80% by weight of the alumina binder substance, on a dry weight basis. 8.92 g of an aqueous solution of nickel nitrate (13.9% by weight of nickel) and 7.85 g of an aqueous solution of ammonium metatungstate (67.3% by weight of tungsten) were combined and the resulting nickel / tungsten solution was diluted with water (6.6 g) and homogenized. 22.76 g of the pellets were impregnated with the homogenized nickel / tungsten solution, dried for 1 hour at 120 ° C and finally calcined for 2 hours at 500 ° C. The pellets contained 4.0% by weight of nickel and 17.0% by weight of tungsten, based on the total composition.

Example 6 Hydrodegradation experiment The catalytic composition of Example 5, which is a catalytic composition according to the present invention, was evaluated by the selectivity of middle distillates in a hydrodisintegration performance test. The test involved contacting a hydrocarbonaceous raw material (a vacuum, heavy, hydrotreated gas oil) with a catalytic composition of Example 5 (conventionally presulphized) in a single pass operation under the following operating conditions: a space velocity 1.5 kg of gas oil per liter of catalytic composition per hour (kg I-1 .1), a partial pressure of hydrogen sulphide of 5.5 bar (5.5 x 105 Pa), an ammonium partial pressure of 0.165 bar ( 1.65 x 104 Pa), a pressure of 140 bar (14 x 106 Pa) and a gas / feed ratio of 1500 Nl / kg. Vacuum, heavy, hydrotreated gas oil had the following properties: Carbon content: 86.7% by weight Hydrogen content: 13.3% by weight Sulfur content 0.007% by weight Nitrogen content 19.0 ppmw Density (70/4) 0.8447 g / ml Initial boiling point 349 ° C 10% by weight boiling point 390 ° C 20% Weight boiling point 410 ° C 30 wt.% Boiling point 427 ° C 40 wt.% Boiling point 444 ° C 50 wt.% Boiling point 461 ° C 60 wt.% Boiling point 478 ° C 70% weight boiling point 498 ° C 80% by weight boiling point 523 ° C 90% by weight boiling point 554 ° C Final boiling point 620 ° C The performance of the catalyst composition was evaluated at 65% by weight of net conversion of the feed components with boiling point at 370 ° C. The selectivity for the middle distillates (ie the boiling point of the fraction in the temperature range of 150 to 370 ° C) shown by the catalytic composition of Example 5 was found to be high at 69.0% w / w.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, it is claimed as property contained in the following: It is noted that in relation to this date, the best method known by the applicant to implement the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (16)

1. A catalytic composition, characterized in that it comprises a molecular sieve having substantially the same structure as the zeolite Y, a constant of unitary cells or mesh (a0) less than or equal to 2.485 nm and a volume of mesoporum, contained in the mesopores having a diameter in the range of 2 to 6 nm of at least 0.05 ml / g, and a binder substance, wherein the ratio between the unit cell or mesh constant (a0) and the mesoporous volume is defined as follows: Cells Unitary Mesoporum Volume (nm) (ml / g) 2.485 > a0 > 2.460 > 0.05 2.460 > a0 = 2.450 > 0.18 2.450 > aQ > 2.427 > 0.23 2.427 > a0 > 0.26

2. A catalytic composition according to claim 1, characterized in that the molecular weight sieve is derived from a Y zeolite.

3. A catalytic composition according to claim 1 or claim 2, characterized in that the molecular sieve has a unit cell or mesh (a0) constant less than or equal to 2460 nm.

4. A catalytic composition according to any of claims 1 to 3, characterized in that the molecular sieve has a mesoporum volume of up to 0.8 ml / g.

5. A catalytic composition according to any of the preceding claims, characterized in that the molecular sieve has a mesoporous volume in the range of 0.3 to 0.8 ml / g.

6. A catalytic composition according to any of the preceding claims, characterized in that the molecular sieve has a mesoporous volume in the range of 0.4 to 0.6 ml / g.

7. A catalytic composition according to any of the preceding claims, characterized in that the molecular sieve has been prepared by a process comprising contacting a Y (modified) zeolite hydrothermally with an aqueous solution having one or more salts dissolved therein, acids, bases and / or organic compounds soluble in water at a temperature above the atmospheric boiling point of the solution, followed by separation and washing with an acid solution,

8. A catalytic composition according to any of the preceding claims, characterized in that the binder substance is an inorganic oxide.

9. A catalyst composition according to any of the preceding claims, characterized in that the binder substance is selected from alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria and mixtures thereof.

10. A catalytic composition according to any of the preceding claims, characterized in that it also comprises at least one hydrogenation component.

11. A catalytic composition according to claim 10, characterized in that at least one hydrogenation component is selected from Group 6B and Group 8 metals, their oxides and sulfides.

12. A. catalytic composition according to claim 10 or claim 11, characterized in that at least one hydrogenation component is selected from molybdenum, tungsten, cobalt, nickel, platinum and palladium, their oxides and sulfides.

13. A process for converting a hydrocarbonaceous raw material into lower boiling materials, characterized in that it comprises contacting the raw material at an elevated temperature with a catalytic composition as defined in any of the preceding claims.

14. A process according to claim 13, characterized in that the raw material is contacted with a catalytic composition as defined in any of claims 10 to 12 under hydrogenation conditions.

15. A process according to claim 14, characterized in that it is carried out at a temperature in the range of 250 to 500 ° C and a total pressure in the range of 50 to 300 bar (5 x 106 to 3 x 107).

16. A process according to claim 14 or claim 15, characterized in that a space velocity in the range of 0.05 to 10 kg of raw material per liter of catalyst composition per hour (kg.l ") is used.