MXPA99007729A - Process for the preparation of a catalyst composition - Google Patents

Abstract

The present invention provides a process for the preparation of a catalyst composition which comprises, as first cracking component, a zeolite beta with a silica to alumina molar ratio of at least 20 comprising crystals less than 100 nm in size, and a second cracking component selected from (i) crystalline molecular sieves having pores with diameters greater than 0.6 nm, and (ii) clays, the process comprising the steps of:(i) preparing a mixture comprising the first cracking component and the second cracking component, the first cracking component being in the form of a sol;(ii) extruding the mixture into catalyst extrudates;and (iii) calcining the extrudates.

Description

PROCESS FOR THE PREPARATION OF A CATALYST COMPOSITION Field of Invention The present invention relates to a process for the preparation of a catalyst composition.

Background of the Invention Of the many conversion processes known in the art of refining, hydrocracking has assumed greater importance over the years since the refiner offers the flexibility of the product combined with the quality of the product.

Considerable effort has been devoted to the development of hydrocracking catalysts that combine high cracking activity with a low tendency towards excessive cracking of light products and, in particular, less valuable C? -C3 gaseous derivatives.

Ref: 030971 Frequently, kerosene or gas oil (middle distillates) are the desired products of a hydrocracking process. However, hydrocracking catalysts with high selectivity towards medium distillates tend to have low cracking activity. Such catalysts are characteristically based on a simple, active cracking component such as alumino-silicate, especially a zeolite Y component.

It is known, for example from the patent E.U.A. No. 5,279,726 and EP-B-559,646, the formation of compounds of two to three different types, one Y zeolite and one beta zeolite for use in the hydrocarbon.

More specifically, in the U.S. Patent. No. 5,279,726 discloses a hydrocracking catalyst having high activity and selectivity for gasoline, which comprises a hydrogenation component in a catalyst support comprising beta zeolite and a Y zeolite having a cell unit size above 2.440. nm (24.40 Angstroms.); in general and preferably the zeolites will be in combination with a porous inorganic refractory oxide such as alumina.

The beta zeolite used in the catalyst support has a molar ratio of silica to alumina of at least 10 to 100, but preferably not more than 40, and even more preferably in the range of 20 to 30. Preferably, the beta zeolite has a glass size from 0.1 to 0.7 microns (100 to 700 nm), a surface area of 500 to 800 m "/ g and an absorption capacity of cyclohexane from 15 to 25 g / 100 g.

Preferably, the Y zeolite used in the catalyst support has a cell unit size between 2,445 and 2,464 nm (24.25 and 24.64 Angstroms) and, typically, an absorption capacity for water vapor at 25 ° C and a p / po value of 0.1 of at least 15% by weight, as applied by zeolites LZY-82 and LZY-84.

The Patent E.U.A. No. 5,279,726 contains a simple example that details the preparation and testing of four hydrocracking catalysts numbered one (1), two (2), three (3) and four (4). All catalysts contain the same amount and type of hydrogenated components but differ in their catalyst supports. Catalyst 1 contains a catalyst support of 80% by weight beta zeolite (molar ratio silica to alumina 26) and 20% by weight alumina; Catalyst 2 contains a catalyst support of 40% by weight beta zeolite (silica to alumina molar ratio 26), 40% by weight zeolite LZ-10 (silica to alumina molar ratio of 5.2, cell unit size 2,430 nm) and 20% by weight alumina; Catalyst 3 contains a catalyst support of 40% by weight beta zeolite (silica to alumina molar ratio 26); 40% by weight LZY-82 zeolite (silica to alumina molar ratio 5.7, cell unit size 2,455 nm) and 20% by weight alumina; and Catalyst 4 contains a catalyst support of 80% by weight zeolite LZY-82 (silica to alumina molar ratio 5.7, cell unit size 2,455 nm) and 20% by weight alum. Catalysts 1, 2 and 4 were catalyzed is comparative while Catalyst 3 was a catalyst according to the invention.

When the hydrocracking performances of the catalysts were evaluated under the second-stage serial flow conditions (referred to in US Patent 5,279,726 as a first stage simulation or ammonia-rich conditions), the results in Table II, column 14 shows that Catalyst 3 of the invention yields more gasoline than comparative Catalyst 4 (a commercial gasoline hydrocarbon catalyst) with a slight reduction in the amount of gaseous derivative C? -C3.

Similarly, EP-B-559,646 discloses a hydrocracking catalyst having high activity and selectivity for gasoline comprising a hydrogenation component in a catalyst support composed of beta zeolite and a Y-dealuminated zeolite having a global molar ratio silica to alumina greater than 6.0. The support may also contain an inorganic, porous refractory oxide such as alumina or silica-a-alumina.

The beta zeo 111 a used in the catalyst has a silica alumina molar ratio of at least 10 to 100, but preferably no greater than about 40 and more preferably in the range of 20 to 30. Preferably, the beta zeolite has a crystal size of 0.1 to 0.7 microns (100 to n C 0 nm), a surface area of 500 to 800 m: / g and an absorption capacity of cyclohexane of 15 to 25 g / 100 g.

Preferably, the Y dealuminous zeolite used in the catalyst support has a global molar ratio of silica to alumina between 6.1 and 20.0 and more preferably between 8.0 and 15.0. The size of the cell unit for the Y dealuminated zeolite is usually between 2.440 and 2.465 nm (24.40 and 24.65 Angstroms). The preferred dealuminated zeolites and zeolites for use are zeolites L Z -210 as described in the patents E.U.A. 4,053,023 and 4,711,770.

There is only one example in EP-B-559,646 that details the preparation and testing of four hydrocracking catalysts numbered one (l), two (2 j, three (3) and four (4).) All catalysts contain the same amount and type of hydrogenation components differ in their catalytic supports Catalyst 1 contains a catalyst support of 80% by weight zeolite zeolite irelation silica to alumina 26) and 20% by weight alumina; Catalyst 2 contains a catalyst support of 30% by weight beta zeolite (silica to alumina molar ratio 26), 50% by weight zeolite LZ-210 (silica to alumina molar ratio of 12, cell unit size 2441 nm) and 20% by weight. % by weight alumina; Catalyst 3 contains a catalyst support of 30% by weight beta zeolite melar silica to alumina 26); 50% by weight LZ-10 zeolite (silica to alumina molar ratio 5.2, cell unit size 2.430 nm) and 20% by weight alumina; and Catalyst 4 contains a catalyst support of 80% by weight zeolite LZY-82 (molar ratio silica to alumina 5.7, cell unit size 2,455 nm) 20% by weight alumina. Catalysts 1, 3 and 4 were comparative catalysts while Catalyst 2 was a catalyst according to the invention.

When the hydrocracking performances of the catalysts were evaluated under the second stage series flow conditions (referred to in US Patent 559,646 as a first stage simulation under ammonia-rich conditions), the results in Taola 3 show that while the Catalyst 2 of the invention produces the highest gasoline yield that the catalysts tested, also produces a significant amount of gaseous derivative C1-C3. Actually, Catalyst 2 produces more gaseous derivative (ie, has a higher gas processing) than Comparative Catalyst 4 (a commercial gasoline hydrocracking catalyst), which is known to yield high gas formations.

WO 94/26847 discloses a process for the hydrocarbon, hydrofluoride and simultaneous hydrodesitrogenation of a hydrocarbon feed by contacting a feed material containing sulfur compounds and nitrogenous compounds, have a boiling range greater than 80 % and boiling above 300 ° C and has not been subjected to any process of hydrodesul furation or preparatory catalytic operation, at elevated temperature and pressure, in the presence of hydrogen, with a catalyst containing a vehicle such as alumina or silica-alumina, a metal component of Group VIB, a metal component of Group VIII, and an alaminos 111 cato without layers, crystalline, inorganic with pores of diameter greater than 1.3 nm and showing, after calcination, an X-ray diffraction pattern with at least one peak in the d-separation greater than 1.8 nm, such as a gamma 111 ca to described in WO93 / 02159, in particular ular the 1 uminos 111 ca t o designated MCM-41.

Although it is indicated on page 7, lines 15 to 19 of WO 94/26847, that other molecular sieves can be incorporated into the catalyst in addition to the 111-mm atoms, such as the Y-zeolites, the ultra-stable Y-zeolites having a cell unit size (a0) from 2.425 to 2.440 nm (24.25 to 24.40 Angstroms), beta zeolite, mordenite and materials of the ZSM-5 type having a silica to alumina ratio in the range of 12 to 300, there are examples in WO 94/2687 on the preparation and testing of said composite catalysts or suggestion as to the use of a specific beta zeolite for this purpose.

Also in WO 91/17829, hydrocracking feed is disclosed by using a catalyst comprising a hydrogenating component and a support comprising beta zeolite and a Y zeolite having (i) a cell unit size below 2.445 nm ( 24.45 Angstroms), or, (n) a water vapor absorption capacity at 25 ° C and a p / ps value or 0.10 less than 10.00% by weight; the zeolites generally and preferably are in greater combination with a porous, inorganic refractory oxide, such as a lumina.

The beta zeolite present in the catalyst support has a silica to alumina molar ratio of at least 10 to 100, but preferably not greater than 40 and more preferably in the range of 20 to 30. Preferably, the beta zeolite has a size of glass of 0.1 to 0.7 microns (100 to 700 nm), a surface area of 500 to 800 m '/ g and an absorption capacity of cyclohexane of 15 to 25 g / 100 g.

The preferred Y zeolites to be used are those which meet the above requirements (i) and (11), for example, zeolites ul t r ahydr ofobi cal Y (UHP-Y) as exemplified in zeolite LZ-10.

The hydrocracking catalyst according to WO 91/17829 can, depending on the selected process conditions, be used for the production of gasoline or medium distillates. However, the catalyst is apparently suitable for the production of gasoline.

The patent E.U.A. 5,413,977 discloses a hydrocracking catalyst having high activity and selectivity for gasoline, comprising a hydrogenation component on a catalyst support composed of beta zeolite and a layered magnesium silicate including hectorite and saponite (both are smectite minerals) and , especially, sepiolite.

The beta zeolite used in the catalyst support has a silica to alumina molar ratio of at least 10 to 100, more preferably no greater than 40 and more preferably in the range of 20 to 30. Preferably, the beta zeolite has a size of glass of 0.1 to 0.7 microns (100 to 700 nm), a surface area of 400 to 800 m2 / g, an absorption capacity of cyclohexane of 15 to 25 g / 100 g, and an absorption capacity of water vapor at 25 ° C and a p / p0 value of 0.10 greater than 5% in oes o.

International patent application No. PCT / EP96 / 05352 (applicant reference TS 478 PCT) discloses a stable hydrocracking catalyst having high activity combined with good selectivity of the medium distillate comprising, as the first cracking component, a beta zeolite which has a molar ratio of silica to alumina of at least 20, which is in the form of crystals less than 100 nm in size; a second cracking component selected from (i) crystalline molecular sieves having pores with diameters greater than 0.6 nm; (n) crystalline mesoporous aluminosilicates having pores of diameters of at least 1.3 nm; and, (111) clays; and at least one hydrogenation component.

It has been observed, when preparing the catalyst of International Patent Application No. PCT / EP 96/05352 that some agglomeration of the beta zeolite crystals in larger crystals may occur. It would be desirable if, in case this agglomeration could be avoided, it would be done since the catalyst would have an even greater activity.

Therefore, the present invention seeks to solve this problem.

Description of the invention.

According to the present invention, there is provided a process for the preparation of a catalyst composition comprising, in the range from 0.5 to 40% by weight of, as the first cracking component, a beta zeolite with a molar ratio silica to alumina of at least 20, comprising crystals less than 100 nm in size, in the range from 0.5 to 90% by weight of a second cracking component selected from (i) crystalline molecular sieves having pores with diameters greater than 0.6 nm, and, (n) clays, and in the range from 0 to 99% by weight of a binder (percentages by weight based on the combination of dry weight of the first and second cracking component and the binder) , the process comprises the steps of: (i) preparing a mixture comprising the first cracking component and the second cracking component, the first cracking component is in the form of a sol (colloidal suspension), optionally together with a binder; (n) Extrude the mixture into catalyst extruders, and (n) calcine the extruded ones.

In the present specification, unless otherwise indicated, the silica to alumina molar ratio of a zeolite is the molar ratio determined based on the total or overall amount of aluminum and silicon (structure and no structure) present in the zeolite. .

In step (i) of the present process, beta zeolite (the first cracking component), which is in the form of a sol (ie, a suspension of colloidal beta zeolite crystals in a liquid), is combined with the second cracking component to form a mixture. The beta zeolite has a molar ratio of silica to alumina of at least 20, preferably at least 25. Beta zeolite with a molar ratio of silica to higher alumina, for example, up to and including 60, 80, 100, 120 or 150 can be used if desired. Thus, beta zeolite can have a molar ratio of silica to alumina in the range from 20 to 60, 25 to 60, 20 nasta 80, 25 to 80, 20 to 100, 25 to 100, 20 to 120, 25 to 120, 20 to 150 or 25 to 150. The crystals of beta zeolite in the sun are less than 100 nm in size, that is, up to 99 nm in size. Preferably, the crystals are in the range from 20 to 95 nm in size, more preferably from 30 to 75 nm in size, even more preferably from 40 to 75 nm in size and particularly from 50 to 70 nm in size.

The beta zeolite sol can be conveniently prepared by the method of Camblor et al., "Progress in Zeolite and Microporous Materials", volume 105, pages 341-348, Elsevier (1997).

Without wishing to be bound by a particular theory, the beta zeolite sol used in the process of the present invention surprisingly seems to supply a better dispersion of the beta zeolite crystals, thus reducing the risk of the beta zeolite crystals becoming algal. the catalyst composition.

The second cracking component that is combined with the beta zeolite sol is selected from (i) crystalline molecular sieves having pores with diameters greater than 0.6 nm (ie, as determined by nitrogen absorption techniques) , and, (ii) clays.

In the context of the present specification, the term "molecular sieve" also includes the corresponding stabilized derivatives (hydr ot érmicamente) and desalummados and those derivatives that can be obtained by isomorphic substitution and change of cation. Methods for change of a cation, stabilization (hydrotrim), demodulation and isomorphic substitution of molecular sieves are well known in the art and will not be discussed in greater detail in the present specification.

The second cracking component can be a simple material (i) or (n), or a combination of two or more of said materials.

Preferably, the second cracking component is selected from (i) crystalline molecular sieves of structure type FAU, EMT, MOR, LTL, MAZ, MTW, OFF, BOG, AET, AFI, AFO, AFR, AFS, AFY, ATS, VFI and CLO as described in "Atlas of Zeolite Structure Types", 3rd. Edition, published in 1992 on behalf of the Structure Commission of the International Zeolite Association; and, (n) Smectite-type clays not supported, for example, montmorillonites, hectorites, saponites and beiddelites.

More preferably, the second cracking component is (i) a crystalline molecular sieve of FAU type structure, eg, a highly ultrastable Y zeolite (VUSY) of cell unit size (a0) less than 2.440 nm (24.40 Angstroms) ), in particular less than 2.435 nm (24.35 Angstrcms) as are known, for example, from EP-A-247,678 and EP-A-247,679.

The VUSY zeolite of EP-A-247,678 or EP-A-247,679 is characterized by a cell unit size below 2.445 nm (24.45 Angstroms) or 2.435 nm (24.35 Angstroms), an absorption capacity of water (at 25 ° c and a value o / p0 of 0.2) of at least 8% by weight of zeolite and a pore volume of at least 0.25 ml / g, where between 10% and 60% of the total volume of pore is formed of pores having a diameter of at least 8 nm.

In addition to the first and second cracking components, the mixture may further comprise a binder, in particular an inorganic oxide binder. Examples of suitable binders include alumina, silica, aluminum phosphate, magnesia, titania, zirconia, yea 11-a-alumina, s-11 ce-zi-coni, silica-boria and combinations thereof. Alumina is the preferred binder.

Step (i) of the present process can be carried out with the aid of grinding the beta zeolite sol and the second cracking component, optionally together with the binder, in the presence of water and a peptizing agent, for example acetic acid. or nitric acid, to form a mixture which is then extruded in catalyst extruders in step (n) and the calcined catalyst extrudates in step (111).

The beta zeolite sol, the second cracking component and the binder are combined in amounts such that any calcined catalyst extrudates comprise in the range from 0.5 to 40% by weight of zeolite betas (first cracking component), in the range from 0.5 to 90% by weight of the second cracking component, and, a range from 0 to 99% by weight of binder; more preferably from 1 to 15% by weight, particularly from 5 to 10% by weight beta zeolite, from 5 to 80% by weight, particularly from 40 to 60% by weight, of second cracking component, and the rest of binder, all percentages by weight are calculated based on combined dry weight of the first cracking component, second cracking component and binder.

Step (n) of the present process can be carried out using any commercially available conventional extruder. In particular, a screw type extruder can be used to force the mixture through the orifices of a die to yield catalyst extruders of the required shape, for example, cylindrical or trilobal. The belts formed at the time of extrusion can then be counted to an appropriate extent. If desired, the catalyst extrudates may be dried, for example, at a temperature of from 100 to 300 ° C for a period of 30 minutes to 3 hours, prior to calcination in step (iii). The calcination is convenient carried out in the air, at a temperature in the range from 300 to 800 ° C for a period from 30 minutes to 4 hours.

The catalyst composition prepared by the process of the present invention will further comprise at least one hydrogenating component. Examples of suitable hydrogenation components include the Group VI components (such as molybdenum and tungsten) and Group VIII components (such as cobalt, nickel, iridium, platinum and palladium). Preferably, at least two hydrogenation components are used, for example, a molybdenum and / or tungsten component in combination with a cobalt and / or nickel or platinum component. Particularly preferred combinations are: nickel / tungsten dye, nickel / mol ibidene and pl ate / palladium.

Said at least one hydrogenation component can be incorporated in several stages during the preparation of the catalyst composition, according to the conventional art techniques. For example, said at least one hydrogenation component can be charged in one or more components of hydrogenation. cracking by means of cation exchange or impregnation of the pore volume before the cracking components are combined in step (i) of the present process. Alternatively, said at least one hydrogenation component can be added in step (i) and / or can be added to the calcined extruders of step (111) at a later stage (? V), characteristically as one or more aqueous solutions (impregnation) of metal salts of Group VI and / or Group VIII.

In a preferred aspect of the present invention, said at least one hydrogenation component is added only during step (iv). Thus the present invention further provides a process for the preparation of a catalyst composition as defined above comprising the steps of: (i) preparing a mixture composed of the first cracking component and the second cracking component, the first cracking component it is in the form of a sol, optionally together with a binder (11) extrude the mixture in catalyzed extrusions, (ni) calcining the extrusions, and, (iv) add at least one hydrogenation component to the calcined extrus i onados.

In a preferred aspect of the invention, the step (?) Is followed by another step v in which the foreign ones are again calcined in the manner described above.

The catalyst composition may contain up to and including 50 parts by weight of hydrogenating component calculated as metal per 100 parts by weight of the total dry catalyst composition. For example, the catalyst composition may contain from 2 to 40, more preferably from 5 to 30, and especially from 10 to 20 pairs by weight of Group VI metals and / or from 0.05 to 10, more preferably from 0.5. up to 8, and advantageously from 1 to 6 parts by weight of Group VIII metals, calculated as metal per 100 parts by weight of total dry catalyst composition.

Said catalyst composition containing a hydrogenation component can be advantageously used in a process for converting a hydrocarbon feedstock into lower boiling materials, which comprises contacting the feedstock with hydrogen at elevated temperatures and high pressures, in the presence of the composition catalyst (a process of hydrocracking).

The hydrocarbon feed materials that can be converted by the above process include atmospheric gas oils, coke gas oils, vacuum gas oils, deasphalted crudes, waxes obtained from a synthesis process Fi s cher-Tropsch, long and short waste, crude of catalytically cracked cycle, thermal or catalytically cracked and syncrude gas oils, optionally originated from tar, shales, processes for the improvement of waste and biomass. The combinations of various hydrocarbons can also be used. The feedstock may comprise hydrocarbons having an initial boiling point from at least 33 ° C down to at least 50 ° C. The boiling range (from the initial boiling point to the end) may be in the range from about 50 to 800 ° C, preferably given to the feedstocks having a boiling range from about 60 to 700 ° C. The feedstock may have a nitrogen content up to 5000 ppm (parts per million by weight) and a sulfur content of up to 6% by weight. Characteristically, the nitrogen content is in a range from 250 to 2000 ppmp and the sulfur content is in the range from 0.2 to 5 amp; in weigh. However, the feedstock may have a lower nitrogen and / or sulfur content; furthermore, it is possible and sometimes desirable to subject part or all of the feed material to a prior treatment, for example, hydrodemrrogenation, hydration or hydrideration, methods known in the art, so that the feed material subjected to hydrocracking have a much lower nitrogen, sulfur and / or metal content.

The hydrocracking process can be carried out at a reaction temperature in the range from 200 to 500 ° C, convenient from 250 to 500 ° C, preferably in the range from 300 to 450 ° C.

Preferably, the process is carried out at a total pressure (at the reactor inlet) in the range from 3 x 106 to 3 x 107 Pa (30 to 300 bar), more preferably from 4 x 106 to 2.5 x 107 Pa (40 to 250 bar), for example, from 8 x 106 to 2 x 107 Pa (80 to 200 bar).

The partial pressure of hydrogen (at the reactor inlet) is preferably within a range from 3 x 106 to 2.9 x 107 Pa (30 to 290 bar), more preferably from 4 x 106 to 2.4 x 107 Pa ( 40 to 240 bar), and even more preferably from 8 x 10 ° to 1.9 x 107 Pa (80 to 190 bar).

It is convenient to use a space velocity in the range from 0.1 to 10 kg of feed material per liter of catalyst per hour (kg.l ^ .T1). Preferably, the special speed is in the range from 0.1 to 8, particularly from 0.2 to 5 Kg.l ~ 1.h ~ 1.

The ratio of hydrogen gas to feedstock (total gas rate) used in the process will be, in general, in a range from 100 to 5000 Nl / kg, more preferably in the range from 200 to 3000 Nl / kg.

The present invention will be improvement understood from the following illustrative examples in which the ratio olar silica to alumina from one to 1 potion 111 to (zeolite) was determined based on the total amount of aluminum and silicon (structure and non-structure) present in the zeolite and the cell unit size (a0) of a lminosis cato (zeolite) was determined according to the standard test method ASTM D 3942-80. In addition the boiling points and The density of hydrocarbon feedstocks was determined according to the standard test methods ASTM D 86 and D 1298 respectively.

E j e pl o I i) Preparation of a beta zeolite sol A colloidal solution or beta zeolite sol is prepared by the method of Camblor et al., "Progress i n Zeolite and Microporous Materials ", volume 105, pages 341-348, Elsevier (1997), as follows.

To an aqueous solution of tetraethylammonium hydroxide (TEAH) free of alkali metal ions (225 g, 40% by weight solution, ex-Alfa) was added aluminum metal (2.93 g) and the solution was heated to 50 ° C. C for 5 hours to effect the total dissolution of the aluminum metal. Once all the aluminum had dissolved, the solution was added, with agitation, to a mixture made by dispersing an amorphous silica "Aerosil 200"(brand name) (162.5 g, ex-Degussa) in an aqueous solution of tetraethylammonium hydroxide (311.9 g TEAH, ex-Alpha, in 407 g of water), which resulted in the formation of A gel (atomic ratio Si / Al of 25) After being stirred for 15 minutes, the gel was transferred to an autoclave operated at 140 ° C and 300 rpm for 240 hours.The contents of the autoclave were quenched with cold water and the solids separated by centrifugation The washing of the solids with distilled water until the pH of the wash water was lower than pH 9 gave the desired product, a beta seolite dol (Si / Al atomic ratio of L4, molar ratio of silica to alumina of 28) The X-ray diffraction and Electron Transmission Microscopy analyzes carried out in the dry sol confirmed that it was pure beta zeolite with an average crystal size of 70 nm (700 Angs t roms). 11 Preparation of a catalyst composition a) A catalyst composition was prepared according to the process of the present invention by combining the beta zeolite sol prepared in (i) above (35.2 g, ignition loss (LOI) of 71, 6%) with alumina (53.8 g, LOI of 25.6%) and a very ultra-stable Y zeolite (VUSY, acronym in English for Very Ultrastable Zeolite Y), in accordance with EP-A-247,678 and EP-A- 247,679 (58.4 g, LOI of 14.4%) having a molar ratio of silica to alumina of 9.9 and a cell unit size of 431 Angstroms). Water and acetic acid were added and the resulting mixture was crushed and then extruded, together with an extrusion aid, into cylindrical granules. The granules were statically dried for 2 hours at 120 ° C and then calcined for 2 hours at 530 ° C. The granules thus obtained had a circular end surface diameter of 1.6 mm and a water pore volume of 0.77 ml / g. The granules comprised beta zeolite of 10% by weight (first cracking component), 50% by weight VUSY zeolite (second cracking component) and 40% by weight of alumina (binder), based on dry weight. b) 40.18 g of an aqueous solution of nickel nitrate (14.1% by weight nickel) and 39.93 g of an aqueous solution of me tat ungs tao ammonium (67.26% by weight of tungsten) were combined. ) and the resulting mixture was diluted with water (34.6 g) and then homogenized. The granules were impregnated with the homogeneous mixture (69.7 ml), dried at room temperature (20 ° C) for 4 hours and then at 120 ° C for 2 hours, and finally calcined for 2 hours at 500 ° C. The granules contained 4% by weight of nickel and 19% by weight of tungsten (hydrogenation components), based on total composition.

Comparative Example A The process of Example 1 (n) was repeated except that a commercially available powdered beta zeolite was used (ex-PQ, silica to alumina molar ratio of 114 and crystal size in the range of 30 to 50 nm (300 to 500 Angstroms) instead of the beta zeolite sol to prepare a catalyst composition as described in Example 1 of International Patent Application No. PCT / EP 96/05352.

Example It was evaluated on the hydrocarbon yield of the catalyst composition of Example 1 (hereinafter referred to as Catalyst 1) in a second flow-stage simulation test. The test was carried out in a microfluidic unit, at one time, which had been loaded with an upper catalyst layer composed of 1 my C-424 catalyst (commercially available 1 from Criterion Catalyst Company) diluted with 1 ml of particles 0.1 mm SiC and a catalyst bottom layer composed of 10 ml of Catalyst 1 diluted with 10 ml of 0.1 mm SiC particles. Both catalyst layers were presulphurized before testing.

The test comprised the sequential contact of a carbonaceous feed material (a heavy gas oil) with the upper catalyst layer and then the catalyst bottom layer in a one-time operation under the following process conditions: a space velocity of 1.5 kg heavy gas oil per liter of catalyst per hour (kg I-1. !! "1), a ratio hydrogen gas / heavy gas oil of 1450 Nl / kg, a partial pressure of hydrogen sulphide of 4.7 x 10B Pa (4.7 bar) and a total pressure of 14 x 106 Pa (140 bar).

The heavy gas oil used had the following properties: Carbon content: 86.69% by weight Hydrogen content 13.35% in pe or n-decylamine added: 12.3 g / kg (equivalent to 1100 ppm N).

Total nitrogen content (N): 1119 ppmp Density (15/4 C): 0.8789 g / ml Density (70/4 C): 0.8447 g / ml Mold weight: 433 g Initial boiling point: 349 ° C Boiling point 50% by weight: 461 ° C Final boiling point: 620 ° C Fraction boiling below 370 ° C 2.0% by weight Fraction boiling above 540 ° C 13.3% by weight The hydrocracking efficiency was evaluated at conversion levels between 45 and 100% by weight conversion of feed components having a boiling point above 370 ° C. The results obtained at 65% by weight net conversion of boiling feed components above 370 ° C are shown in Table I below.

Comparative Example The test procedure of Example 2 was repeated except that the catalyst bottom layer composed of 10 ml of catalyst composition of Comparative Example A (hereinafter referred to as Catalyst A) was diluted with 10 ml of 0.1 mm particles. Sic. The hydrocracking efficiency was evaluated at conversion levels between 45 'and 100% by weight conversion of feed components with a boiling point above 370 ° C. The results obtained at 65% by weight net conversion of feed components that boil above 370 ° C are presented in Table I below.

Table I Catalyst system C-424 / Cat. A C-4242 / Cat.l Temp. (° C) weight 371.5 368.5 net conversion Product selectivities n in weight on feed Gas (Ci-C; 0, 8 0, 9 C «2.7 3, 1 Naphtha (C5-150 ° C) 34 34 Kerosene (150-250 ° C) 36 37 Diesel (250-370 ° C) 26, 5 25 Iso / Normal ratio of 2.4 2, 7 butanes It can be seen from Table I that while Catalyst 1 (prepared by the process of the present invention) and Comparative Catalyst A both produced the same average distillate yields with very little gaseous derivative C i-C 3, this was achieved at a lower temperature using Catalyst 1 (368, 5 ° C) than using Catalyst A (371.5 ° C). Thus, Catalyst 1 demonstrates greater activity without loss in the selectivity of the middle distillate in relation to Catalyst A. Moreover, while the iso / normal ratio for butanes is only mentioned higher for Catalyst 1 than for Catalyst A, a similar result Could be expected for the other products. In this way, the higher the iso / normal ratio, the better the quality of the product. 3 Granules comprising 10% by weight beta zeolite, 50% by weight VUSY zeolite and 40% by weight alumina were prepared following the procedure of Example 1 n) a) above. .79 g of an aqueous solution of Pt (NH3) 4 (N03) 2 (2.99% by weight platinum) and 0.98 of an aqueous solution of Pd (NH3) 4 (N03) 2 (6, 56% by weight palladium) and the resulting mixture was diluted with water to 24.9 ml and homogenized. 31.84 g of granules are impregnated with the homogenized mixture, and then removed / calcined in air in a rotary tube at 10 rpm at the following heating rate: heating at 180 ° C at 15 ° C per minute; maintaining the temperature at 180 ° C for 10 minutes; heating at 300 ° C to 30 ° C per minute; Maintenance at 300 ° C for 15 minutes.

The resulting granules contained a charge of metals of 1% by weight platinum and 0.2% by weight palladium (hydrogenated components) on the basis of total composition.

E j empl o 4 The hydrocracking efficiency of the catalyst composition of Example 3 (hereinafter referred to as Catalyst 2) was evaluated in a simulation test of wax hydrocracking. The test was carried out on a single-time microflower, which had been loaded as a catalyst layer comprising 10 ml of Catalyst 2 diluted with 10 ml of 0.1 mm SiC particles. The catalyst layer was reduced with hydrogen prior to the test.

The test involved the contact of a hydrocarbon feed material to (a Fischer-Tropsch wax) with the catalyst layer in a one-time operation under the following process conditions: a space velocity at 1.15 Kg wax per liter of catalyst per hour (kg .1 ~ l. n "1), a hydrogen gas / heavy gas oil ratio of 750 Nl / kg and a total pressure of 4 x 10 c Pa (40 bar).

The heavy gas oil used had the following properties: Carbon content: 85.35% by weight Hydrogen content: 14.62% by weight Sulfur content (S): < 10 ppmp Density (125/4 C): 0.7437 g / ml Kinetic viscosity (100 ° C): 3, 9 mm2 / s (3.9 cSt) Initial boiling point: 65 ° C Boiling point 50% by weight 442 ° C Final boiling point: 700 ° C Fraction boiling below 370 ° C: 20.6% by weight Boiling fraction above 540 ° C: 19.1% by weight Performance of hydrocracking was evaluated at conversion levels between 35 and 80% by weight conversion of feed components having a boiling point above 370 ° C. The results obtained at 60% by weight of net conversion of boiling feed components above 370 ° C are shown in Table II below.

Table II Catalyst system Catalyst 2 Temp. (° C) to 65% weight 241 net conversion Product selectivities (% by weight over the element) Gas (Ci-C 0, 5 C, 2, 1 Naphtha (C5-140 ° C) 19 Kerosma (140-220 ° C) 24 Diesel (220 - 370 ° C) 54 Iso / Normal ratio of 3, 6 butanes It can be seen from Table II that Catalyst 2 (prepared by the process of the present invention) produced the same yields of middle distillates with very little gaseous derivatives C i - C3 and a high iso / normal ratio for butanes.

It is noted that in relation to this date, the best method known by 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, the content of the following is claimed as property.

Claims (13)

Claims

1. A process for the preparation of a catalyst composition and composition, for example ranging from 0.5 to 40% by weight of, as the first cracking component, a beta zeolite with a silica to alumina molar ratio of at least 20 composed of size smaller than 100 nm, in the range from 0.5 to 90% by weight of a second cracking component selected from (i) crystalline molecular sieves having pores with diameters of 0.6 nm, and (ii) arcilas, and in the range from 0 to 99% by weight of a binder (percentages by weight based on the combination of dry weight of the first and second cracking component and the binder), the process is characterized by the size of the binder.; (i) preparing a composite mixture of the first cracking component and the second cracking component, the first cracking component is in the form of a sol (colloidal solution), optionally together with the binder, (ii) extruding the mixture into extruded of catalyst, (m) calcining the ext ru si onados.

2. The process according to claim 1, characterized in that the binder is an inorganic oxide binder.

3. The process according to claim 2, characterized in that the binder is selected from alumina, silica, aluminum phosphate, magnesia, titania, zirconia, silica-alumina, yes 11 cezo irconia, silica-bopa and combinations of the same.

4. The process according to any of claims 1 to 3, characterized in that it comprises the steps of: (i) grinding the first and second cracking components, optionally together with the binder, in the presence of water and a peptizing agent to form a mixture, (11) extrude the mixture in extruded catalyst solutions, and (m) calcinate the extruded products.

5. The process according to any of the preceding claims, characterized in that the catalyst composition further comprises at least one hydrogenation component.

6. The process according to claim 5, characterized in that at least one component of oxidation is added in step (i) and / or is added to the calcined extrusions of stage (m) in a later stage (iv).

7. The process according to any of the preceding claims, characterized in that the beta zeolite comprises elaborate crystals of a size from 20 to 95 nm.

8. The process according to any of the preceding claims, characterized in that the second cracking component is selected from crystalline molecular sieves of structure type FAU, EMT, MOR, LTL, MAZ, MTW, OFF, BOG, AET , AFI, AFO, AFR, AFS, AFY, ATS, VFI and CLO, and, (n) clays of the smectite type not supported.

9. The process according to the claim 8, characterized in that the second cracking component is (i) a crystalline molecular sieve of structure type FAU.

10. A catalyst composition as defined in claim 1, characterized in that it can be obtained by a process as claimed in any of the preceding claims.

11. The use of a catalyst composition as claimed in claim 10, in a process for converting a hydrocarbon feedstock into lower boiling materials.

12. A process for converting a hydrocarbon feed material into lower boiling materials, characterized in that it comprises contacting the feed material at elevated temperature in the presence of a catalyst composition prepared by a process according to any of claims 1 to 9.

13. The use of a beta zeolite sol in the preparation of a catalyst composition as defined in claim 1.