RU2366505C2 - Catalyst carrier and catalytical composition, methods of their preparation and application - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: mould catalyst for hydrocracking contains at least zeolite Y and inorganic high-melting oxide with monomodal pores distribution (by mercury porosimetre) whereat at least 50% of total volume is represented with pores having diametre in the range from 4 to 50 nm and the volume at least 0.4 ml/g. The method for carrier preparation and the carrier obtained with this method are described; the said method includes moulding of the mixture containing at least zeolite Y and high-melting oxide with calcinations losses in the range (LIR) from 55 to 75%. The catalytical composition for hydrocracking includes said carrier, at least one component of hydrogenating metal selected from the metal of groups V1B and group V111 and optionally at least one promoting element selected from silicon boron in the case when carrier virtually does not contain the alumosilicate zeolite. The method for catalytical composition preparation and composition obtained with this method are described; the said method includes optional calcinations of the said carrier, precipitation of the at least one hydrogenating metal selected from described above ones in the corresponding amount; the said precipitation is carried out by impregnation with solution containing organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. The hydrocracking method with application of the aforementioned catalytical composition is described. ^ EFFECT: enhancing of the catalytical composition activity, selectivity and hydrogenation ability. ^ 18 cl, 5 tbl

Description

FIELD OF THE INVENTION

The present invention relates to a catalyst carrier suitable for a hydrocracking catalyst, a catalyst composition comprising said carrier, to a carrier, as well as a catalyst composition and the use of this catalyst composition as a hydrocracking catalyst.

State of the art

Methods that include treating crude oil and other types of crude oil with hydrogen in the presence of a catalyst are well known. One such method is hydrocracking, in which the hydrocarbons of heavy distillates under pressure of hydrogen are converted into products with a lower molecular weight in the presence of a catalyst. Hydrocracking is used in the oil industry to produce a wide range of materials ranging from C3 / C4 hydrocarbons to lubricating oils.

Hydrocracking can be carried out either as a one-stage or as a two-stage process. Two-stage hydrocracking includes a first stage, which is mainly a hydrotreatment stage, in which impurities and unsaturated compounds are hydrogenated in the presence of a first catalyst having high hydrogenating activity, and a second stage, in which cracking mainly occurs in the presence of a second catalyst having high cracking activity. In one-stage hydrocracking, the processing and cracking stages proceed in one reactor, and they can be carried out using a single catalyst. The catalysts used in hydrocracking are mainly obtained from a support material on which catalytically active metals are deposited, such as nickel, molybdenum, tungsten, palladium and others.

The higher the activity of the hydrocracking catalyst, the greater will be the conversion efficiency of the feed. In particular, a more active catalyst can operate at a lower temperature than a catalyst with less activity to achieve the same degree of conversion. This is advantageous since, with a decrease in operating temperature, the catalyst service life is increased and operating costs are reduced. Accordingly, there is always a need to improve catalytic activity. In addition, there is a continuing need to improve the selectivity of the catalytic effect, in particular to increase the yield of middle distillate fractions and to reduce the yield of light gaseous materials (C ₁ -C ₄ ).

Previous decisions to improve selectivity and activity have mainly focused on the proposal of new active materials, such as modified Y zeolites or aluminosilicate materials, or new formulations containing several active components in order to simultaneously improve selectivity and activity. The prior art solutions are described in US 2002/0160911 and in documents WO 00/12213 and WO 2004/047988.

Disclosure of invention

The present invention provides a molded catalyst support that includes at least one inorganic refractory oxide, the support having a unimodal pore size distribution in which at least 50% of the total pore volume are pores having a diameter in the range of 4 to 50 nm, and in which the pore volume in these pores is at least 0.4 ml / g, where all measurements were performed by mercury porosimetry.

The inorganic refractory oxide material may be any conventional oxide material suitable for hydroconversion processes. Accordingly, this material is selected from alumina, silica, silica-alumina or a mixture of two or more such materials. However, zirconia, clays, aluminum phosphate, magnesium oxide, titanium oxide, silicon dioxide-zirconium oxide and silicon dioxide-boron oxide can also be used, although they are rarely used in the prior art. This oxide material may be amorphous or crystalline, or may be a mixture of two or more such materials. Suitable zeolite materials are crystalline aluminosilicates; faujasitic zeolites, such as Y-zeolite materials, are very suitable.

Preferred refractory oxides are those that are capable of hydrocracking, and they can be selected from amorphous aluminosilicate and ultrastable Y-zeolite oxide materials.

The term “amorphous” indicates the absence of a crystalline structure, which is determined by the X-ray diffraction method, of the support material, although there may be some short range order. An amorphous aluminosilicate suitable for use in the preparation of a catalyst support is commercially available. Conventional homogeneous amorphous aluminosilicate materials can be used, as well as heterogeneous dispersions of finely ground aluminosilicates in an alumina matrix, as described in US Pat. Nos. 4,097,365 and 4,419,271. Alternatively, aluminosilicates can be prepared by a co-gelation method or by a formulation method that are well known in the art . Preferably, the amorphous aluminosilicate contains silicon dioxide in an amount of from 25 to 95 wt.%, As calculated on one carrier (i.e., based on a common carrier). More preferably, the amount of silica in the carrier is more than 35 wt.%, And most preferably at least 40 wt.%. A very suitable amorphous aluminosilicate for use in preparing the catalyst carrier of this invention contains 45 wt.% Silica and 55 wt.% Alumina and is commercially available (formerly Criterion Catalysts & Technologies, USA).

Preferred Y-zeolite materials are ultra-stable zeolite Y (USY) or highly ultra-stable zeolite Y (VUSY) with a unit cell size (a ₀ ) of less than 2.440 nm (24.40 Angstroms), especially less than 2.435 nm (24, 35 Angstrom), and the ratio of silica to alumina is from 4 or more, for example, from 4 to 100. Suitable Y-zeolite materials are known, for example, from the description of patents EP No. 247678 and 247679 and document WO 2004/047988.

Although USY and VUSY Y zeolites are preferred forms of the cracking component used in the present invention, other forms of Y zeolites are also suitable for use, for example, known ultrahydrophobic Y zeolites.

The preferred VUSY zeolite from documents EP-A-247678 or EP-A-247679 is characterized by a unit cell size of less than 2.445 nm (24.45 Angstroms) or 2.435 nm (24.35 Angstroms), water adsorption capacity (at 25 ° C. and p / p _about 0.2), at least 8 wt.% zeolite and a pore volume of at least 0.25 ml / g, and between 10 and 60% of the total pore volume are pores having a diameter at least 8 nm.

Most preferred are Y-zeolite materials with a small unit cell size and a large surface area, as described in WO 2004/047988. Such materials can be described as a faujasitic zeolite having a unit cell size in the range of 24.10 to 24.40 Å, a volumetric ratio of silica to alumina (OKA) of more than 12, and a surface area of at least 850 m ² / g as measured by the BET method and ASTM D 4365-95 standard nitrogen adsorption at a value of p / p ₀ of 0.03. These materials are obtained by a method that includes:

a) providing an initial faujasite zeolite structure having a silica to alumina ratio of from 4.5 to 6.5 and an alkali content of less than 1.5 wt.%;

b) hydrothermal treatment of the specified source of zeolite at a temperature in the range from 600 to 850 ° C, preferably from 600 to 700 ° C, more preferably from 620 to 680 ° C and particularly preferably from 630 to 670 ° C and at a partial pressure of steam, preferably applied externally, in the range from 0.2 to 1 atmosphere, for a time that is sufficient to obtain an intermediate zeolite having a unit cell size of 24.30 to 24.45 Å, and accordingly is in the range from 0.5 to 5 hours , more appropriate from 1 to 3 hours;

c) contacting the intermediate zeolite with an acidified solution containing an acid and optionally an ammonium salt, under conditions effective to obtain a zeolite with a large surface area having a unit cell size in the range of 24.10 to 24.40 Å, the molar ratio of silicon dioxide to oxide more than 12 aluminum and a surface area greater than

850 m ² / g, the result is a zeolite with a large surface area; and

d) isolating said zeolite with a large surface area.

Particularly preferred materials with a large surface area have one or more of the following features:

the unit cell size is in the range from 24.14 to 24.38 Å, preferably from 24.24 Å, more preferably from 24.30 to 24.38 Å, preferably up to 24.36 Å, especially up to 24.35 Å and, for example, may be in the range of 24.14 to 24.33 Å;

the ratio of OKA in the range from 20 to 100, preferably from 20 to 80, especially up to 50;

a surface area of at least 875, preferably at least 890, for example at least 910 m ² / g;

micropore volume, which is determined by the method of nitrogen porosimetry (using the t-graph method, also known as the t-method, using nitrogen as an adsorbate, as described in Lippens, Linsen and de Boer, Journal of Catalysis, 3-32, (1964 )), more than 0.28 ml / g, expediently more than 0.30 ml / g. Typically, the micropore volume will be less than 0.40 ml / g, suitably less than 0.35 ml / g. Here, micropores are pores having a diameter of less than 2 nm.

The mercury indentation porosimetry method is a traditional method for determining the specific mesoporosity and macroporosity of a refractory oxide or other solid porous material, since this method allows you to determine the distribution of pore volumes from 4 nm or higher. Here, mesopores mean pores having a diameter in the range of 4 to 50 nm; Macropores mean pores having a diameter above 50 nm. The aim of the present invention is really to maximize the mesoporosity, while minimizing the macroporosity of the media, and at least increase the number of mesopores, without increasing the number of macropores in the media.

The shaped carrier of this invention has a monomodal distribution. This means that on the traditional pore size distribution diagram (RRS), on which dD is plotted relative to dV / dD, there is a single peak, respectively, a single sharp peak, which, in the case of the carrier according to the invention, is in the mesopore range: the pore diameter is in range from 4 to 50 nm. Here, D is pore diameter and V is pore volume. For the carriers according to the invention, it is possible that on such a RRS graph, in the mesopore range there is also a smoothed or bell-shaped curve; that is, in the understanding of this text is not a peak.

Preferably, the pore volume in the mesopore range is at least 0.45 ml / g, preferably at least 0.5 ml / g. Preferably, the pore volume in the mesopore range is at least 0.8 ml / g, more preferably at least 0.7 ml / g. The nature of the inorganic refractory oxide may affect the most preferred pore volume in the mesopore range for the shaped support of this invention. When the nature of the refractory oxide is completely or predominantly amorphous, for example alumina, silica or amorphous aluminosilicate material, then the pore volume for the mesopores is most preferably in the range from 0.5 to 0.8 ml / g, preferably from 0.6 to 0 75 ml / g, and more preferably from 0.65 to 0.70 ml / g. When the refractory oxide material includes or contains crystalline material, for example aluminosilicate zeolite, especially a Y-zeolite material, then the pore volume for the mesopores is most suitably in the range from 0.4 to 0.6 ml / g, preferably from 0.45 to 0.6 ml / g, more preferably 0.5 to 0.6 ml / g.

Preferably, the proportion of the pore volume, which are mesopores, is at least 60% and not more than 90%. And in this case, the nature of the refractory oxide material may affect the most preferred ratios. When the refractory oxide material is a fully or predominantly amorphous material, as indicated above, then the most appropriate fraction of the pore volume in the mesopore range is from 75 to 90%, preferably from 80 to 90%, and more preferably from 85 to 90%. When the refractory oxide material includes or contains crystalline material, as described above, then the most appropriate fraction of the pore volume in the mesopore range is from 50 to 75%, preferably from 60 to 75%.

The effect of this high proportion of mesopores in the pore volume is manifested in the fact that the value of the compact bulk density (COP) of the catalyst carrier is significantly reduced. Typically, this reduction in CPC may be desirable, as this means reducing the required amount of expensive catalyst. There are various ways to reduce the compact bulk density, however, other methods do not lead to increased activity or selectivity of the catalyst for middle distillate. By using the catalyst carrier according to the invention, the CPC value of the final catalyst is reduced, which provides a more economical catalyst loading for refiners, however, in addition, the activity of the catalyst unexpectedly increases, along with increased selectivity for middle distillate and for aromatics hydrogenation. This is noticeably manifested when the preferred zeolite materials are used in the catalysts of the present invention, i.e., high surface area Y-zeolite materials described herein.

An additional advantage of the catalyst carrier according to the invention is that this increased activity of the final catalyst is maintained over time and thus the stability of the catalyst is greatly increased. This is noticeably manifested for catalyst supports obtained completely or predominantly (for example, from 95 to 100 wt.%) From amorphous refractory oxide materials.

Another advantage of the molded catalyst support according to the invention is that when the support is in the form of an extrudate, it exhibits increased strength and abrasion resistance and thus provides a longer service life of the catalyst used.

It is advisable that the CPC value of the carrier according to the invention is in the range from 0.35 to 0.50 g / ml, preferably from 0.35 to 0.45 g / ml, more preferably from 0.38 to 0.43 g / ml.

When forming the catalyst carrier of the present invention, it is advisable to mix the refractory oxide material (s) with an amorphous binder material. This amorphous binder material may be any other refractory inorganic oxide or a mixture of oxides traditionally used in such compositions. Typically, such an oxide material does not have a cracking ability and can be selected, for example, from alumina, silica, or a mixture thereof, alumina being preferred, but aluminosilicate containing silica in the range of 5 to 95 wt. %; most suitable are amorphous aluminosilicate materials mentioned earlier. However, in this case, zirconia, clays, aluminum phosphate, magnesium oxide, titanium oxide, silicon dioxide-zirconia and silicon dioxide-boron oxide can also be used, although they are rarely used in this technical field. Typically, the amount of binder is in the range from 0 to 70 wt.%, And suitably less than 50 wt.%, And possibly less than 30 wt.%. However, if zeolite is present in the carrier, the amount of zeolite in the catalyst carrier, in which a binder is also present, can be up to 90 wt.%, But is preferably in the range from 2%, more preferably from 10%, especially from 20% to 80 wt. .%, calculated on the total catalyst carrier, with the rest being a binder.

It is possible, and in some cases it may be preferable for the catalyst carrier and, thus, for the catalytic composition of the present invention, that the carrier also includes a second cracking component. Preferably, it is a second zeolite. Most preferably, the second zeolite is selected from zeolite beta, zeolite ZSM-5, or zeolite Y with a different unit cell size. When a second zeolite Y is used, preferably its unit cell size is greater than 24.40 Å. The second cracking component may be present in an amount up to 20 parts by weight, based on the total zeolite plus a binder, but preferably it is present in an amount in the range from 0.5 to 10 parts by weight.

It should be noted that amorphous aluminosilicate can play the role of both a second cracking component and a binder material. It is most effectively used as a cracking component under conditions of high process temperature; it has been found that as a binder, it is effective in protecting the zeolite from loss of crystallinity and therefore from loss of activity when used in any process in which water and / or fluorides are present or formed.

The molded carrier can be obtained by any conventional method of pressing refractory oxides in special forms. The usual procedure is to control the mesoporosity formed upon receipt of the materials. Pressing can be performed by tabletting, extrusion or using other pressing techniques adopted in the prior art. Applicants have found that a more stable mesoporous molded carrier of the present invention can be obtained if the oxides are prepared from a mixture having a given PPP (calcination loss). The material acquires additional stability if this mixture has a given pH range.

The present invention provides a method for producing a molded catalyst support according to the invention, which comprises molding a mixture containing said at least one refractory oxide, in which this mixture has an SPP in the range of 55 to 65%.

Here, the calcination loss (SPP) of a material is the relative amount of mass lost by heating the material, i.e. water content. Unless otherwise specified in the description, this indicator is determined here by heating the material to 540 ° C according to the following procedure. The sample is well mixed to eliminate any heterogeneity. The weighted sample is transferred to a pre-calcined suspended crucible. This crucible is placed in a preheated oven at 540 ° C for at least 15 minutes, but usually for 1 hour. The crucible containing the dried sample is weighed again and the SPP is determined by the following formula:

SPP% = (ww _proc ) / w100%

where w is the initial weight of the sample, w _proc means the weight of the calcined sample after heating in the oven, both values are given minus the weight of the crucible.

The mixture can be obtained from refractory oxide materials and additional components, for example, a binder, with an aqueous liquid, most suitable with water. Typically, oxide and binder materials are used in the form of powders or crystals. Most expediently and preferably molding is carried out by extrusion.

Conventional extrusion blends have a PPP index, which is determined by the need to combine dispersed materials in a mold that can be extruded as a combined homogeneous object, and the shear and generated heat cause the components to combine into a molded product that can maintain its integrity when use over time, i.e. retains mechanical strength. Traditionally, the extrusion mixture is molded as a pasty material by kneading or dispersing with the addition of water. Water will penetrate into the pores of materials, as well as into the voids between particles of materials. Therefore, the PPP value of the mixture for extrusion is different depending on the nature (porosity) of the materials and particle size and is often in the range from 50 to 70%. In General, for the method of the present invention requires a higher water content for the mixture compared to commonly or traditionally used for the materials used. Thus, if 54% of the SPP is usually required for the mixture, then an increased SPP, for example 58%, will increase the mesoporosity of the carrier.

Most expediently, the SPP value is at least 56%, very expedient at least 57%, preferably at least 58%, more preferably at least 59%, especially at least 60% or slightly higher 60% Since PPP can be estimated with high accuracy, the term “higher” includes, for example, 60.01%. Most preferably, the SPP value is in the range of 60, or slightly above 60, to 75%, especially for carriers in which the refractory oxide is completely or predominantly represented by amorphous aluminosilicate.

Preferably, the extrusion mixture has an acidic pH, i.e. pH 7.0 or lower. Most preferably, the pH is in the range from 3.5, suitably from 4.0 to 7.0, more preferably from 4.0 to 5.0, especially from 4.2 to 4.7.

A suitable combination of PPP and pH indicators are as follows: PPP from 58%, very appropriate from 60 or slightly above 60, to 75% and a pH in the range from 3.5, preferably from 4.0 to 5.0.

Any monobasic acid can be used to adjust the pH and acidify the solution; examples are nitric acid and acetic acid. During extrusion, conventional extrusion agents may be used; a common extrusion agent is Superfloc from Nalco.

Extrusion may be carried out using any conventional, commercially available extruder. In particular, a worm-type extrusion machine can be used to force the mixture to extrude through openings in the matrix disk to obtain extrudates of a carrier of a given shape, for example, cylindrical or three-leaf. Then, continuous billets formed during extrusion can be cut to an appropriate length.

As is known in the art, the shape of the extrudates of the carrier can also affect the activity of the final catalyst. A very appropriate form is the traditional three-petal TRILOBE ^TM (trademark), a spiral three-petal or four-petal form. An effective shape may be a molded trefoil, as described in international application WO 03/013725. Thus, elongated, shaped particles having three protrusions, each of which is attached to the central part and extends from the central part oriented along the central longitudinal axis of the particles, can be an effective shape, the particle cross-section occupying a region surrounded by the outer edges of six outer circles around the central circle, minus the area occupied by three alternating outer circles, where each of the six outer circles touches two adjacent outer circles and de three alternating outer circles are equidistant from the central circle, have the same diameter and may be attached to the central circle. Preferably, these three alternating outer circles have a diameter of 0.74 to 1.3 times the diameter of the center circle, and more preferably have the same diameter as the center circle. Most suitably, such particles have a length to diameter (L / D) ratio of at least 2, preferably in the range of 2 to 5, the length being in the range of 1 to 25 mm.

If desired, the extrudates of the carrier can be dried before calcination, for example, at a temperature of from 100 to 300 ° C for from 30 minutes to 3 hours.

It is advisable to calcine in air, at a temperature in the range from 300 to 850 ° C, preferably from 400 to 825 ° C, for from 30 minutes to 4 hours.

Specifically, upon receipt of a molded carrier, when the oxide is an amorphous material, especially amorphous aluminosilicate, any general carrier preparation techniques known in the art can be used, wherein the SPP and pH are selected as described above. A preferred method for preparing such carriers includes dispersing a mixture of amorphous aluminosilicate in a suitable liquid, extruding the mixture and drying it by heating the resulting extrudates at a temperature in the range of 400 to 850 ° C., as described, for example, in WO-9410263, but the range is preferred from 650 to 850 ° C, more preferably from 700 to 825 ° C, especially from 750 to 810 ° C. The extrudates may be of any suitable form known in the art, for example, cylindrical, hollow cylindrical, multi-leaf or spiral multi-leaf. A preferred form of catalyst particles is multi-leaf, for example three-leaf. Typically, the extrudates have a nominal diameter of from 0.5 to 5 mm, preferably from 1 to 3 mm. After extrusion, the extrudates are dried. Drying can be carried out at elevated temperatures, preferably up to 300 ° C, more preferably up to 200 ° C. The drying period usually lasts up to 5 hours, preferably from 30 minutes to 3 hours. Then, after drying, the extrudates are preferably calcined at a very high temperature as described above, usually for a period of up to 5 hours, preferably from 30 minutes to 4 hours.

In addition, the present invention provides a catalyst composition which comprises a carrier of the present invention and at least one metal hydrogenation component selected from group VIb and group VIII.

At least one metal hydrogenation component is introduced into the catalyst according to the invention. This addition can be carried out at any stage of the catalyst preparation process using conventional techniques. For example, a hydrogenation component may be added to the oxide or to a mixture of oxide and binder during co-milling. However, preferably the hydrogenation component is added to the molded extrudates either before or after optional calcination using conventional impregnation techniques, for example, in one or more aqueous impregnating solutions of Group VIB and / or Group VIII metal salts. If the impregnation is carried out after calcining the molded extrudates, then it is advisable to use the procedure of additional drying and optional calcination.

In the description, references are made to the Periodic Table of Elements, which is shown on the inside cover of the CRC Handbook of Chemistry and Physics ('The Rubber Handbook'), 66th edition and uses the CAS version notation.

A suitable hydrogenation component is selected from nickel, cobalt, molybdenum, tungsten, platinum and palladium.

Examples of hydrogenating components that can thus be properly used include metals from group VIB (e.g. molybdenum and tungsten) and metals from group VIII (e.g. cobalt, nickel, iridium, platinum and palladium), their oxides and sulfides. Preferably, the catalyst composition may contain at least two hydrogenating 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 favorable results are obtained when metals in sulfide form are used for these combinations.

The catalyst composition according to the invention may contain up to 50 parts by weight of a hydrogenating component, based on metal, per 100 parts by weight (dry weight) of the total 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 parts by weight of the metal (s) from group VIB and / or from 0.05 to 10, more preferably from 0.5 to 8 and preferably from 1 to 6 parts by weight of metal (metals) from group VIII, calculated on the metal, per 100 parts by weight (dry weight) of the total catalyst composition.

Specifically, when the oxide is an amorphous and especially amorphous aluminosilicate, the amount of metal from group VIII and metal from group VIB in the catalyst may vary depending on the type of metal and the intended purpose of the catalyst, however, the amount of metal from group VIII will preferably be in the range of 0.5 up to 10 wt.%, while the amount of metal from group V1B will preferably be in the range from 3 to 30 wt.%, calculated on the metal, on the total weight of the catalyst. A preferred catalyst according to the present invention contains Nickel in an amount in the range from 1 to 6 wt.%, More preferably from 3 to 5 wt.%; and the amount of molybdenum is in the range from 6 to 18 wt.%, preferably from 10 to 15 wt.%, or the amount of tungsten is in the range from 10 to 25 wt.%, preferably from 15 to 22 wt.%.

As indicated previously, Group VIII and Group VIB metals can be deposited onto the support using any suitable methods known in the art, for example, by ion exchange, competing ion exchange, or by impregnation. Suitably, the metals can be precipitated by impregnating the support with an impregnating solution comprising the appropriate metal-containing compounds and optionally a chelating agent such as ethylene glycol, ethylenediamine, tartaric acid, malonic acid, citric acid, malic acid, nitrile acetic acid or ethylenediaminetetraacetic acid (EDTA). After impregnation, the catalyst is preferably dried at temperatures up to 200 ° C, then heated or calcined at a temperature in the range from 200 to 600 ° C.

It was found that the mesoporous carrier of the present invention provides for the formed catalyst an increased degree of metal incorporation with greater metal availability, as well as a lower CPC. In turn, this provides such an increased hydrogenation activity that not only a higher degree of hydrogenation of aromatic hydrocarbons is achieved, but also desulfurization can be carried out. This means that to meet the existing requirements for low sulfur content in the fuel, there is no need to use additional fuel treatment with a desulfurization catalyst.

In addition to the fact that the carrier according to the invention has an unusually low value of compact bulk density (COP), the catalyst composition of this invention has a CPC of not more than 0.70, preferably not more than 0.68 ml / g. Typically, the COP value is at least 0.55 ml / g; respectively, at least 0.6 ml / g, and preferably at least 0.62 ml / g. Typically, a catalyst composition based on an amorphous aluminosilicate carrier, especially a composition that is substantially free of aluminosilicate zeolite, has a CPC in the range of 0.60 to 0.65 ml / g.

Thus, for most preferred formulations containing amorphous aluminosilicates or Y-zeolite oxide materials, it is preferred that the Group VIb metal is tungsten and is present in an amount of from 20 to 27 wt.%, Most preferably from 21 to 27 wt.%, especially 21 wt.%, calculated on the basis of the trioxide and based on the total weight of the catalyst, and that the metal of group VIII is nickel and is present in an amount of 4 to 6 wt.%, preferably 5 to 6 wt.%, especially 5 wt. %, based on oxide and based on amounts molecular weight of the catalyst.

It may be difficult to introduce such a large amount of metals using conventional carrier impregnation with solutions. Applicants have found that the use of organic compounds having at least two functional groups selected from carboxyl, carbonyl and hydroxyl, but especially from carboxyl groups, promotes impregnation.

Therefore, the present invention provides a method for producing the catalyst composition of the invention, which comprises drying or calcining the support of the present invention, if necessary or desired, and precipitating at least one hydrogenation metal selected from group VIb and group VIII in the corresponding amount, and the deposition is carried out by impregnation with a solution containing an organic compound having at least two functional groups selected from carboxyl, carbonyl and g and hydroxyl groups. After precipitation, this composition is suitably dried at elevated temperature or aged at room temperature until drying takes place. It is most advisable to carry out drying at a temperature of from 100 to 200 ° C, for example 120 ° C. Preferably, the calcination is carried out at a temperature which, for example, is in the range of 200 to 500 ° C., but the calcination is optional.

Preferably, the method uses organic compounds, which are organic acids selected from citric acid, tartaric acid, oxalic acid, malonic acid and malic acid.

If the inorganic refractory oxide support material is an amorphous material and especially an amorphous alumina or, more preferably, an amorphous aluminosilicate that is substantially free of zeolite material, then it may be appropriate for the catalyst composition to further contain one or more promoting elements.

Promoters that enhance the performance of catalysts based on amorphous support materials are known and described in the art. For example, silicon promotion is disclosed for amorphous catalyst compositions for a variety of applications in WO 95/11753, US-A-5507940, EP-A-533451 and EP-A-586196. Other promoters are also known, especially for use in amorphous support hydrocracking catalysts, for example, US-A 2002/0160911 and US Pat. No. 6,251,261 describe the use of boron and phosphorus added as promoters to silicon.

Thus, the catalytic composition according to the invention, when using a molded carrier of this invention, essentially consisting of an amorphous inorganic refractory oxide material, may contain a promotion element selected from silicon, boron and phosphorus, preferably silicon and boron, especially silicon, in an amount of from 0 up to 20 wt.%, preferably from 0.1 to 15 wt.% and more preferably from 0.1 to 10 wt.%. When the promoter is silicon and the oxide contains silicon dioxide material, then the amount of silicon promoter is additional to the amount of silicon that is present in the silicon oxide material. A preferred oxide is aluminosilicate, and the promoter is selected from silicon and boron; most preferably, the promoter is silicon.

Various sources of silicon may be used. Thus, for example, Si (OEt) ₄ ethyl orthosilicate, siloxanes, polysiloxanes, silicones, silicone emulsions, halosilicates such as ammonium fluorosilicate (NH ₄ ) ₂ SiF ₆ or sodium fluorosilicate Na ₂ SiF _{6 can be used} . In addition, silicon molybdenum acid and its salts and silicon tungsten acid and its salts can advantageously be used. In addition, silicon can be added, for example, by impregnation with a solution of ethyl silicate in a water-alcohol mixture. Silicon can be added, for example, by impregnation with a silicon compound of the silicone type or silicic acid, which is suspended in water.

The source of boron can be boric acid, preferably orthoboric acid H ₃ BO ₃ , ammonium biborate or ammonium pentaborate, boron oxide or boric acid esters. Boron can be introduced, for example, as a mixture of boric acid, oxidized water and a basic organic compound that contains nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds from the pyridine and quinoline family, and compounds from the pyrrole family. Boron can be introduced, for example, in the form of a solution of boric acid in a water-alcohol mixture.

Suitable sources of phosphorus are orthophosphoric acid H ₃ PO ₄ and its salts and esters such as ammonium phosphates. For example, phosphorus can be introduced as a mixture of phosphoric acid and a basic organic compound that contains nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds from the pyridine and quinoline family, and compounds from the pyrrole family.

Applicants have found that the increase in catalytic activity resulting from the treatment of a hydrocracking catalyst with a liquid silicon-containing compound is mainly limited to catalysts based on an amorphous aluminosilicate carrier and is not observed when using an aluminosilicate zeolite carrier. Indeed, it has been found that in the presence of an aluminosilicate zeolite material in an amorphous aluminosilicate carrier, the beneficial properties imparted by the addition of a promoter are weakened. Accordingly, when the catalyst according to the invention contains a promoting element, then the support should be substantially free of aluminosilicate zeolite, i.e. the amount of aluminosilicate zeolite in the carrier is less than 1 wt.%, based on the total carrier, more preferably less than 0.5 wt.%, and even more preferably less than 0.1 wt.%. Most preferably, the carrier does not contain aluminosilicate zeolite.

The promoted hydrocracking catalyst used in the method of the present invention preferably contains at least 0.5 wt.% Silicon, based on the total weight of the catalyst, this silicon being introduced into the catalyst by treating the amorphous aluminosilicate support with a liquid silicon-containing compound. To avoid uncertainty, the amount of silicon introduced by treatment with a liquid silicon-containing compound is additional to the amount of silicon in the amorphous aluminosilicate carrier. Additional silicon can be introduced by treating the carrier with a liquid silicon-containing compound either before or after the metal components are deposited on the carrier, however, in a preferred embodiment of the present invention, the carrier is treated with a liquid silicon-containing compound after the metal components are deposited on the carrier.

A liquid silicon-containing compound can be any silicon-containing compound that can act as a source of silicon and which can be applied to a carrier in liquid form. Preferably, the liquid silicon-containing compound has the general formula:

in which each U, V, W, X, Y, and Z individually and independently may be —R, —OR, —Cl, —Br, —SiH ₃ , —COOR, —SiH _n Cl _m , wherein R is either an atom hydrogen, or an alkyl, cycloalkyl, aromatic, alkylaromatic, alkylcycloalkyl radical having from 1 to 30 carbon atoms, n and m are integers in the range from 1 to 3 and a is an integer in the range from 0 to 1000. Preferably, a is not more than 100, more preferably not more than 80, since liquids in which a is more than 100 have a high viscosity, and thus they are not it is convenient to put on the carrier.

In a particularly preferred embodiment, the liquid silicon-containing compound has the general formula:

in which each U, V, W, X, Y, and Z can individually and independently be —R or —OR, wherein R is either a hydrogen atom or an alkyl, cycloalkyl, alkylcycloalkyl radical having from 1 to 30 carbon atoms, and and is an integer in the range from 0 to 60.

Examples of liquid silicon-containing compounds that can be advantageously used in the present invention include alkyl orthosilicates such as ethyl orthosilicate (Si (OEt) ₄ ), methyltriethylsiloxane (Si (OEt) ₃ Me), and silicone oils such as polydimethylsiloxane.

A convenient way of treating the carrier with a liquid silicon-containing compound is to add liquid to the carrier, followed by heating the carrier treated with the silicon-containing liquid at an elevated temperature, usually in the range of 100 to 400 ° C. In order to facilitate processing, the liquid silicon-containing compound may optionally be dissolved in a suitable organic solvent, such as a lower alkane, however, in some circumstances, for example, when preparing a large amount of the catalyst, the liquid silicon-containing compound can be applied in pure form. As those skilled in the art can recognize, the amount of liquid silicon-containing compound deposited on the carrier may vary depending on the particular silicon-containing compound used, however, it is preferable that the amount of silicon deposited on the carrier, which is determined by elemental analysis, is at least at least 1 wt.%, calculated on the total catalyst. More preferably, this amount of silicon is in the range of 1 to 10 wt.%, Even more preferably 1 to 5 wt.%, Based on the total catalyst.

In a preferred embodiment of the present invention, a promoted hydrocracking catalyst is obtained by a method that involves impregnating an amorphous aluminosilicate carrier with a compound of a metal from group VIII and a metal from group VIB, heating the impregnated carrier at a temperature in the range of 150 to 500 ° C., treating the impregnated media liquid silicon-containing compound, followed by heating the catalyst treated with a silicon-containing liquid at a temperature in the range from 100 to 300 ° C.

In preparing the hydrocracking catalyst according to the aforementioned preferred embodiment, the activity of the catalyst can be optimized by varying the temperature at which the catalyst is heated. In this regard, very good results were achieved when the heating temperature, after impregnation with the metal compound, is in the range from 150 to 250 ° C, and the heating temperature, after treatment with the silicon compound, is in the range from 150 to 250 ° C.

In the method of the present invention, all hydrocracking catalysts according to the invention, promoted or non-promoted, are preferably sulfidized prior to use. These catalysts can be sulfidized by any technique known in the art, such as sulfidation outside the preparation zone or in the catalyst preparation zone. For example, sulfidation can be carried out by contacting the catalyst with a sulfur-containing gas, such as a mixture of hydrogen and hydrogen sulfide, a mixture of hydrogen and carbon disulfide, or a mixture of hydrogen and mercaptan, such as butyl mercaptan. Alternatively, sulfidation can be carried out by contacting the catalyst with hydrogen and a sulfur-containing hydrocarbon oil fraction, such as sulfur-containing kerosene or gas oil. In addition, sulfur can be introduced into the hydrocarbon oil fraction by adding an appropriate sulfur-containing compound, for example, dimethyl disulfide or tert-nonyl polysulfide.

In addition, the present invention has developed a method for converting hydrocarbon feedstocks to materials with a lower boiling point, which involves contacting the feedstock with hydrogen at an elevated temperature and elevated pressure in the presence of a catalyst composition according to the invention. Usually this method is called "hydrocracking".

Examples of such methods include one-stage hydrocracking, two-stage hydrocracking and sequentially ongoing hydrocracking. Definitions of these processes can be found in the book Introduction to zeolite science & practice, pp. 602 and 603, chapter 15 (entitled Hydrocarbon processing with zeolites), ed. van Bekkum, Flanigen, Jansen; published by Elsevier, 1991.

It has been found that especially for catalysts containing supports which preferably include amorphous aluminosilicates and / or zeolite materials according to the invention and with a high content of the metals mentioned above, the resulting catalyst also performs hydrodesulfurization of the remaining sulfur in conventional hydrocracking feedstocks. Moreover, the nitrogen-containing impurities present in the feed do not impede or deactivate the catalysts of the invention.

It can be recognized that the hydroconversion methods of the present invention can be carried out in any reaction vessel conventional in the art. Thus, the method can be carried out in a fixed bed reactor or with a moving catalyst bed. In addition, the catalyst according to the invention can be used in combination with any suitable cocatalyst or other materials conventional in the art. So, for example, the catalyst according to the invention can be used to form a packaged layer, together with one or more other catalysts used for hydroprocesses, for example, with a catalyst containing another zeolite, with a catalyst containing faujasite zeolite with a different unit cell size, with a catalyst containing an amorphous carrier, and the like. Various combinations of a packaged catalyst bed are proposed in the literature, for example, WO-99/32582; EP-A-310164; EP-A-310165 and EP-A-428224. As indicated above, in the case of the preferred catalyst compositions of the present invention, further post-treatment of the product with a hydroprocessing catalyst may be eliminated to remove residual sulfur.

The hydrocarbon feed used in the method according to the invention can boil over a wide range of temperatures. Types of raw materials include atmospheric gas oil; gas oil of the coking process; vacuum gas oil; deasphalted oils; fractions, for example, Fischer-Tropsch derived gas oils and waxes, wide and narrow residual fractions, recycle catalytic cracking products, thermal or catalytic cracking gas oils, and synthetic petroleum feedstock, optionally derived from tar sands, shale oil, biomass and boosting processes quality residuals. In addition, combinations of various hydrocarbon fractions can be used. Typically, the feed may include hydrocarbons having a boiling point of at least 330 ° C. The boiling range of the raw materials is usually from about 330 to 650 ° C, with preference being given to types of raw materials having a boiling range of from about 340 to 620 ° C. The feed may have a nitrogen content of up to 5000 parts by weight per million (parts by weight per million) and a sulfur content of up to 6% by weight. Typically, the nitrogen content is in the range from 250 to 2000 parts by weight per million and the sulfur content is in the range from 0.2 to 5 wt.%. It is possible and sometimes it may be desirable to subject part or all of the raw materials to pre-treatment, for example, hydrodeazotization, hydrodesulfurization (GES) or hydrodemetallization, all of these processes are known in the art.

The method according to the invention can be suitably carried out at a reaction temperature of from 250 to 500 ° C, preferably in the range from 300 to 450 ° C.

Preferably, the method of the invention is carried out at a total pressure (at the inlet of the reactor) in the range from 3 × 10 ⁶ to 3 × 10 ⁷ Pa, more preferably from 4 × 10 ⁶ to 2.5 × 10 ⁷ Pa, and even more preferably from 8 × 10 ⁶ to 2 × 10 ⁷ Pa. When the hydrocracking process is carried out at low pressure, for example, from 4 × 10 ⁶ to 1.2 × 10 ⁷ Pa, such a process may be called “soft hydrocracking”.

The partial pressure of hydrogen (at the inlet to the reactor) is preferably in the range from 3 × 10 ⁶ to 2.9 × 10 ⁷ Pa, more preferably from 4 × 10 ⁶ to 2.4 × 10 ⁷ Pa, and even more preferably from 8 × 10 ⁶ to 1.9 × 10 ⁷ Pa.

Usually use a volumetric feed rate in the range from 0.1 to 10 kg of raw material per 1 liter of catalyst per hour (kg · l ^-1 · h ^-1 ). Preferably, the volumetric feed rate is in the range from 0.1 to 10, especially from 0.2 to 8, and preferably from 0.5 to 5 kg · l ⁻¹ · h ⁻¹ .

The ratio of gaseous hydrogen to feed (total gas velocity or gas / feed ratio) used in the method according to the invention can usually be in the range from 100 to 5000 nl / kg, but the preferred range is from 200 to 3000 nl / kg, more preferably from 250 to 2000 nl / kg.

The hydrocracking method of the present invention can be used with particular advantage in a one-stage hydrocracking process, where the method provides a good indicator of the degree of conversion even when using raw materials containing nitrogen and sulfur impurities.

One application of one-stage hydrocracking is the production of middle distillate fractions. Middle distillate fractions are liquid fractions boiling over in the temperature range from 150 to 370 ° C and include products such as kerosene (from 150 to 250 ° C) and gas oil (from 250 to 370 ° C). There is a growing demand for middle distillate products, and essentially, there is always a need for a hydrocracking process for which high selectivity for middle distillates is observed with minimal formation of gaseous (C ₁ -C ₄ ) materials, i.e. aluminosilicate in a process whose products contain small amounts of gaseous materials and large quantities of middle distillate. In this regard, it was found that the hydrocracking method according to the invention has very high selectivity in the process of converting heavy distillate feedstocks, such as heavy gas oil or deasphalted oils, into middle distillate fractions.

Thus, a preferred embodiment of the present invention provides a one-step conversion of heavy gas oil or deasphalted oil to a middle distillate fraction.

The present invention will now be illustrated by the following examples.

Examples

Following the general procedure, catalyst supports and catalysts were prepared using different amounts of zeolite and inorganic refractory oxide in each catalyst formulation, as described below.

General methodology

The catalyst carrier is obtained by mixing zeolite with a refractory inorganic oxide in predetermined proportions. Water and acid are added in order to obtain the desired SPP and pH values and the mixture is milled in a mixer until a mixture suitable for extrusion is formed. The mixture is then extruded, together with an extrusion additive (Superfloc), to obtain extrudates having a three-leaf cross-sectional shape. These extrudates are dried under static conditions for 2 hours at 120 ° C and then calcined for 2 hours at 535 ° C. The catalyst particles thus obtained are cut into particles of the same length, their diameter being either 1.5 mm or 2.5 mm, which is measured from the top to the bottom of the nominal three-petal triangle.

Then, the components of the hydrogenating metals — nickel and tungsten — are introduced by impregnating the granules with a homogenized aqueous solution of nickel nitrate and ammonium metatungstate. Citric acid or malic acid is added to some impregnating solutions as indicated. The impregnated extrudates are dried at ambient conditions, in hot circulating air for 1 hour and then at 120 ° C for 2 hours and finally calcined at 500 ° C for 2 hours.

Activity Tests

The characteristics of the hydrocracking catalysts are determined in a number of model tests with a second stage sequential stream. The test is carried out in a single flow through microreactor, in which the upper catalyst layer containing 1 ml of C-424 catalyst (industrial catalyst from Criterion Catalysts & Technologies USA), diluted with 1 ml of particles (0.1 mm) of SiC, and the lower catalyst layer are loaded, containing 10 ml of the test catalyst, diluted with 10 ml of particles (0.1 mm) of SiC. The catalysts in both layers are pre-sulfidated prior to testing.

Each test involves the sequential contact of hydrocarbon feed (heavy gas oil) with the upper catalyst layer and then with the lower catalyst layer in a single flow mode of operation under the following operating conditions: volumetric feed rate of 1.5 kg of heavy gas oil per 1 liter of catalyst per hour (kg · l ^-1 · h ^-1 ), the ratio of gaseous hydrogen / heavy gas oil is 1440 nl / kg, the partial pressure of hydrogen sulfide is 5.6 × 10 ⁵ Pa (5.6 bar) and the total pressure is 14 × 10 ⁶ Pa ( 140 bar).

As a raw material for testing, a standard heavy gas oil was used, which has the following properties:

Carbon content 86.64 wt.% Hydrogen content 13.36 wt.% Sulfur Content (S) 122 ppm Nitrogen content (N) 12 ppm N-decylamine supplement 12.3 g / kg (equivalent to 1100 parts by weight / million nitrogen) Total Nitrogen (N) 1112 ppm Density (15/4 ° C) 0.8805 g / ml Density (70/4 ° C) 0.8463 g / ml Molecular mass 433 g Boiling point 355 ° C Boiling point 50 wt.% 425 ° C Boiling point 606 ° C The fraction boiling below 370 ° C 2.57 wt.% Fraction boiling above 540 ° С 10.0 wt.%

Hydrocracking rates are evaluated at a total conversion of between 40 and 90 wt.% For feed components boiling above 370 ° C. To compare the activity, the results, expressed as the temperature required to achieve a total conversion of 65 wt.% For the components of the feed boiling above 370 ° C, are shown in the tables below.

The activity of hydrodesulfurization (GOS) is determined using the same raw materials for testing and under the same conditions as indicated above, but in the absence of adding hydrogen sulfide.

Loss on ignition (IFR) is determined using the methodology described previously. Compact bulk density (COP) is determined following the method of ASTM D 4180-03, except that the ramming weight is placed on top of the test sample inside a 250 ml graduated cylinder tightly placed on a vibrating table, and the sample is evaluated without preliminary drying, separately introduced dry weight correction according to the formula:

Here, the SPP is determined in the same manner as previously described, but with heating to 485 ° C.

The total pore volume and mesopore volume are determined by mercury indentation porosimetry using ASTM D4284-03.

In carriers from C to K, the same USY zeolite Y is used with a large surface area, which is a very ultrastable zeolite Y, having a unit cell size of 24.32 Å, a molar ratio of silicon dioxide to alumina (OKA) of 29, BET surface area is 893 m ² / g and micropore volume is 0.298 ml / g. This zeolite is prepared as described in document WO 2004/047988. In this invention, the unit cell size is determined by x-ray diffraction using ASTM D 3942-80; OKA indicator is given for the volume or total OKA and is determined using chemical analysis; BET surface area is determined using the Brunauer, Emmett and Teller method (J.Am. Chm. Soc., 60, 309 (1938)) and ASTM D4365-95 using a single nitrogen adsorption point estimate for p / p ₀ equal to 0.03; micropore volume was estimated by the t-graph method using nitrogen as an adsorbate, as described by Lippens, Linsen and de Boer, Journal of Catalysis, 3-34 (1964).

The carriers used had the composition indicated below. All percentages are by weight based on the total carrier. Unless otherwise indicated, amorphous aluminosilicates are Al-Si: 55-45 wt.%, And alumina is wide-porous alumina, both supports are available from Criterion Catalysts and Technologies, USA (CC&T).

Carrier A has 10% USY of zeolite Y with an OKA of 10; 22.5% alumina; 62.5% of amorphous aluminosilicates.

Carrier B has 10% USY zeolite with an OKA value of 10; 90% amorphous aluminosilicates.

Carrier C has 48% USY zeolite Y with a large surface area; 8% alumina; 44% amorphous aluminosilicates.

Carrier D has a 50% USY zeolite Y with a large surface area; 8% alumina; 42% amorphous aluminosilicates.

Carrier E has 45% USY zeolite Y with a large surface area; 9% alumina; 46% amorphous aluminosilicates.

Carrier F has 45% USY zeolite Y with a large surface area; 9% alumina; 46% amorphous aluminosilicates.

Carrier G has 35% USY zeolite Y with a large surface area; 34% aluminosilicates (contains 6% silica, available from CC&T); 31% wide-porous alumina (available from CCIC).

Carriers H to K have 35% USY zeolite Y with a large surface area; 10% alumina; 55% amorphous aluminosilicates.

The catalysts used have the following metal content, expressed as wt.% Based on the total weight of the catalyst.

Catalysts 1, 2 and 14 have 5 wt.% Nickel and 21 wt.% Tungsten.

Catalysts 3, 4, 7 and 13 have 3.3 wt.% Nickel and 16 wt.% Tungsten.

Catalysts 5, 6 and 8-11 have 4 wt.% Nickel and 17 wt.% Tungsten.

The catalyst 12 has 2 wt.% Nickel and 6.5 wt.% Tungsten.

In the tables below, TL stands for triple leaf shape; TX means a molded trefoil, such as described in document WO 03/013725.

Carrier The form PPP mixture for extrusion, wt.% The pH of the extrusion mixture COP, g / ml Total pore volume (OD) for mercury, ml / g The volume of mesopores (for mercury), ml / g. % OD in mesopores BUT 1.6 mm 0.52 0.66 AT 1.6 mm 0.44 0.917 FROM 2.5 mm 54.80 3.4 0.52 0.516 0.368 71.31 D 2.5 mm 59.60 3.6 0.40 0.740 0.520 70.27 E 2.5 mm 56.80 3,7 0.43 0.696 0.490 70.40 F 2.5 mm 56.80 3,7 0.38 0.696 0.487 69.97 G 2.5 mm 60.40 5.8 0.42 0.864 0.459 53.12 N 2.5 mm 61,20 7.0 0.39 0.862 0.491 56.96 I 2.5 mm 61.60 4.2 0.42 0.782 0.558 71.35 J 2.5 mm 61.00 4.7 0.40 0.839 0.579 69.01 TO 2.5 mm 58.60 4.4 0.42 0.778 0.576 74.04

The effect of CPC / pore volume of the carrier

Catalyst Carrier CPC media, g / ml The pore volume of the carrier (Hg), ml / g T ° C for 65 wt.% 370 ° C + C1-C4 wt.% C5-150 ° C. Wt.% 150-370 ° C. Wt.% Monoar,% beats Diar,% beats Triarom. +% beats one BUT 0.52 0.66 398 2,8 27.4 69.8 47 81 75 2 AT 0.44 0.92 399 2,3 27.7 70.1 44 80 75 3 FROM 0.52 0.52 374 4.7 36.8 58.4 28 71 64 four D 0.40 0.74 371 4.1 34.5 61,4 44 85 78 % beats means wt.% removal compared to the original amount in the feed.

In catalysts 1 and 2, a decrease in CPC alone gives a slight improvement in activity or selectivity. However, a decrease in CPC and an increase in the mesopore volume shown in catalyst 4 according to the invention leads to increased activity, selectivity and hydrogenation ability compared to catalyst 3.

Effect of shape and surface area / metal content

Catalyst Carrier Shape mm CPC media, g / ml The surface area of the carrier (Hg), m ² / g Ni% W% T ° C for 65 wt.% 370 ° C + C1-C4 wt.% C5-150 ° C. Wt.% 150-370 ° C. Wt.% Monoar,% beats Diar,% beats Triarom. +% beats 5 E TL2.5 0.43 257 four 17 377 4.8 35,2 60.0 37 82 76 6 F TX2.5 0.38 257 four 17 376 4,5 33.5 62.0 38 81 74 7 ² F TX2.5 0.38 257 3.3 fourteen 375 3.2 33.8 63.0 38 82 78

The effect of mesopore volume

Catalyst Carrier CPC carrier g / ml Carrier Pore Volume (Hg) ml / g Mesopore Volume (Hg) ml / g T ° C for 65 wt.% 370 ° C + C1-C4 wt.% C5-150 ° C. Wt.% 150-370 ° C. Wt.% Monoar. % beats Diar,% beats Triarom. +% beats 8 ² G 0.42 0.86 0.46 381 4.4 34.3 61.3 37 81 70 9 ² H 0.39 0.86 0.49 380 4.3 33.8 61.9 39 82 76 10 ² I 0.42 0.78 0.56 380 4.0 34.1 61.9 43 85 75 11 ¹ J 0.40 0.84 0.58 377 3.3 33.6 63.1 42 83 77

Effect of metal content

Catalyst Carrier Ni,% W% T ° C for 65 wt.% 370 ° C + C1-C4 wt.% C5-150 ° C. Wt.% 150-370 ° C. Wt.% Monoar. % beats Diarom. % beats Triarom. +% beats GOS,% beats 12 ¹ TO 2 6.5 382 3.8 35 61.0 44 81 72 76 13 ¹ TO 3.3 16,2 380 3.3 33 63,2 71 91 83 92 14 ¹ TO 5 21 378 3,5 31 65,4 77 94 87 93 ¹ impregnating solution contains citric acid;
² impregnating solution contains malic acid;
% beats means wt.% removal compared to the original amount in the feed.

Claims (18)

1. A molded carrier for a hydrocracking catalyst that contains at least zeolite Y and one inorganic refractory oxide, the support having a unimodal pore size distribution in which at least 50% of the total pore volume are pores having a diameter of the range from 4 to 50 nm, and in which the pore volume in these pores is at least 0.4 ml / g, where all measurements were performed by mercury porosimetry. 2. The catalyst carrier according to claim 1, in which the pore volume in pores with a diameter of from 4 to 50 nm is at least 0.5 ml / g, preferably in the range from 0.5 to 0.8 ml / g . 3. The catalyst carrier according to claim 1 or 2, in which at least 60%, preferably in the range from 60 to 90% of the total pore volume, are pores having a diameter in the range from 4 to 50 nm. 4. The catalyst carrier according to any one of claims 1 and 2, which contains an amorphous material from aluminosilicates or crystalline aluminosilicate faujasite material. 5. The catalyst carrier according to any one of claims 1 and 2, which has a value of compact bulk density in the range from 0.35 to 0.50 g / ml 6. A method of obtaining a catalyst carrier for hydrocracking according to any one of claims 1 to 5, which includes forming a mixture containing at least zeolite Y and a refractory oxide, in which the mixture has an annealing loss (IFR) in the range from 55 to 75% 7. The method according to claim 6, in which the molding is carried out by extrusion. 8. The method according to claim 7, in which the mixture is an extrusion mixture, which has a pH value in the range from 3.5 to 7.0. 9. The method according to any one of claims 6 to 8, in which the PPP value is in the range from 58 to 75%, preferably from 60 to 65%, and the pH is in the range from 3.5 to 5.0, preferably from 4, 0 to 5.0. 10. The method of claim 8, in which to adjust the pH in the extrusion mixture add acid, which is selected from acetic acid and nitric acid. 11. The catalyst carrier for hydrocracking, which is obtained by the method according to any one of claims 6 to 10. 12. The catalytic composition for hydrocracking, which includes a carrier according to any one of claims 1 to 5 and 11, at least one component of a hydrogenating metal, which is selected from metals of group VIB and group VIII, and optionally at least one a promotion element selected from silicon and boron in the case when the carrier practically does not contain aluminosilicate zeolite. 13. The catalytic composition according to item 12, in which the metal of group VIB is tungsten, present in an amount of from 20 to 27 wt.%, Preferably 21 wt.%, Calculated on the trioxide and based on the total weight of the catalyst, and a metal of group VIII represents nickel, present in an amount of from 4 to 6 wt.%, preferably 5 wt.%, calculated on the oxide and based on the total weight of the catalyst. 14. A method of obtaining a catalytic composition for hydrocracking according to item 12 or 13, which includes optional calcination of the carrier according to any one of claims 1 to 5 and 11, and the deposition of at least one hydrogenating metal selected from group VIB and group VIII, in an appropriate amount, the precipitation being carried out by impregnation with a solution containing an organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. 15. The method according to 14, in which the organic compound is an organic acid selected from citric acid, tartaric acid, oxalic acid, malonic acid and malic acid. 16. The catalytic composition for hydrocracking, which is obtained by the method according to 14 or 15. 17. The hydrocracking method, which includes contacting the hydrocarbon feed with the catalytic composition according to any one of paragraphs.12, 13 and 16 at elevated temperature and elevated pressure. 18. The use of the catalytic composition according to any one of paragraphs.12, 13 and 16 as a combined hydrocracking catalyst and additionally desulfurization of hydrocarbons.