RU2796542C2 - Phosphorus-containing molecular sieve with high silicon dioxide content, its production and application - Google Patents

Abstract

FIELD: molecular sieves; hydrocracking

SUBSTANCE: group of inventions relates to the field of molecular sieves and hydrocracking, in particular, to a phosphorus-containing molecular sieve with a high content of silicon dioxide, a hydrocracking catalyst containing it, their production and use. A phosphorus-containing molecular sieve for the production of a hydrocracking catalyst is presented, containing from 86.5 to 99.8 wt.% silicon, from 0.1 to 13.5 wt.% aluminium and from 0.01 to 6 wt.% of phosphorus in terms of oxides and relative to the dry weight of the molecular sieve, wherein the molecular sieve is characterized by an x-ray diffraction pattern containing at least three diffraction peaks, the first intense peak being present at a diffraction angle of 5.9 to 6.9°; the second intense peak is present at a diffraction angle of 10.0 to 11.0°; and a third intense peak is present at a diffraction angle of 15.6° to 16.7°, and a method for producing the same, comprising the steps of: a) hydrothermally treating a phosphorus-containing molecular sieve raw material; b) adding water to the hydrothermally treated molecular sieve material obtained in step a) to form a first slurry, heating the first slurry, and adding the first acid solution to the first slurry; carrying out the reaction and collecting the first solid product; c) adding water to the first solid product obtained in step b) to form a second slurry, heating the second slurry and adding a second acid solution to the second slurry; carrying out the reaction and collecting the second solid product, drying it. In another variant, a hydrocracking catalyst is provided containing, based on the dry weight of the catalyst, from 45 to 90 wt.% of the carrier, on a dry matter basis; from 1 to 40 wt.% component of the first metal in terms of metal oxides; and from 1 to 15 wt.% component of the second metal in terms of metal oxides; the carrier contains a phosphorus-containing molecular sieve with a high content of silicon dioxide and a refractory inorganic oxide, and the mass ratio of the phosphorus-containing molecular sieve with a high content of silicon dioxide and refractory inorganic oxide is 0.03:1 to 20:1; wherein the first metal component contains a Group VIB metal, the second metal component contains a Group VIII metal, as well as a method for producing the same, comprising the following steps: i) mixing a phosphorus-containing molecular sieve with a high content of silicon dioxide with a refractory inorganic oxide to form a carrier; and ii) contacting the carrier with an impregnation solution containing the first metal precursor and the second metal precursor to impregnate, then drying and calcining the impregnated material. Also provided is the use of a hydrocracking catalyst in the hydrocracking of a hydrocarbon feedstock.

EFFECT: group of inventions provides a phosphorus-containing molecular sieve with a high content of silicon dioxide and a method for its production, wherein said molecular sieve exhibits increased hydrocracking activity in the presence of nitrogen-containing compounds when used in the production of hydrocracking catalysts.

22 cl, 1 dwg, 5 tbl, 6 ex

Description

Cross-reference to related applications

The present application claims the priority of PRC Patent Application No. 201811259943.0 entitled "Phosphorus-Containing High Silica Molecular Sieve, Its Production and Use" filed on October 26, 2018, and PRC Patent Application No. 201811261400.2 entitled "Hydrocracking Catalyst Containing Molecular Sieve with a high content of silicon dioxide, its production and application" and filed on October 26, 2018, the contents of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD OF THE INVENTION

The present application relates to the field of molecular sieves and hydrocracking, in particular, to a phosphorus-containing molecular sieve with a high content of silicon dioxide, a hydrocracking catalyst containing it, their preparation and use.

State of the art of the present invention

Commercial hydrocracking feedstocks contain heavy and low grade fractions such as vacuum gas oil (VGO), which contain large amounts of polycyclic aromatics and naphthenes, as well as significant amounts of nitrogen compounds. The weight percentage of nitrogen in hydrocracking feedstocks is typically 0.1% to 0.2%. However, as a result of secondary petrochemical processing such as coking, solvent deasphalting, etc., nitrogen-containing compounds are often formed in a significant amount, and the nitrogen content in the resulting final material often exceeds 0.3% and in some cases even reaches 0, 6%, which makes it difficult to reduce the nitrogen content after treatment with conventional refinery catalysts to the level of 10 to 100 ppm that conventional types of molecular sieve hydrocracking catalysts can withstand. Typically, weakly acidic amorphous aluminum silicate or silicic alumina is used as the main acid component of high nitrogen hydrocracking catalysts.

According to prior art documents, the synthesis of weakly acidic aluminum silicate is generally carried out at the desired pH by using a brine containing silica and alumina, or by adding alumina to a silica precursor or adding silica to an alumina precursor and carrying out and then reacting with obtaining a tetrahedral structure of double alumina, as a result of which an acid center is created in the sample.

PRC Patent No. ZL97121663.0 discloses a hydrocracking catalyst particularly suitable for producing middle distillates, which contains an amorphous silica alumina component, an alumina microporous binder, at least one Group VIB element, and at least one Group VIB element. VIII, wherein the content of amorphous double silica and alumina is 30 to 60 wt.%, the total content of hydrogenation-catalyzing metal oxides is 20 to 35 wt.%, and the remaining mass is microporous binder based on alumina, and this catalyst is different in that its specific surface area is from 150 to 300 m ² /g, the pore volume is from 0.25 to 0.50 ml/g, in the distribution of pores from 4 to 15 nm are from 60 to 90%, and determined according to the infrared spectrum, the acidity is from 0.30 to 0.50 mmol / g.

Although materials with a certain acidity can be obtained by these methods, during the synthesis, in order to maintain the stability of the matrix structure, the resulting product contains a large amount of non-framework six-coordinate aluminum. As a result, the structure of the resulting material has only a short-range order, and it is difficult to obtain a structure from a long-range order.

Brief summary of the present invention

The object of the present application is to provide a phosphorus-containing high silica molecular sieve containing its hydrocracking catalyst, their preparation and use, said molecular sieve to exhibit increased hydrocracking activity in the presence of nitrogen-containing compounds when used in the preparation of hydrocracking catalysts.

To solve the above problem, according to an aspect of the present application, a phosphorus-containing molecular sieve with a high content of silicon dioxide is provided, containing from about 86.5 to 99.8 wt.% silicon, from about 0.1 to 13.5 wt.% aluminum, and from about 0.01 to 6 wt.% phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve,

moreover, the molecular sieve is characterized by an X-ray diffraction pattern containing at least three diffraction peaks, while the first intense peak is present at a diffraction angle of approximately 5.9 to 6.9 °, the second intense peak is present at a diffraction angle of approximately 10, 0 to 11.0°, and a third intense peak is present at a diffraction angle of approximately 15.6 to 16.7°,

preferably the molecular sieve has a pore volume of about 0.20 to 0.50 ml/g and a specific surface area of about 250 to 670 m ² /g.

According to another aspect of the present application, a process is provided for producing a phosphorus-containing molecular sieve with a high content of silicon dioxide, comprising the following steps:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 8.0 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material; moreover, the source material of the phosphorus-containing molecular sieve has a phosphorus content of approximately 0.1 to 15 wt.%, a sodium content of approximately 0.5 to 4.5 wt.%, a silicon content of approximately 70 to 85 wt. %, and an aluminum content of approximately 16.0 to 21.0 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) to form a first slurry, heating the first slurry to a temperature of about 40 to 95° C., then adding the first acid solution to the first slurry while maintaining the temperature at such that the acidified first slurry has a pH of about 2.3 to 4.0, reacting at a constant temperature for about 0.5 to 20 hours and collecting the first solid product;

c) adding water to the first solid product obtained in step (b) to form a second slurry, heating the second slurry to a temperature of about 40 to 95° C., then, while maintaining a constant temperature, adding a second acid solution to the second slurry in such amount such that the acidified second slurry has a pH of about 0.8 to 2.0, reacting at a constant temperature for about 0.5 to 20 hours, and collecting the second solid.

According to a further aspect of the present application, the use of a high silica phosphorus-containing molecular sieve according to the present application in the hydrocracking of a hydrocarbon feedstock is provided, comprising the step of contacting the hydrocarbon feedstock with a hydrocracking catalyst containing said high-silica phosphorus-containing molecular sieve.

According to a further aspect of the present application, a hydrocracking catalyst is provided comprising, based on the dry weight of the catalyst, from about 45 to 90% by weight of carrier, on a dry matter basis; from about 1 to 40 wt.% component of the first metal in terms of metal oxides and from about 1 to 15 wt.% component of the second metal in terms of metal oxides;

wherein the carrier comprises a high silica phosphorus molecular sieve and a refractory inorganic oxide, wherein the weight ratio of the high silica phosphorus molecular sieve to the refractory inorganic oxide is about 0.03:1 to about 20:1;

wherein the first metal component comprises a Group VIB metal, the second metal component comprises a Group VIII metal, and the high silica phosphorus molecular sieve is the high silica phosphorus molecular sieve of the present application.

According to a further aspect of the present application, there is provided a process for the preparation of a hydrocracking catalyst comprising the following steps:

mixing a phosphorus-containing molecular sieve with a high content of silicon dioxide according to the present application with a refractory inorganic oxide to form a carrier; And

contacting the carrier with an impregnation solution containing the first metal precursor and the second metal precursor for impregnation.

According to a further aspect of the present application, the use of the hydrocracking catalyst of the present application in the hydrocracking of a hydrocarbon feedstock is provided, comprising the step of contacting the hydrocarbon feedstock with said hydrocracking catalyst.

According to the present application, the starting material of the phosphorus-containing molecular sieve is subjected to hydrothermal treatment and two stages of acid treatment are carried out under certain conditions to obtain a phosphorus-containing molecular sieve with a high content of silicon dioxide and new structural features. The high silica phosphorus-containing molecular sieve of the present application exhibits enhanced hydrocracking activity in the presence of nitrogen-containing compounds when used to prepare hydrocracking catalysts. Accordingly, a hydrocracking catalyst prepared using a phosphorus-containing molecular sieve with a high content of silica also exhibits an enhanced hydrocracking activity.

Other features and advantages of the present application will be detailed below in the description of this document.

Brief description of the figures

The figures are presented to assist in the understanding of the present application and should be considered as part of the present description. The present application will be illustrated with the presentation of figures and embodiments, which are described hereinafter, and which should not be construed as limiting.

Among the figures in Fig. 1 shows X-ray diffraction patterns of the molecular sieves obtained in Preparative Examples 1 and 2 and Comparative Preparative Examples 1-3.

Detailed disclosure of the present invention

Hereinafter, the present application will be described in more detail and by introducing the relevant embodiments and figures, and it should be noted that the embodiments described herein are presented solely for the purpose of illustrating and clarifying the present application, and at the same time they are not contemplated in any way in as restrictive.

Any numerical values (including the end values of numerical ranges) that are presented herein are not limited to the respective exact values, but should be construed as representing any values in the vicinity of the specified exact value, for example, all possible values within 5% of specified exact value. In addition, for any numerical range provided herein, one or more new numerical ranges may be obtained by an arbitrary combination of end values of the range, a particular end value and another value that is within the range, or various specific values that are within the range. . Such new numerical ranges should also be considered as specifically described herein.

Unless otherwise indicated, terms used herein have the meanings commonly understood by those skilled in the art; and if terms are defined herein and their definitions differ from the common understanding in the art, then the definitions provided herein shall prevail.

According to the present application, the dry weight of the material means the weight of the solid product obtained by calcining the material at a temperature of 600°C for 3 hours.

In the context of the present application, in addition to objects that are specified in a certain way, one or more objects that are not mentioned are considered the same as objects known in the art, without any change. In addition, any of the embodiments that are described herein may be freely combined with one or more of the other embodiments that are described herein, and the technical solutions or ideas thus obtained are considered as part of the original disclosure. or the original description of the present application, and should not be considered as a new subject that was not described or predicted in this document, unless experts in the art understand that such a combination is clearly unreasonable.

All patent and non-patent documents cited herein, including, but not limited to, tutorials and journal articles, are hereby incorporated by reference in their entirety.

According to the first aspect of the present application, a phosphorus-containing high silica molecular sieve containing from about 86.5 to 99.8 wt.%, preferably from about 90 to 99.8 wt.% silicon, from about 0.1 to 13, 5 wt.%, preferably from about 0.1 to 9.0 wt.% aluminum and from about 0.01 to 6 wt.%, preferably from about 0.01 to 2.5 wt.% phosphorus in terms of oxides and relative to the dry weight of the molecular sieve. Optionally, the molecular sieve may further contain sodium in a small amount, which may be from about 0.01 to 1.0 wt.%, for example, from about 0.01 to 0.6 wt.% in terms of oxide and in relation to dry weight of the molecular sieve.

In a preferred embodiment, the phosphorus-containing high silica molecular sieve contains from about 90 to 99.8 wt.% silicon, from about 0.1 to 9.0 wt.% aluminum, and from about 0.01 to 2.5 wt. .% phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve. Optionally, the molecular sieve may further contain from about 0.01 to 1.0 wt.%, for example, from about 0.01 to 0.6 wt.%, sodium in terms of oxide and in relation to the dry weight of the molecular sieve.

According to a further preferred embodiment, the phosphorus-containing high silica molecular sieve contains from about 95.0 to 99.0 wt.% silicon, from about 0.5 to 5.0 wt.% aluminum, and from about 0.1 to 1 0 wt.% phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve. Optionally, the molecular sieve may further contain from about 0.01 to 0.6 wt.% sodium, calculated as oxide and based on the dry weight of the molecular sieve.

In a preferred embodiment, the molecular sieve may have a pore volume of about 0.20 to 0.50 ml/g, preferably about 0.30 to 0.45 ml/g, such as about 0.33 to 0.42 ml/g; and/or the molecular sieve may have a specific surface area of from about 250 to 670 m ² /g, preferably from about 260 to 600 m ² /g, for example, from about 400 to 600 m ₂ /g.

According to a further preferred embodiment, the molecular sieve has a pore volume of about 0.20 to 0.50 ml/g and a specific surface area of about 260 to 600 m ₂ /g.

According to the present application, the molecular sieve has structural features that differ from traditional aluminosilicate materials. In particular, the molecular sieve is characterized by an X-ray diffraction pattern containing at least three diffraction peaks, wherein the first intense peak is present at a diffraction angle of about 5.9 to 6.9°, preferably from about 6.1 to 6.8° ; the second intense peak is present at a diffraction angle of about 10.0 to 11.0°, preferably about 10.2 to 10.7°; and the third intense peak is present at a diffraction angle of about 15.6 to 16.7°, preferably about 15.8 to 16.5°, wherein the diffraction angle is a value of 26 at which the diffraction peak in the X-ray diffraction pattern reaches its highest value.

According to the present application, the ordinal numbers "first", "second", "third", etc. in expressions denoting the first, second and third intense peaks, etc., are a sequence of relative intensities of said diffraction peaks, determined by the height of the respective peaks, where the first intense peak means the diffraction peak with the highest peak height in the X-ray diffraction pattern, the second intense peak means the diffraction peak with the second highest peak height in the X-ray diffraction pattern, the third strong peak means the diffraction peak with the third largest peak height in the X-ray diffraction pattern, and so on.

It is well known to those skilled in the art that when examining the structure of a material by X-ray diffraction analysis (XRD), the D value (interplanar spacing) can generally be calculated from the wavelength and diffraction angle, and the structure can be tentatively identified based on the features of three the most intense diffraction peaks (i.e. the first, second and third peaks mentioned in this application). The concept of three intense peaks can be found in Methods for the Study of Heterogeneous Catalysts, ed. Yuangen Yin, Beijing Chemical Industry Press, 1988, p. 140-170.

According to a preferred embodiment, on a molecular sieve x-ray diffraction pattern, I ₁ /I _23.5-24.5° may be from about 3.0 to 11.0, including from about 4.0 to 10.5, or from about 4, 6 to 10.1; I ₂ /I _23.5-24.5° may be from about 2.5 to 8.0, including from about 2.9 to 7.0 or from about 3.0 to 6.4; I ₃ / I _23.5-24.5° may be from about 1.0 to 4.5, including about 1.5 to 4.0 or about 2.1 to 3.8; where I ₁ is the peak height for the first intense peak, I ₂ is the peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for peak at a diffraction angle of approximately 23.5 to 24.5°.

According to a further preferred embodiment, in a molecular sieve X-ray diffraction pattern, I ₁ /I _23.5-24.5° may be from about 3.0 to 11.0, I ₂ /I _23.5-24.5° can be from about 2.9 to 7.0, I ₃ /I _23.5-24.5° may be from about 1.0 to 4.0, while I ₁ is the peak height for the first intense peak, I ₂ is the height peak for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of about 23.5 to 24.5°.

According to some of the following preferred embodiments, in a molecular sieve x-ray diffraction pattern, I ₁ /I _23.5-24.5° may be approximately 4.0 to 10.5, I ₂ /I _23.5-24.5° may be approximately from 2.9 to 7.0, I ₃ /I _23.5-24.5° may be from about 1.5 to 4.0, while I ₁ is the peak height for the first intense peak, I ₂ is peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of about 23.5 to 24.5°.

In some of the following preferred embodiments, the molecular sieve is characterized by an X-ray diffraction pattern containing at least five diffraction peaks, wherein the fourth intense peak may be present at a diffraction angle of about 20.4 to 21.6°, preferably about 20.8 to 21 .4° and the fifth intense peak may be present at a diffraction angle of about 11.8 to 12.8°, preferably about 12.1 to 12.6°.

According to a further preferred embodiment, I ₄ /I _23.5-24.5° may be from about 1.0 to 4.0, including from about 1.1 to 3.0 or from about 1.2 to 2, 3, I ₅ /I _23.5-24.5° may be from about 1.0 to 2.0, including from about 1.0 to 1.6 or from about 1.0 to 1.2, and I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24 .5°. The concept of the fourth intense peak and the fifth intense peak can be understood with reference to the description of the three intense peaks, and will not be re-described here.

According to some of the following preferred embodiments, I ₄ /I _23.5-24.5° may be from about 1.1 to 3.0, I ₅ /I _23.5-24.5° can be from about 1.0 to 1.6, where I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24.5°.

The high silica phosphorus-containing molecular sieve of the present application exhibits enhanced hydrocracking activity in the presence of nitrogen-containing compounds when used to prepare hydrocracking catalysts.

According to a second aspect of the present application, there is provided a process for producing a high silica content phosphorus-containing molecular sieve, comprising the steps of:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 8.0 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material; moreover, the source material of the phosphorus-containing molecular sieve has a phosphorus content of approximately 0.1 to 15 wt.%, a sodium content of approximately 0.5 to 4.5 wt.%, a silicon content of approximately 70 to 85 wt. %, and an aluminum content of approximately 16.0 to 21.0 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) to form a first slurry, heating the first slurry to a temperature of about 40 to 95° C., then adding the first acid solution to the first slurry while maintaining the temperature at in such an amount that the acidified first slurry has a pH of about 2.3 to 4.0, preferably about 2.5 to 4.0, reaction at constant temperature for about 0.5 to 20 hours, and collecting first solid product; And

c) adding water to the first solid product obtained in step (b) to form a second slurry, heating the second slurry to a temperature of about 40 to 95° C., then, while maintaining a constant temperature, adding a second acid solution to the second slurry in such amount such that the acidified second slurry has a pH of about 0.8 to 2.0, preferably about 1.0 to 2.0, reacting at a constant temperature for about 0.5 to 20 hours, and collecting the second solid product.

According to a preferred embodiment, the process for producing a high silica content phosphorus-containing molecular sieve comprises the steps of:

a) carrying out hydrothermal treatment of the phosphorus-containing molecular sieve starting material at a temperature of about 400 to 650°C, for example, about 560°C, a pressure of about 0.5 to 5 MPa, for example, about 0.8 MPa, and in the presence of steam for about 1 to 7 hours, such as about 3 hours, to form a hydrothermally treated molecular sieve material; wherein the starting material of the phosphorus-containing molecular sieve has a phosphorus content of approximately 0.1 to 6 wt.%, for example, approximately 1.37 wt.%, a sodium content of approximately 0.5 to 3.0 wt.%, for example, about 1.44 wt.%, a silicon content of about 70 to 80 wt.%, for example, about 76.7 wt.%, and an aluminum content of about 18.0 to 21.0 wt.% , for example, approximately 20.5 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) to form a first slurry, heating the first slurry to a temperature of about 50 to 85°C, for example about 80°C, then adding the first acid solution into the first suspension while maintaining the temperature in such an amount that the acidified first suspension has a pH value of about 2.5 to 3.5, for example, about 2.8, carrying out the reaction at a constant temperature for about 1 to 10 hours, for example, approximately 4 hours and collection of the first solid product; And

c) adding water to the first solid product obtained in step (b) to form a second slurry, heating the second slurry to a temperature of about 50 to 85°C, for example about 80°C, then adding the second acid solution into the second suspension in such an amount that the acidified second suspension has a pH value that is from about 1.0 to 1.8, for example, about 1.4, carrying out the reaction at a constant temperature for about 1 to 10 hours, for example, approximately 3 h and the collection of the second solid product.

In some embodiments of the present application, in step (a), the phosphorus-containing molecular sieve feedstock means a phosphorus-containing molecular sieve. In the case of using the raw material of the phosphorus-containing molecular sieve according to the present application, phosphorus oxide and aluminum compounds outside the framework of the molecular sieve can improve the stability of the framework, and as a result, the performance of the molecular sieve can be further improved. The phosphorus-containing molecular sieve starting material may have a faujasite-type molecular sieve structure, and is preferably a phosphorus-containing Y molecular sieve, which may have a lattice parameter of about 2.425 to 2.47 nm, such as about 2.456 nm, a specific surface area of about from 250 to 750 m ² /g, for example, about 672 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g, for example, about 0.357 ml/g.

In addition, the selection of the Y molecular sieve can vary widely, provided that the phosphorus-containing molecular sieve starting material can meet the above requirements. For example, the Y molecular sieve may be selected from the group consisting of NaY, HNaY (H type Y molecular sieve), REY (rare earth Y molecular sieve), USY (Ultra stable Y molecular sieve), etc. The cationic positions of the phosphorus-containing Y molecular sieve may be occupied by one or more sodium ions, ammonium ions, and hydrogen ions; or, alternatively, sodium, ammonium and hydrogen ions can be replaced in whole or in part with other ions by conventional ion exchange before or after the introduction of phosphorus into the molecular sieve. The starting material of the phosphorus-containing molecular sieve may be a commercial product, or it may be obtained in accordance with any existing methods. For example, the raw material of the phosphorus-containing molecular sieve can be obtained according to the method described in PRC Patent No. ZL00123139.1 for producing USY molecular sieves, or the method described in PRC Patent No. ZL200410071122.6 for producing PUSY molecular sieves, and other methods, the details of which are not described in this document.

According to the present application, the suspension formation procedure (also known as suspension) carried out in step (b) and step (c) is well known to those skilled in the art. In some preferred embodiments, in step (b), the weight ratio of the water in the first slurry resulting from the slurry to the dry weight of the phosphorus-containing molecular sieve feedstock may be from about 14:1 to about 5:1, such as about 10:1; and/or in step (c), the weight ratio of the water in the second slurry to the dry weight of the phosphorus-containing molecular sieve feedstock may be from about 0.5:1 to about 20:1, for example, about 10:1.

In some preferred embodiments of the present application, in step (b), the first slurry is heated to a temperature of about 50 to 85°C, such as about 80°C, then the first acid solution is continuously added to the first slurry while maintaining the temperature to until the desired pH of the acidified first slurry is obtained. The amount of first acid solution added may vary widely depending on the nature of the phosphorus-containing molecular sieve starting material and the conditions of the hydrothermal treatment in step (a). As those skilled in the art would appreciate, the first acid solution may be added in any amount sufficient to ensure the pH of the acidified first slurry is within the desired range, as described above. The rate of addition of the first acid solution is not limited in a certain way and may vary over a wide range.

According to some preferred embodiments of the present application in step (b), the addition of the first acid solution may be repeated (for example, 1 to 5 times), the resulting mixture may be allowed to react at a constant temperature for a period of time after each addition of the acid, and then further additions of acid may be made until the acidified first slurry has a pH within the desired range. The first acid solution may have an acid concentration of about 0.1 to 15.0 mol/l, preferably about 0.1 to 5.0 mol/l, such as about 2.0 mol/l, and the pH is from about 0.01 to 3. The acid in the first acid solution may be any conventional inorganic acid and/or organic acid, and for example, it may be at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid, and preferably selected from sulfuric acid and nitric acid.

According to some preferred embodiments of the present application, in step (c), the second slurry is heated to a temperature of about 50 to 85°C, such as about 80°C, and then the second acid solution is continuously added to the second slurry while maintaining the temperature to until the desired pH of the acidified second slurry is obtained. The addition of the second acid solution can be carried out as follows: the second acid solution is added to the second suspension at a rate of from about 0.05 to 15 mol/h, preferably from about 0.05 to 10 mol/h, more preferably from about 2 to 8 mol/h, for example, approximately 5 mol/h in terms of H ⁺ and in relation to 1 l of the second suspension. According to the present application, the acid is added at a relatively low rate in step (c) such that the dealumination process becomes more moderate, which is favorable for improving the performance of the molecular sieve.

According to some preferred embodiments of the present application in step (c), the addition of the second acid solution may be repeated (for example, 1 to 5 times), the resulting mixture may be allowed to react at a constant temperature for a period of time after each addition of the acid, and then further additions of acid may be made until the pH of the acidified second slurry is within the desired range. The second acid solution may have an acid concentration of about 0.1 to 15.0 mol/l, preferably about 0.1 to 5.0 mol/l, such as about 2.0 mol/l, and the pH is from about 0.01 to 3. The acid in the second acid solution may be any conventional inorganic acid and/or organic acid, and for example, it may be at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid, and preferably selected from sulfuric acid and nitric acid. The second acid solution and the first acid solution may be the same or different in type and concentration, and preferably they are the same acid solution.

According to some preferred embodiments of the present application, the method may further include the steps of collecting the second solid product and then washing with water and drying to obtain a phosphorus-containing molecular sieve with a high content of silicon dioxide. Washing with water and drying are traditional procedures carried out to obtain molecular sieves, and in this respect there is no specific limitation in this application. For example, drying may be carried out using an oven, mesh belt, converter, or the like, and drying may be carried out under the following conditions: the temperature is about 50 to 350°C, preferably about 70 to 200°C, for example, about 180 °C; the drying time is about 1 to 24 hours, preferably about 2 to 6 hours, such as about 3 hours.

According to the present application, the raw material of the phosphorus-containing molecular sieve is subjected to a specific hydrothermal treatment and two stages of acid treatment, and as a result, a phosphorus-containing molecular sieve with a high content of silica and novel structural features can be obtained.

The phosphorus-containing high silica molecular sieve of the present application can be used in a variety of acid catalysts suitable for use in catalytic cracking, hydroisomerization, alkylation, hydrocracking, and other reactions, and is particularly suitable for use in hydrocarbon feed hydrocracking. to obtain hydrocarbon fractions having lower boiling points and lower molecular weights.

Thus, according to the third aspect of the present application, the use of a phosphorus-containing high silica molecular sieve according to the present application in the hydrocracking of a hydrocarbon feedstock, including the step of contacting the hydrocarbon feedstock with a hydrocracking catalyst containing said phosphorus-containing molecular sieve with a high content of silica, is provided.

According to the present application, a variety of heavy mineral oils or synthetic oils, or appropriate mixed distillates, such as direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, distillation products can be selected as hydrocarbon feedstock. cokers, catalytically cracked distillates, shale oils, oil sands oils, liquid coal gasification products, and the like.

In particular, the high silica phosphorus-containing molecular sieve catalyst of the present application is particularly suitable for use in the hydrocracking of heavy and low grade distillates to produce a middle distillate having a distillation range of about 149 to 371° C., in particular, approximately 180 to 370°C.

According to the present application, the hydrocracking reaction may be one or more hydrocracking reactions carried out using conventional equipment such as fixed bed, fluidized bed, slurry bed, suspended bed, etc. reactors.

According to the present application, when the high silica phosphorus-containing molecular sieve catalyst of the present application is used in the hydrocracking of distillate oils, the catalyst can be used in conventional hydrocracking conditions. For example, hydrocracking can be carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C, the pressure in the reactor is from about 3 to 24 MPa, preferably from about 4 to 15 MPa, hour the liquid space velocity is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 , and the volume ratio of hydrogen to oil is from about 100 to 5000.

According to the fourth aspect of the present application proposed hydrocracking containing, in relation to the dry weight of the catalyst, from about 45 to 90 wt.%, for example, from about 60 to 90 wt.% carrier in terms of dry matter; from about 1 to 40 wt.%, for example, from about 5 to 35 wt.% component of the first metal in terms of metal oxides; and from about 1 to 15 wt.%, for example, from about 2 to 12 wt.% component of the second metal in terms of metal oxides, and the carrier contains a phosphorus-containing molecular sieve with a high content of silicon dioxide according to the present application and a refractory inorganic oxide in a mass ratio , which is from about 0.03:1 to about 20:1, for example, from about 0.05:1 to about 19:1; wherein the first metal component comprises a Group VIB metal; and the second metal component contains a Group VIII metal.

According to the present application, the refractory inorganic oxide can be used to increase the strength of the catalyst, as well as to improve and control the physico-chemical properties of the catalyst, including to improve the porous structure of the catalyst. In some embodiments, the refractory inorganic oxide can be any inorganic oxide commonly used in hydrogenation catalyst supports, such as alumina, silica, titanium dioxide, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and etc. According to a preferred embodiment of the present application, the refractory inorganic oxide is alumina, and hydrargillites such as gibbsite, bayerite, nordstrandite and monohydrate bauxite such as boehmite, diaspore, pseudoboehmite can be present as alumina.

According to preferred embodiments of the present application, the first metal component is selected from the group consisting of molybdenum components, tungsten components, and any combination thereof; and/or the second metal component is selected from the group consisting of iron components, nickel components, cobalt components, and any combination thereof.

According to the fifth aspect of the present application, there is provided a process for producing a hydrocracking catalyst according to the present application, comprising the following steps:

i) mixing a phosphorus-containing high silica molecular sieve according to the present application with a refractory inorganic oxide to form a carrier; And

ii) contacting the carrier with an impregnating solution containing a first metal precursor and a second metal precursor for impregnation.

According to the present application, the contacting of the support with the impregnating solution and the impregnation can be carried out by any method known in the art, such as the method which is described in PRC Patent No. ZL200810241082.3, and which includes depositing a Group VIB metal component, a Group VIII metal component, and an organic catalyst support additives.

Methods for obtaining a carrier are well known in the art, and in this respect there is no specific limitation in this application. For example, the method may include the following steps: mixing a phosphorus-containing molecular sieve with a high content of silicon dioxide according to the present application with a refractory inorganic oxide, and then molding and drying to obtain a support. The molding can be carried out using a variety of conventional methods such as tablet molding, ball rolling molding, or extrusion molding.

The shape of the carrier according to the present application is not particularly limited, and may be a sphere, a plate, a hollow plate, a hollow sphere, a block, etc., and the plate-shaped carrier may have a multi-blade shape such as a trefoil shape, a quatrefoil shape, and the like. ., or the corresponding modified form.

According to some embodiments of the present application, the first metal precursor is a compound that contains the first metal and is soluble in the impregnation solution, including, but not limited to, at least one compound, which is selected as first metal inorganic acids, inorganic salts of the first metal, oxides of the first metal and organometallic compounds of the first metal; wherein the inorganic salt may be at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the first metal organometallic compound may be at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group. For example, when the first metal is molybdenum, the first metal precursor may be at least one selected from the group consisting of molybdic acid, paramolybdic acid, molybdate, paramolybdate, and molybdenum oxide; and when the first metal is tungsten, the first metal precursor may be at least one compound selected from the group consisting of tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstate.

In some embodiments of the present application, the second metal precursor is a compound that contains a second metal and is soluble in the impregnation solution, including, but not limited to, second metal inorganic acids, second metal inorganic salts, second metal oxides, and second metal organometallic compounds. metal; wherein the inorganic salt may be at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate, and chloride; and the organic substituent in the second metal organometallic compound may be at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group.

According to some embodiments of the present application, the impregnating solution may further include an organic additive, which may be present in an amount of from about 2 to 300 g/l. The organic additive may be an oxygen-containing organic compound and/or a nitrogen-containing organic compound. In particular, the oxygen-containing organic compound may be at least one selected from the group consisting of ethylene glycol, glycerol, polyethylene glycol (having a molecular weight that may be from about 200 to 1500), diethylene glycol, butanediol, acetic acid, maleic acid. , oxalic acid, nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid; the nitrogen-containing organic compound may be at least one selected from the group consisting of ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine,

nitrilotriacetic acid, ethylenediaminetetraacetic acid and ammonium ethylenediaminetetraacetate.

In the process for producing the hydrocracking catalyst of the present application, the contacting and impregnating temperatures are not particularly limited, and may be various temperatures that can be achieved with the impregnating solution used. The duration of the impregnation is also not particularly limited, provided that the catalyst carrier can be loaded in a desired amount of the metal active component precursor. In general, the higher the impregnation temperature and impregnation solution concentration, the shorter the time required to reach that level of impregnation (ie the difference between the weight of the catalyst support after impregnation and the weight of the catalyst support before impregnation); and vice versa. Once the desired soak levels and conditions are selected, the appropriate soak duration can be readily determined by one of ordinary skill in the art in view of the disclosure herein.

The impregnation method is also not particularly limited, and the impregnation may be saturation impregnation or supersaturation impregnation. The impregnation conditions are not particularly limited, and the impregnation may be carried out under sealed conditions or under open conditions according to conventional methods, and the loss of aqueous solvent during the impregnation may or may not be replenished. Various gases such as air, nitrogen, steam, etc. may be introduced during the impregnation process, or there may be no introduction of new components.

According to some embodiments of the present application, the process for producing a hydrocracking catalyst may further include the step of drying and calcining the impregnated material, which step is traditionally used to obtain catalysts and is not limited in a certain way according to the present application. For example, drying can be carried out under the following conditions: the temperature is about 80 to 350°C, preferably about 100 to 300°C, and the drying time is about 0.5 to 24 hours, preferably about 1 to 12 hours. can be carried out under the following conditions: the temperature is from about 350 to 600°C, preferably from about 400 to 550°C; and the calcination time is about 0.2 to 12 hours, preferably about 1 to 10 hours.

The hydrocracking catalyst of the present application can be used as an acid catalyst for catalytic cracking, hydroisomerization, alkylation, hydrocracking, and other reactions, and is particularly suitable for use in the hydrocracking of a hydrocarbon feed to produce hydrocarbon cuts having lower boiling points and lower molecular weights.

Thus, according to the sixth aspect of the present application, the use of the hydrocracking catalyst according to the present application in the hydrocracking of a hydrocarbon feedstock is provided, including the step of contacting the hydrocarbon feedstock with said hydrocracking catalyst.

According to the present application, a variety of heavy mineral oils or synthetic oils or appropriate mixed distillates, such as direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, distillation products can be selected as hydrocarbon feedstock. cokers, catalytically cracked distillates, shale oils, oil sands oils, liquid coal gasification products, etc.

In particular, the catalyst of the present application can be used in the hydrocracking of heavy and low grade distillates to produce a middle distillate having a distillation range of about 149 to 371°C, in particular about 180 to 370°C.

In the case of a hydrocracking feedstock, the hydrocracking catalyst of the present application is preferably presulfurized using sulfur, hydrogen sulfide, or a sulfur-containing feedstock in the presence of hydrogen at a temperature of about 140 to 370°C before use. The pre-sulphurization can be carried out outside the reactor or inside the reactor at the point of use of the catalyst so as to convert it to the sulfide form.

When the catalyst of the present application is used in distillate hydrocracking, the catalyst can be used under conventional hydrocracking conditions. For example, the hydrocracking reaction can be carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C; the pressure in the reactor is about 3 to 24 MPa, preferably about 4 to 15 MPa; the hourly space velocity of the liquid is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to about 5000.

The hydrocracking reaction may be carried out using any equipment that contacts and reacts a hydrocarbon feedstock with a catalyst under hydrogenation conditions, which may be, for example, a fixed bed, moving bed, fluidized bed or slurry bed reactor.

According to the preferred embodiments of the present application, the following technical solutions are proposed.

A1: a phosphorus-containing high silica molecular sieve containing about 90 to 99.8 wt.% silicon, about 0.1 to 9.0 wt.% aluminum, and about 0.01 to 2.5 wt. % phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve,

moreover, the molecular sieve is characterized by an X-ray diffraction pattern containing at least three diffraction peaks, while the first intense peak is present at a diffraction angle of approximately 5.9 to 6.9 °, the second intense peak is present at a diffraction angle of approximately 10, 0 to 11.0°, the third intense peak is present at a diffraction angle of approximately 15.6 to 16.7°,

preferably, the molecular sieve has a pore volume of about 0.20 to 0.50 ml/g and a specific surface area of about 260 to 600 m ² /g.

A2: A high silica phosphorus molecular sieve according to solution A1, wherein in the X-ray diffraction pattern of the molecular sieve, the first intense peak is present at a diffraction angle of approximately 6.1 to 6.8°, the second intense peak is present at a diffraction angle of approximately from 10.2 to 10.7°, and the third intense peak is present at a diffraction angle of approximately 15.8 to 16.5°.

A3: A high silica phosphorus-containing molecular sieve according to any of the preceding solutions, wherein I ₁ /I _23.5-24.5° is about 3.0 to 11.0, I ₂ /I ₂₃ in the X-ray diffraction pattern of the molecular sieve _.5-24.5° is from about 2.9 to 7.0, I ₃ /1 gz.5-24.5° is from about 1.0 to 4.0, while I ₁ is the peak height for first intense peak, I ₂ is the peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23 .5 to 24.5°.

A4: A high silica phosphorus-containing molecular sieve according to any one of the preceding solutions, wherein the molecular sieve is characterized by an X-ray diffraction pattern containing at least five diffraction peaks, wherein the fourth intense peak is present at a diffraction angle of approximately 20.4 to 21, 6° and the fifth intense peak is present at a diffraction angle of approximately 11.8 to 12.8°.

A5: A high silica phosphorus molecular sieve according to solution A4, wherein in the X-ray diffraction pattern of the molecular sieve, the fourth intense peak is present at a diffraction angle of approximately 20.8 to 21.4° and the fifth intense peak is present at a diffraction angle of about 12.1 to 12.6°; and/or I ₄ /I _23.5-24.5° is approximately 1.0 to 4.0, and I ₅ /I _23.5-24.5° is approximately 1.0 to 2.0, where I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24.5°.

A6: A process for producing a phosphorus-containing molecular sieve with a high content of silicon dioxide, comprising the following steps:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 8.0 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material; moreover, the source material of the phosphorus-containing molecular sieve has a phosphorus content of approximately 0.1 to 15 wt.%, a sodium content of approximately 0.5 to 4.5 wt.%, a silicon content of approximately 70 to 85 wt. %, and an aluminum content of approximately 16.0 to 21.0 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) and suspending to form a first slurry, heating the first slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, then adding the first acid solution to the first slurry while maintaining the temperature, wherein the first acid solution is added in such an amount that the acidified first slurry has a pH value of about 2.5 to 4, carrying out the reaction at a constant temperature for about 0.5 to 20 h and collection of the first solid product; And

c) adding water to the first solid product obtained in step (b) and suspending to form a second slurry, heating the second slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, then maintaining constant temperature addition of the second acid solution to the second suspension, in which the second acid solution is added in such an amount that the acidified second suspension has a pH value of about 1.0 to 2.0, carrying out the reaction at a constant temperature for about 0, 5 to 20 h and collection of the second solid product.

A7: The method according to solution A6, wherein in step (a) the phosphorus-containing molecular sieve starting material is a phosphorus-containing Y molecular sieve having a lattice parameter of about 2.425 to 2.47 nm, a specific surface area of about 250 to 750 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g.

A8: A process according to solution A6 or A7 wherein in step (b) the weight ratio of the water in the first slurry to the dry weight of the phosphorus-containing molecular sieve starting material is about 14:1 to about 5:1.

A9: A process according to any one of Solutions A6-A8, wherein in step (c) the weight ratio of the water in the second slurry to the dry weight of the phosphorus-containing molecular sieve starting material is about 0.5:1 to about 20:1.

A10: The method according to any one of solutions A6-A9, wherein in step (c) the addition of the second acid solution is carried out by adding the second acid solution to the second suspension at a rate of from about 0.05 to 15 mol/h, preferably from about 0 05 to 10 mol/h, more preferably from about 2 to 8 mol/h in terms of H ⁺ and in relation to 1 l of the second suspension.

A11: The method of any one of Solutions A6-A10, wherein in step (b) the first acid solution has an acid concentration of about 0.01 to 15.0 mol/L, preferably about 0.1 to 5.0 mol /l, and the acid in the first acid solution is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid, preferably selected from sulfuric acid and nitric acid; and/or in step (c) the second acid solution has an acid concentration of about 0.01 to 15.0 mol/l, preferably about 0.1 to 5.0 mol/l, and the acid in the second acid solution is is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid, preferably selected from sulfuric acid and nitric acid.

A12: The process of any one of Solutions A6-A11, further comprising: collecting the second solid product, then washing with water and drying to obtain a high silica phosphorus-containing molecular sieve; preferably the drying is carried out under the following conditions: the temperature is from about 50 to 350°C, preferably from about 70 to 200°C; and the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

A13: A high silica content phosphorus-containing molecular sieve prepared by the process of any one of Solutions A6-A12.

A14: The use of a phosphorus containing high silica molecular sieve according to any one of Solutions A1-A5 and A13 in the hydrocracking of a hydrocarbon feedstock.

A15: application according to solution A14 wherein the hydrocarbon feedstock is selected from the group consisting of direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coker distillation products, catalytically cracked distillation products, shale oils, oil sands oils, liquid coal gasification products, and a combination of two or more of these materials; and/or

the hydrocracking reaction is carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C; the pressure in the reactor is about 3 to 24 MPa, preferably about 4 to 15 MPa; the hourly space velocity of the liquid is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to about 5000.

A16: A hydrocracking catalyst containing, based on the dry weight of the catalyst, from about 45% to about 90% by weight of carrier, on a dry basis, from about 1% to about 40% by weight of a first metal component, based on metal oxides, and from about 1 up to 15 wt.% component of the second metal in terms of metal oxides;

the carrier comprises a phosphorus-containing high silica molecular sieve and a refractory inorganic oxide, wherein the weight ratio of the phosphorus-containing high silica molecular sieve to the refractory inorganic oxide is about 0.03:1 to about 20:1;

wherein the first metal component comprises a Group VIB metal; and the second metal component contains a Group VIII metal; And

the phosphorus-containing high silica molecular sieve contains from about 90 to 99.8 wt.% silicon, from about 0.1 to 9.0 wt.% aluminum and from about 0.01 to 2.5 wt.% phosphorus in terms of on oxides and in relation to the dry weight of the molecular sieve, and a phosphorus-containing molecular sieve with a high content of silicon dioxide is characterized by an X-ray diffraction pattern containing at least three diffraction peaks, with the first intense peak present at a diffraction angle of approximately 5.9 to 6 .9°, the second intense peak is present at a diffraction angle of about 10.0 to 11.0°, and the third intense peak is present at a diffraction angle of about 15.6 to 16.7°, preferably a phosphorus-containing molecular sieve with high silica content has a pore volume of about 0.20 to 0.50 ml/g and a specific surface area of about 260 to 600 m ² /g.

A17: A hydrocracking catalyst according to solution A16 wherein, in an X-ray diffraction pattern of a phosphorus-containing high silica molecular sieve, the first intense peak is present at a diffraction angle of about 6.1 to 6.8°, the second intense peak is present at a diffraction angle , ranging from approximately 10.2 to 10.7°, and the third intense peak is present at a diffraction angle of approximately 15.8 to 16.5°.

A18: The hydrocracking catalyst according to solution A16 or A17, in which, in the X-ray diffraction pattern of a phosphorus-containing molecular sieve with a high content of silicon dioxide, I ₁ /I _23.5-24.5° is approximately 3.0 to 11.0, I ₂ /I _23.5-24.5° is about 2.9 to 7.0 and I ₃ /I _23.5-24.5° is about 1.0 to 4.0 where I ₁ is the height of the peak for the first intense peak, I ₂ is the peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24.5°.

A19: The hydrocracking catalyst of any one of Solutions A16-A18, wherein the high silica phosphorus-containing molecular sieve exhibits an X-ray diffraction pattern containing at least five diffraction peaks, with a fourth intense peak present at a diffraction angle of about 20.4 to 21.6° and the fifth intense peak is present at a diffraction angle of approximately 11.8 to 12.8°.

A20: The hydrocracking catalyst according to solution A19, wherein in the X-ray diffraction pattern of the high silica phosphorus-containing molecular sieve, the fourth intense peak is present at a diffraction angle of about 20.8 to 21.4° and the fifth intense peak is present at a diffraction angle, comprising approximately from 12.1 to 12.6°; and/or I ₄ /I _23.5-24.5° is approximately 1.0 to 4.0, and I ₅ /I _23.5-24.5° is approximately 1.0 to 2.0, wherein I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 up to 24.5°.

A21: The hydrocracking catalyst according to any one of Solutions A16-A20, wherein the high silica content phosphorus-containing molecular sieve is produced by a process comprising the following steps:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 8.0 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material; wherein the phosphorus-containing molecular sieve feedstock has a phosphorus content of about 0.1 to 15 wt.%, a sodium content of about 0.5 to 4.5 wt.%, a silicon content of about 70 to 85 wt. .%, and an aluminum content of approximately 16.0 to 21.0 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) and suspending to form a first slurry, heating the first slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, then adding the first acid solution to the first suspension while maintaining the temperature, in which the first acid solution is added in such an amount that the acidified first suspension has a pH value of about 2.5 to 4, carrying out the reaction at a constant temperature for about 0.5 up to 20 h and collection of the first solid product; And

c) adding water to the first solid product obtained in step (b) and suspending to form a second slurry, heating the second slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, then maintaining constant temperature adding the second acid solution to the second suspension, in which the second acid solution is added in such an amount that the acidified second suspension has a pH value of about 1.0 to 2.0, carrying out the reaction at a constant temperature for about 0, 5 to 20 h and collection of the second solid product.

A22: The hydrocracking catalyst according to solution A21, wherein in step (a) the phosphorus-containing molecular sieve feedstock is a phosphorus-containing Y molecular sieve having a lattice parameter of about 2.425 to 2.47 nm, a specific surface area of about 250 up to 750 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g.

A23: A hydrocracking catalyst according to solution A21 or A22 wherein in step (b) the weight ratio of the water in the first slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1.

A24: The hydrocracking catalyst of any one of Solutions A21-A23, wherein in step (c) the weight ratio of the water in the second slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 0.5:1 to about 20:1.

A25: A hydrocracking catalyst according to any one of solutions A21-A24 wherein in step (c) the addition of the second acid solution is carried out by adding the second acid solution to the second slurry at a rate of from about 0.05 to 15 mol/h, preferably from about 0.05 to 10 mol/h, more preferably from about 2 to 8 mol/h in terms of H ⁺ and in relation to 1 l of the second suspension.

A26: A hydrocracking catalyst according to any one of solutions A21-A25, wherein in step (b) the first acid solution has an acid concentration of about 0.01 to 15.0 mol/l, preferably about 0.1 to 5.0 mol/l, and the acid in the first acid solution is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid, preferably selected from sulfuric acid and nitric acid; and/or in step (c) the second acid solution has an acid concentration of about 0.01 to 15.0 mol/l, preferably about 0.1 to 5.0 mol/l, and the acid in the second acid solution is is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid, preferably selected from sulfuric acid and nitric acid.

A27: A hydrocracking catalyst according to any one of Solutions A21-A26, wherein the process for producing a phosphorus-containing high silica molecular sieve further comprises the steps of: collecting a second solid product, then washing with water and drying to obtain a phosphorus-containing high silica molecular sieve; preferably the drying is carried out under the following conditions: the temperature is from about 50 to 350°C, preferably from about 70 to 200°C; and the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

A28: A hydrocracking catalyst according to any one of Solutions A21-A27, wherein the refractory inorganic oxide is selected from the group consisting of alumina, silica, titanium dioxide, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and a combination of two or more of these materials; and/or the first metal component is a molybdenum component and/or a tungsten component; and the second metal component is an iron component, a nickel component, a cobalt component, and a combination of two or more of these materials.

A29: A process for preparing a hydrocracking catalyst according to any one of Solutions A16-A28, comprising the step of contacting the support with an impregnating solution containing a first metal precursor and a second metal precursor for impregnation, wherein the support contains a high silica content phosphorus-containing molecular sieve and a refractory inorganic oxide.

A30: The method according to solution A29, further comprising the steps of mixing a phosphorus-containing molecular sieve with a high content of silica with a refractory inorganic oxide, then shaping, drying and calcining to obtain a support.

A31: The method of Solutions A29 or A30, wherein the first metal precursor is a first metal inorganic acid, a first metal inorganic salt, or a first metal organometallic compound; wherein the inorganic salt is at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the first metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group; and/or the second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organometallic compound of the second metal; wherein the inorganic salt is at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the second metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group.

A32: a method according to any of solutions A29-A31, further comprising the steps of drying and calcining the impregnated material;

preferably the drying is carried out under the following conditions: the temperature is from about 80 to 350°C, preferably from about 100 to 300°C and the drying time is from about 0.5 to 24 hours, preferably from about 1 to 12 hours; and/or preferably, the calcination is carried out under the following conditions: the temperature is from about 350 to 600°C, preferably from about 400 to 550°C, and the calcination time is from about 0.2 to 12 hours, preferably from about 1 to 10 hours.

A33: The use of a hydrocracking catalyst according to any of Solutions A16-A28 in the hydrocracking of a hydrocarbon feedstock.

A34: Use according to solution A33, wherein the hydrocarbon feedstock is selected from the group consisting of direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coker distillation products, catalytically cracked distillation products, shale oils, oil sands oils, liquid coal gasification products, and a combination of two or more of these materials; and/or the hydrocracking reaction is carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C; the pressure in the reactor is about 3 to 24 MPa, preferably about 4 to 15 MPa; the hourly space velocity of the liquid is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to about 5000.

B1: a phosphorus-containing high silica molecular sieve, characterized in that the molecular sieve has a pore volume of about 0.20 to 0.50 ml/g, a specific surface area of about 260 to 600 m ² /g, and the molecular sieve has a silicon content of about 90 to 99.8 wt.%, an aluminum content of about 0.1 to 9.0 wt.%, and a phosphorus content of about 0.01 to 2.5 wt.% in terms of oxides and in relation to the dry weight of the molecular sieve; wherein the molecular sieve is characterized by an X-ray diffraction pattern containing a first intense peak at a diffraction angle of approximately 5.9 to 6.9°, a second intense peak at a diffraction angle of approximately 10.0 to 11.0°, and a third intense peak at a diffraction angle of approximately 15.6 to 16.7°.

B2: molecular sieve according to solution B1, wherein the molecular sieve is characterized by an X-ray diffraction pattern containing a first intense peak at a diffraction angle of approximately 6.1 to 6.8°, a second intense peak at a diffraction angle of approximately 10.2 to 10 .7° and a third intense peak at a diffraction angle of approximately 15.8 to 16.5°.

B3: Molecular sieve according to solution B1 or B2, and in the X-ray diffraction pattern of the molecular sieve I ₁ /I _23.5-24.5° is approximately 3.0 to 11.0, I ₂ /I _{23.5-24.5 °} is from about 2.9 to 7.0, and I3/I _23.5-24.5° is from about 1.0 to 4.0, where I ₁ is the peak height for the first intense peak, I ₂ represents is the peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24.5° .

B4: molecular sieve according to solution B1 or B2, wherein the molecular sieve is characterized by an X-ray diffraction pattern containing a fourth intense peak at a diffraction angle of approximately 20.4 to 21.6°, and a fifth intense peak at a diffraction angle of approximately 11, 8 to 12.8°.

B5: molecular sieve according to solution B4, wherein the molecular sieve is characterized by an X-ray diffraction pattern containing a fourth intense peak at a diffraction angle of approximately 20.8 to 21.4° and a fifth intense peak at a diffraction angle of approximately 12.1 to 12.6°; and/or I ₄ /I _23.5-24.5° is approximately 1.0 to 4.0, I ₅ /I _23.5-24.5° is approximately 1.0 to 2.0, with where I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 to 24.5°.

B6: A process for producing a high silica content phosphorus-containing molecular sieve according to any one of Solutions B1-B5, comprising the following steps:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 2 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain hydrothermally processed molecular sieve material; wherein the phosphorus-containing molecular sieve feedstock has a phosphorus content of about 0.1 to 15% by weight and a sodium content of about 0.5 to 4.5% by weight, based on oxides and based on dry weight source material phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) and suspending to form a first slurry, heating the first slurry to a temperature of about 40 to 95° C., then adding the first acid solution to the first slurry while maintaining temperature in such an amount that the acidified first suspension has a pH of about 2.5 to 4, the reaction at a constant temperature for about 0.5 to 20 hours and the collection of the first solid product;

c) adding water to the first solid product obtained in step (b) and suspending to form a second slurry, heating the second slurry to a temperature of about 40 to 95° C., then adding the second acid solution continuously while maintaining a constant temperature to the second a slurry in which the second acid solution is added in such an amount that the acidified second slurry has a pH value of about 1.0 to 2.0, the reaction is carried out at a constant temperature for about 0.5 to 20 hours and the second solid is collected product.

B7: The method according to solution B6, wherein in step (a), the phosphorus-containing molecular sieve starting material is a phosphorus-containing Y molecular sieve having a crystal lattice parameter of about 2.425 to 2.47 nm, a specific surface area of about 250 to 750 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g.

B8: The method according to solution B6, wherein in step (b) the weight ratio of the water in the first slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1.

B9: The process according to solution B6 wherein in step (c) the weight ratio of the water in the second slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 0.5:1 to about 20:1.

B10: the method according to solution B6, in which in step (c) the addition of the second acid solution is carried out by adding the second acid solution to the second suspension at a rate of approximately 0.05 to 10 mol/h in terms of H ⁺ and with respect to 1 liter of the second suspension.

B11: The method according to solution B6, wherein in step (b) the first acid solution has an acid concentration of about 0.01 to 15.0 mol/l, the acid in the first acid solution is at least one acid selected from a group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid; and/or in step (c) the second acid solution has an acid concentration of about 0.01 to 15.0 mol/l and the acid in the second acid solution is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid.

B12: the method according to solution B6, wherein the method further comprises: collecting the second solid product, then washing with water and drying to obtain a phosphorus-containing aluminosilicate molecular sieve; and/or drying is carried out under the following conditions: the temperature is from about 50 to 350°C, preferably from about 70 to 200°C; and the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

B13: The use of a phosphorus-containing molecular sieve with a high content of silica according to any of the solutions B1-B5 in the hydrocracking of the original hydrocarbon material.

B14: application according to solution B13, in which the hydrocarbon feedstock is selected from the group consisting of direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillation products, catalytically cracked distillation products, shale oils, oil sands oils, liquid coal gasification products, and a combination of two or more of these materials; and/or the hydrocracking reaction is carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C; the pressure in the reactor is about 3 to 24 MPa, preferably about 4 to 15 MPa; the hourly space velocity of the liquid is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to about 5000.

C1: hydrocracking catalyst, characterized in that the catalyst contains, in relation to the dry weight of the catalyst, from 45 to 90 wt.% of the carrier, calculated on the dry matter; from 1 to 40 wt.% component of the first metal in terms of metal oxides; and from 1 to 15 wt.% component of the second metal in terms of metal oxides;

the carrier comprises a phosphorus-containing high silica molecular sieve and a refractory inorganic oxide, wherein the weight ratio of the phosphorus-containing high silica molecular sieve to the refractory inorganic oxide is about 0.03:1 to about 20:1; wherein the first metal component is a metal component selected from Group VIB metals; the second metal component is a metal component selected from Group VIII metals;

the phosphorus-containing high silica molecular sieve has a pore volume of about 0.20 to 0.50 ml/g, a specific surface area of about 260 to 600 m ² /g, and a phosphorus-containing high silica molecular sieve has a silicon content of about 90 to 99.8 wt.%, an aluminum content of about 0.1 to 9.0 wt.% and a phosphorus content of about 0.01 to 2.5 wt.% in in terms of oxides and in relation to the dry weight of the molecular sieve; and a phosphorus-containing molecular sieve with a high content of silicon dioxide is characterized by an X-ray diffraction pattern containing a first intense peak at a diffraction angle of about 5.9 to 6.9°, a second intense peak at a diffraction angle of about 10.0 to 11.0 °, and a third intense peak at a diffraction angle of approximately 15.6 to 16.7°.

C2: catalyst according to solution C1, in which a phosphorus-containing molecular sieve with a high content of silica is characterized by an X-ray diffraction pattern containing a first intense peak at a diffraction angle of approximately 6.1 to 6.8°, a second intense peak at a diffraction angle of approximately from 10.2 to 10.7°, and a third intense peak at a diffraction angle of approximately 15.8 to 16.5°.

C3: catalyst according to solution C1 or C2, wherein in the X-ray diffraction pattern of a phosphorus-containing molecular sieve with a high content of silicon dioxide, I ₁ /I _23.5-24.5° is approximately 3.0 to 11.0, I ₂ /I _{23, 5-24.5°} is about 2.9 to 7.0, and I ₃ /I _23.5-24.5° is about 1.0 to 4.0, where I ₁ is the peak height for the first intense peak, I ₂ is the peak height for the second intense peak, I ₃ is the peak height for the third intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of about 23, 5 to 24.5°.

C4: Catalyst according to solution C1 or C2, in which the phosphorus-containing molecular sieve with a high content of silica is characterized by an X-ray diffraction pattern containing a fourth intense peak at a diffraction angle of approximately 20.4 to 21.6°, and a fifth intense peak at a diffraction angle , which is approximately from 11.8 to 12.8°.

C5: catalyst according to solution C4, in which the phosphorus-containing molecular sieve with a high content of silicon dioxide is characterized by an X-ray diffraction pattern containing a fourth intense peak at a diffraction angle of approximately 20.8 to 21.4°, and a fifth intense peak at a diffraction angle of about 12.1 to 12.6°; and/or I ₄ /I _23.5-24.5° is approximately 1.0 to 4.0, and I ₅ /I _23.5-24.5° is approximately 1.0 to 2.0, wherein I ₄ is the peak height for the fourth intense peak, I ₅ is the peak height for the fifth intense peak, and I _23.5-24.5° is the peak height for a peak at a diffraction angle of approximately 23.5 up to 24.5°.

C6: catalyst according to solution C1 or C2, in which a phosphorus-containing molecular sieve with a high content of silicon dioxide is obtained by a method comprising the following steps:

a) subjecting the phosphorus-containing molecular sieve raw material to hydrothermal treatment at a temperature of about 350 to 700° C., a pressure of about 0.1 to 2 MPa, and in the presence of steam for about 0.5 to 10 hours to obtain hydrothermally processed molecular sieve material; wherein the phosphorus-containing molecular sieve feedstock has a phosphorus content of about 0.1 to 15% by weight and a sodium content of about 0.5 to 4.5% by weight, based on oxides and based on dry weight source material phosphorus-containing molecular sieve;

b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) and suspending to form a first slurry, heating the first slurry to a temperature of about 40 to 95° C., then adding the first acid solution to the first slurry while maintaining temperature in such an amount that the acidified first suspension has a pH value of about 2.5 to 4, the reaction at a constant temperature for about 0.5 to 20 hours and the collection of the first solid product;

c) adding water to the first solid product obtained in step (b) and suspending to form a second slurry, heating the second slurry to a temperature of about 40 to 95° C., then adding the second acid solution continuously while maintaining a constant temperature to the second a slurry in which the second acid solution is added in such an amount that the acidified second slurry has a pH value of about 1.0 to 2.0, the reaction is carried out at a constant temperature for about 0.5 to 20 hours and the second solid is collected product.

C7: catalyst according to solution C6, wherein in step (a) the phosphorus-containing molecular sieve starting material is a phosphorus-containing Y molecular sieve having a lattice parameter of about 2.425 to 2.47 nm, a specific surface area of about 250 to 750 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g.

C8: catalyst according to solution C6 wherein in step (b) the weight ratio of the water in the first slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1.

C9: catalyst according to solution C6 wherein in step (c) the weight ratio of water in the second slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 0.5:1 to about 20:1.

C10: catalyst according to solution C6, in which in step (c) the addition of the second acid solution is carried out by adding the second acid solution to the second suspension at a rate of approximately 0.05 to 10 mol/h in terms of H ⁺ and with respect to 1 liter of the second suspension.

C11: catalyst according to solution C6, wherein in step (b) the first acid solution has an acid concentration of about 0.01 to 15.0 mol/l, the acid in the first acid solution is at least one acid selected from a group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid; and/or in step (c) the second acid solution has an acid concentration of about 0.01 to 15.0 mol/l and the acid in the second acid solution is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid.

C12: catalyst according to solution C6, wherein the process for producing a phosphorus-containing high silica molecular sieve further comprises the steps of: collecting a second solid product, then washing with water and drying to obtain a phosphorus-containing high silica molecular sieve; and/or drying is carried out under the following conditions: the temperature is from about 50 to 350°C, preferably from about 70 to 200°C; and the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

C13: Catalyst according to Solution C1 wherein the refractory inorganic oxide is selected from the group consisting of alumina, silica, titanium dioxide, zirconium dioxide, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, or cadmium oxide and a combination of two or three the above substances; and/or the first metal component is a molybdenum component and/or a tungsten component; and the second metal component is an iron component, a nickel component, a cobalt component, or a combination of two or three of the above.

C14: A process for preparing a hydrocracking catalyst according to any one of Solutions C1-C13, comprising the step of contacting the carrier with an impregnating solution containing a first metal precursor and a second metal precursor for impregnation.

C15: The method according to solution C14, the method further comprising the steps of mixing a phosphorus-containing molecular sieve with a high silica content with a refractory inorganic oxide, and then shaping, drying and calcining to obtain a carrier.

C16: the method according to solution C14, wherein the first metal precursor is a first metal inorganic acid, a first metal inorganic salt, or a first metal organometallic compound; the inorganic salt is selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the first metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group; and/or the second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organometallic compound of the second metal; the inorganic salt is selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the second metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group.

C17: the method according to solution C14, wherein the method further comprises the steps of drying and calcining the impregnated material; and/or

the drying is carried out under the following conditions: the temperature is about 80 to 350° C. and the drying time is about 0.5 to 24 hours; and/or

the calcination is carried out under the following conditions: the temperature is about 350 to 600°C, and the calcination time is about 0.2 to 12 hours.

C18: Use of a hydrocracking catalyst according to any of Solutions C1-13 in the hydrocracking of a hydrocarbon feedstock.

C19: use according to solution C18, wherein the hydrocarbon feedstock is selected from the group consisting of direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coker distillation products, catalytically cracked distillation products, shale oils, oil sands oils, liquid coal gasification products, and a combination of two or more of these materials; and/or the hydrocracking reaction is carried out under the following conditions: the reaction temperature is from about 200 to 650°C, preferably from about 300 to 510°C; the pressure in the reactor is about 3 to 24 MPa, preferably about 4 to 15 MPa; the hourly space velocity of the liquid is from about 0.1 to 50 h ^-1 , preferably from about 0.2 to 30 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to about 5000.

Examples

The present application will be further illustrated by presenting the following examples, which are not intended to be limiting.

Devices and methods

In the following examples and comparative examples, the pore volume and specific surface area of the molecular sieve were measured by the low-temperature nitrogen adsorption/desorption method according to the national standard GB/T5816-1995 using an ASAP 2400 automatic adsorption instrument from Micromeritics Instrument Corporation (USA). In particular, the studied molecular sieve was kept in vacuum and degassed at a temperature of 250°C and a pressure of 1.33 Pa for 4 hours, and then an adsorbate (nitrogen) was brought into contact with it at a temperature of -196°C in the process of static adsorption until until the adsorption balance has been reached; the amount of nitrogen adsorbed by the adsorbent was calculated from the difference between the amount of incoming nitrogen gas and the amount of residual nitrogen in the gas phase after adsorption, then the pore size distribution was calculated using the Barret-Joyner-Halenda (BJH) equation, and the specific surface area and pore volume were calculated using the Brunauer-Emmett-Teller (BET) equation.

The crystal structure of the molecular sieve was determined using a D5005 X-ray diffractometer from Siemens (Germany) according to industrial standard SH/T0339-92. The experiment was carried out under the following conditions: Cu target, Kα radiation, solid-state detector, tube voltage 40 kV, tube current 40 mA, stepped scanning with a step of 0.02°, pretreatment duration 2 s, scanning range from 5° to 70°. The diffraction angle is the value of 20 at which the height of the diffraction peak reaches its largest value.

The silicon content, aluminum content, phosphorus content, and sodium content of the molecular sieve were measured using a 3271E X-ray fluorescence spectrometer from Rigaku Industrial Corporation (Japan). Specifically, a tablet was made from the powder sample, the intensity of the spectral line of each element was determined using a rhodium target, a laser voltage of 50 kV, a laser current of 50 mA, a scintillation counter and a proportional counter, and quantitative and semi-quantitative analysis of element content was carried out using an external standard method.

Molecular Sieve Production Examples

Preparative Examples 1, 2 provide exemplary high silica phosphorus-containing molecular sieves of the present application and methods for their preparation.

Preparation 1

500 g of phosphorus-containing molecular sieve (USY molecular sieve supplied by Changling Branch of Sinopec Catalyst Co., Ltd., which has a crystal lattice parameter of 2.456 nm, a specific surface area of 672 m ² /g, a pore volume of 0.357 ml/g , the content of Na ₂ O is 1.44 wt.%, the content of P ₂ O ₅ is 1.37 wt.%, the content of SiO ₂ is 76.7 wt.% and the content of Al ₂ O ₃ is 20.5 wt.%) was loaded into a hydrothermal treatment reactor, an atmosphere containing 100% steam was introduced, hydrothermal treatment was carried out for 3 hours at a temperature of 560° C. and a pressure of 0.8 MPa, and then the hydrothermally treated molecular sieve material was collected.

500 ml of deionized water was added to 50 g (dry weight) of the hydrothermally treated molecular sieve material and suspended during mixing to obtain the first suspension. The suspension was heated to a temperature of 80°C, a solution of 2.0 mol/l sulfuric acid was added to it, and the addition of acid was stopped when the measured pH value of the acidified first suspension reached 2.8, then the resulting mixture was kept to carry out the reaction at a constant temperature for 4 h and filtered to obtain 40 g of the first solid product.

400 ml of deionized water was added to the first solid product and suspended during mixing to obtain a second suspension. The suspension was heated to a temperature of 80°C, a 2 mol/l sulfuric acid solution was added to the second suspension at a rate of 5 mol/h in terms of H ⁺ and relative to 1 l of the second suspension, and the addition of acid was stopped when the measured pH value of the acidified second suspension reached a level of 1.4, then the resulting mixture was kept to carry out the reaction at a constant temperature for 3 hours, filtered, and then collected the second solid product. The collected solid product was dried at 180°C for 3 hours to obtain a phosphorus-containing molecular sieve with a high content of silicon dioxide Y-1, and the corresponding X-ray diffraction pattern is presented in Fig.1. The X-ray diffraction peaks of the resulting molecular sieve are shown in Table 1, the corresponding peak heights are shown in Table 2, and other properties are shown in Table 3.

Preparation 2

A phosphorus-containing Y2 molecular sieve with a high silica content was prepared as described in Preparation 1, except that the second acid solution was added at a rate of 15 mol/h. An X-ray diffraction pattern of a phosphorus-containing Y-2 molecular sieve with a high content of silicon dioxide is presented in Fig.1. The X-ray diffraction peaks of the resulting molecular sieve are shown in Table 1, the corresponding peak heights are shown in Table 2, and other properties are shown in Table 3.

Comparative Preparative Examples 1-3 provide exemplary molecular sieves not in accordance with the present invention and methods for their preparation.

Comparative Preparative Example 1

The PSRY molecular sieve that was prepared as described in Example 1 of PRC No. ZL98117286.5 is designated DY-1 molecular sieve, and the corresponding X-ray diffraction pattern is shown in FIG. 1. The X-ray diffraction peaks of the obtained molecular sieve are shown in Table 1, the corresponding peak heights are shown in Table 2, and other properties are shown in Table 3.

Comparative Preparative Example 2

500 g of phosphorus-free HY molecular sieve (which is sold under the trade name HY by Changling Branch of Sinopec Catalyst Co., Ltd., and has a lattice parameter of 2.465 nm, a specific surface area of 580 m ² /g, a pore volume of 0 33 ml/g, the content of Na ₂ O is 0.3 wt.%, the content of SiO ₂ is 77.7 wt.%, and the content of Al ₂ O ₃ is 22 wt.%) was loaded into the reactor for hydrothermal treatment, introduced the atmosphere containing 100% steam, hydrothermal treatment was carried out for 1 hour at a temperature of 500° C. and a pressure of 2.0 MPa, and then the hydrothermally treated molecular sieve material was collected.

500 ml of deionized water was added to 80 g (dry weight) of hydrothermally treated molecular sieve material and suspended during mixing to obtain the first suspension. The suspension was heated to a temperature of 80°C, a solution of 1.0 mol/l sulfuric acid was added to it, and the addition of acid was stopped when the measured pH value of the acidified first suspension reached 3.0, then the resulting mixture was kept to carry out the reaction at a constant temperature for approximately 4 hours and filtered to obtain 65 g of the first solid product.

600 ml of deionized water was added to the first solid product and suspended during mixing to obtain a second suspension. The suspension was heated to a temperature of 80°C, 1.0 mol/l phosphoric acid solution was added to the second suspension at a rate of 2 mol/h in terms of H ⁺ and relative to 1 l of the second suspension, and the addition of acid was stopped when the measured pH value acidified second suspension reached a level of 1.4, then the resulting mixture was kept to carry out the reaction at a constant temperature for 3 hours, filtered, and then collected the second solid product. The collected solid product was dried at 180° C. for 3 hours to obtain a phosphorus-containing aluminosilicate molecular sieve DY-2, the corresponding X-ray diffraction pattern being shown in FIG. 1. The X-ray diffraction peaks of the obtained molecular sieve are shown in Table 1, the corresponding peak heights are shown in Table 2, and other properties are shown in Table 3.

Comparative Preparative Example 3

500 g of a phosphorus-containing molecular sieve (same as in Example 1) was loaded into a hydrothermal treatment reactor, an atmosphere containing 100% steam was introduced, hydrothermal treatment was carried out at a temperature of 560°C and a pressure of 0.8 MPa for 3 hours, and then the hydrothermally treated molecular sieve material was collected.

500 ml of deionized water was added to 60 g (dry weight) of hydrothermally treated molecular sieve material and suspended during mixing to obtain the first suspension. The suspension was heated to a temperature of 90°C, a solution of 2.0 mol/l sulfuric acid was added to it, and the addition of acid was stopped when the measured pH value of the acidified first suspension reached 2.5, then the resulting mixture was kept to carry out the reaction at a constant temperature for approximately 4 hours and filtered to obtain 60 g of the first solid product. The collected solid product was dried at 180°C for 3 hours to obtain a phosphorus-containing aluminosilicate molecular sieve DY-3, and the corresponding X-ray diffraction pattern is shown in Fig.1. The X-ray diffraction peaks of the resulting molecular sieve are shown in Table 1, the corresponding peak heights are shown in Table 2, and other properties are shown in Table 3.

Examples of catalysts

Examples 1-6 provide exemplary hydrocracking catalysts of the present application and methods for their preparation. Comparative Examples 1-3 provide exemplary hydrocracking catalysts not in accordance with the present invention and methods for making the same.

Example 1

80 g (dry weight) of Y-1 molecular sieve and 28.8 g of pseudoboehmite (supplied under the trade name PB90 by Changling Branch of Sinopec Catalyst Co., Ltd. and having a dry weight proportion of 70 wt. %) were mixed, where the dry weight proportion means the ratio of the weight of the sample obtained after calcination at 600°C for 3 hours and the initial weight of the sample; the same condition applies below), the mixture was extruded to obtain plastics in the form of a trefoil with a circumscribed circle diameter of 1.6 mm, dried at 120° C for 3 h and calcined at 600°C for 3 h to obtain a carrier CS-1.

After cooling to room temperature, 100 g of CS-1 carrier was impregnated using 70 ml of an aqueous solution containing 34.65 g of ammonium metatungstate (having a tungsten oxide content of 82 mass% and supplied by Sichuan Zigong Cemented Carbide Works) and 24.37 g of nitrate nickel (having a nickel oxide content of 27.85 mass% and supplied by Beijing Xinguang Chemical Reagent Works) was dried at 120°C for 3 hours and calcined at 480°C for 4 hours to obtain a hydrocracking catalyst whose composition is shown in table 4.

Example 2

The catalyst was prepared as described in Example 1, except that a Y-2 molecular sieve was used instead of a Y-1 molecular sieve. The composition of the obtained catalyst is presented in table 4.

Example 3

95 g (dry weight) of Y-1 molecular sieve and 7.2 g of pseudo-boehmite were mixed, the mixture was extruded into plastics in the form of a trefoil with a circumscribed circle diameter of 1.6 mm, dried at 120°C for 3 hours and calcined at 600° C for 3 h to obtain a carrier CS-3.

After cooling to room temperature, 100 g of CS-3 support was impregnated using 45 ml of an aqueous solution containing 13.86 g of ammonium metatungstate and 8.16 g of nickel nitrate, dried at 120° C. for 3 hours, and calcined at 480° C. for 4 hours to obtain a hydrocracking catalyst, the composition of which is presented in table 4.

Example 4

5 g (dry weight) of Y-1 molecular sieve and 135.7 g of pseudo-boehmite were mixed, the mixture was extruded into plastics in the form of a trefoil with a circumscribed circle diameter of 1.6 mm, dried at 120°C for 3 hours and calcined at 600° C for 3 h to obtain carrier CS-4.

After cooling to room temperature, 100 g of CS-4 carrier was impregnated using 70 ml of an aqueous solution containing 74 g of ammonium metatungstate and 43 g of nickel nitrate, dried at 120°C for 3 h, and calcined at 480°C for 4 h. obtaining a hydrocracking catalyst, the composition of which is presented in table 4.

Example 5

50 g (dry weight) of Y-1 molecular sieve, 10 g of titanium dioxide (supplied by Beijing Chemical Reagent Works and having a purity of 99%) and 57.1 g of pseudoboehmite were mixed, and the mixture was extruded to obtain plastics in the form of a trefoil with a circumcircle diameter of 1 .6 mm, dried at 120°C for 3 hours and calcined at 600°C for 3 hours to obtain support CS-5.

After cooling to room temperature, 100 g of CS-5 support was impregnated using 80 ml of an aqueous solution containing 69 g of ammonium metatungstate and 17 g of nickel nitrate, dried at 120°C for 3 h, and calcined at 480°C for 4 h. obtaining a hydrocracking catalyst, the composition of which is presented in table 4.

Example 6

30 g (dry weight) of Y-1 molecular sieve, 160 g of silica sol (supplied under the trade name JN-25 by Beijing Feilongma Trade Co., Ltd. and having a silica content of 25% and a silica particle size of 9 to 11 nm) and 42.9 g of pseudoboehmite (supplied under the trade name PB90 by Changling Branch of Sinopec Catalyst Co., Ltd. and having a dry weight ratio of 70% by mass), the mixture was extruded to obtain plastics in the form of a trefoil with a diameter of the circumscribed circle 1.6 mm, dried at 120°C for 3 hours and calcined at 600°C for 3 hours to obtain support CS-6.

After cooling to room temperature, 100 g of CS-6 carrier was impregnated using 95 ml of an aqueous solution containing 29 g of molybdenum trioxide supplied by Luoyang Jinduicheng Molybdenum Industry and having a purity of 99.6%) with 67 g of cobalt nitrate (having a cobalt oxide content of 27 .85 wt.% and supplied by Beijing Xinguang Chemical Reagent Works) and 11.8 g of phosphoric acid (supplied by Beijing Chemical Reagent Works and having a purity of 85%), dried at 120°C for 3 hours and calcined at 480°C within 4 hours to obtain a hydrocracking catalyst, the composition of which is presented in table 4.

Comparative Examples 1-3

The catalyst was prepared as described in Example 1, except that DY-1, DY-2, and DY-3 molecular sieves, respectively, were used instead of Y-1 molecular sieve. The composition of the obtained catalyst is presented in table 4.

Study examples

This study example was used to evaluate the catalytic activity of the catalysts obtained in examples 1-3 and comparative examples 1-3 in relation to hydrocracking reactions.

Catalyst activity in hydrocracking reactions was evaluated using a small fixed bed hydrocracking reactor and n-octane feedstock containing 5.61% tetralin and 0.29% pyridine, catalyst loading was 0.2 ml, reaction temperature was 320° C, the pressure in the reactor was 4.0 MPa, the volume ratio of hydrogen and oil was 3600, and the hourly space velocity of the liquid was 30 h ^-1 . After 4 hours of stable reaction, the percentage of tetralin converted to product was determined, which reflected the activity of the catalyst, and the corresponding results are presented in Table 5.

From the results presented in Table 5, it can be seen that, under comparable conditions, the hydrocracking activity of the catalysts containing the phosphorus-containing high-silica molecular sieve according to the present application, in the presence of a high concentration of nitrogen-containing compounds (for example, pyridine) is increased by at least 7% compared to catalysts containing a phosphorus-containing aluminosilicate molecular sieve not in accordance with the present invention.

The present application is illustrated in detail above in this document with the presentation of preferred embodiments, but is not intended to be limited to these embodiments. Various modifications can be made in accordance with the inventive concept of the present application, and these modifications should be within the scope of this application.

It should be noted that the various technical features described in the above embodiments may be combined in any suitable manner without conflict, and in order to prevent unnecessary repetition, various possible combinations are not described in this application, but such combinations should also be within the scope of this application. .

In addition, the various embodiments of the present application may be combined arbitrarily, provided that they should not deviate from the idea of the present application, and such combined embodiments should be considered as a disclosure of the present application.

Claims (41)

1. Phosphorus-containing molecular sieve with a high content of silicon dioxide for the production of a hydrocracking catalyst containing from 86.5 to 99.8 wt.% silicon, from 0.1 to 13.5 wt.% aluminum and from 0.01 to 6 wt. % phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve, wherein the molecular sieve is characterized by an x-ray diffraction pattern containing at least three diffraction peaks, wherein the first intense peak is present at a diffraction angle of 5.9 to 6.9°; the second intense peak is present at a diffraction angle of 10.0 to 11.0°; and a third intense peak is present at a diffraction angle of 15.6 to 16.7°. 2. The molecular sieve of claim 1, wherein the high silica molecular sieve contains 90 to 99.8 wt. % silicon, 0.1 to 9.0 wt. % aluminum, and 0.01 to 2.0 wt. 5 wt.% phosphorus in terms of oxides and in relation to the dry weight of the molecular sieve, and at the same time in the X-ray diffraction pattern of the molecular sieve, the first intense peak is present at a diffraction angle of 6.1 to 6.8°; the second intense peak is present at a diffraction angle of 10.2 to 10.7°; and a third intense peak is present at a diffraction angle of 15.8 to 16.5°. 3. A molecular sieve according to claim 1 or 2, wherein the molecular sieve has a pore volume of 0.20 to 0.50 ml/g and a specific surface area of 250 to 670 m ² /g. 4. A molecular sieve according to claim 1 or 2, wherein the molecular sieve has a pore volume of 0.30 to 0.45 ml/g and a specific surface area of 260 to 600 m ² /g. 5. Molecular sieve according to claim 1 or 2, and on the X-ray diffraction pattern of the molecular sieve I1/I23.5-24.5° is from 3.0 to 11.0, I2/I23.5-24.5° is from 2 .9 to 7.0, and I3/I23.5-24.5° is from 1.0 to 4.0, where I1 is the peak height for the first intense peak, I2 is the peak height for the second intense peak, and I3 is the peak height for the third intense peak, and I23.5-24.5° is the peak height for the peak at a diffraction angle of 23.5 to 24.5°. 6. Molecular sieve according to PP. 1-5, wherein the molecular sieve is characterized by an x-ray diffraction pattern containing at least five diffraction peaks, with a fourth intense peak present at a diffraction angle of 20.4 to 21.6°; and the fifth intense peak is present at a diffraction angle of 11.8 to 12.8°. 7. The molecular sieve according to claim 6, wherein in the X-ray diffraction pattern of the molecular sieve, the fourth intense peak is present at a diffraction angle of 20.8 to 21.4°; and the fifth intense peak is present at a diffraction angle of 12.1 to 12.6°. 8. A molecular sieve according to claim 6 or 7, wherein in the X-ray diffraction pattern of the molecular sieve, I4/I23.5-24.5° is from 1.0 to 4.0 and I5/I23.5-24.5° is from 1.0 to 2.0, where I4 is the peak height for the fourth intense peak, I5 is the peak height for the fifth intense peak, and I23.5-24.5° is the peak height for the peak at a diffraction angle of 23.5 to 24.5°. 9. A method for producing a phosphorus-containing molecular sieve with a high content of silicon dioxide, including the following stages: a) carrying out hydrothermal treatment of the raw material of the phosphorus-containing molecular sieve at a temperature of 350 to 700°C, a pressure of 0.1 to 8.0 MPa and in the presence of steam for 0.5 to 10 hours, to obtain a hydrothermally processed molecular sieve material; wherein the starting material of the phosphorus-containing molecular sieve has a phosphorus content of 0.1 to 15 wt.%, a sodium content of 0.5 to 4.5 wt.%, a silicon content of 70 to 85 wt.%, and a content of aluminum, comprising from 16.0 to 21.0 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve; b) adding water to the hydrothermally treated molecular sieve material obtained in step (a) to form a first slurry, heating the first slurry to a temperature of 40 to 95° C., then adding the first acid solution to the first slurry while maintaining the temperature at that the amount that the acidified first suspension has a pH value of 2.3 to 4.0, carrying out the reaction at a constant temperature for 0.5 to 20 hours and collecting the first solid product; And c) adding water to the first solid product obtained in step (b) to form a second slurry, heating the second slurry to a temperature of 40 to 95° C., then adding the second acid solution to the second slurry in such an amount while maintaining a constant temperature that the acidified second slurry has a pH of 0.8 to 2.0, reacting at a constant temperature for 0.5 to 20 hours, and collecting the second solid, and drying the second solid to obtain a phosphorus-containing molecular sieve with a high silicon dioxide content. 10. The method according to claim 9, in which in step (a), hydrothermal treatment of the phosphorus-containing molecular sieve raw material is carried out at a temperature of 400 to 650° C., a pressure of 0.5 to 5 MPa, and in the presence of steam for 1 to 7 hours; the phosphorus-containing molecular sieve starting material having a phosphorus content of 0.1 to 6 wt.%, a sodium content of 0.5 to 3.0 wt.%, a silicon content of 70 to 80 wt.%, and an aluminum content of 16.0 to 21.0 wt.% in terms of oxides and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve; in step (b) the first suspension is heated to a temperature of 50 to 85°C, the acidified first suspension has a pH of 2.5 to 4.0 and the reaction is carried out for 1 to 10 hours; And in step (c), the second suspension is heated to a temperature of 50 to 85°C, the acidified second suspension has a pH of 1.0 to 2.0, and the reaction is carried out for 1 to 10 hours. 11. The method according to claim 9 or 10, wherein in step (a) the phosphorus-containing molecular sieve starting material is a phosphorus-containing Y molecular sieve having a crystal lattice parameter of 2.425 to 2.47 nm, a specific surface area of 250 up to 750 m ² /g, and a pore volume of 0.2 to 0.95 ml/g. 12. The method according to any one of paragraphs. 9-11, wherein in step (b) the ratio of the weight of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is between 14:1 and 5:1; and/or in step (c), the weight ratio of the water in the second slurry to the dry weight of the phosphorus-containing molecular sieve starting material is between 0.5:1 and 20:1. 13. The method according to any one of paragraphs. 9-12, in which in step (c) the addition of the second acid solution is carried out by adding the second acid solution to the second suspension at a rate of 0.05 to 15 mol/h, calculated as H + and with respect to 1 l of the second suspension . 14. The method according to any one of paragraphs. 9-13, wherein in step (b) the first acid solution has an acid concentration of 0.01 to 15.0 mol/L, and the acid in the first acid solution is at least one acid selected from the group which are phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid; and/or in step (c), the second acid solution has an acid concentration of 0.01 to 15.0 mol/l, and the acid in the second acid solution is at least one acid selected from the group consisting of phosphoric acid, sulfuric acid , nitric acid, hydrochloric acid, citric acid, tartaric acid, formic acid and acetic acid. 15. The method according to any one of paragraphs. 9-14, according to which the drying is carried out under the following conditions: the temperature is from 50 to 350°C and the drying time is from 1 to 24 hours. 16. Hydrocracking catalyst containing, in relation to the dry weight of the catalyst, from 45 to 90 wt.% of the carrier in terms of dry matter; from 1 to 40 wt.% component of the first metal in terms of metal oxides; and from 1 to 15 wt.% component of the second metal in terms of metal oxides; the carrier contains a phosphorus-containing molecular sieve with a high content of silicon dioxide and a refractory inorganic oxide, and the mass ratio of the phosphorus-containing molecular sieve with a high content of silicon dioxide and refractory inorganic oxide is 0.03:1 to 20:1; wherein the first metal component comprises a Group VIB metal, the second metal component comprises a Group VIII metal, and the high silica phosphorus molecular sieve is the high silica phosphorus molecular sieve of any one of claims. 1-3 or a phosphorus-containing molecular sieve with a high content of silicon dioxide, obtained by the method according to any one of paragraphs. 9-15. 17. The hydrocracking catalyst of claim 16, wherein the refractory inorganic oxide is selected from the group consisting of alumina, silica, titanium dioxide, zirconium dioxide, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and any combination thereof. ; the first metal component is selected from the group consisting of a molybdenum component, a tungsten component, and any combination thereof; and/or the second metal component is selected from the group consisting of an iron component, a nickel component, a cobalt component, and any combination thereof. 18. A method for producing a hydrocracking catalyst according to claim 16 or 17, including the following steps: i) mixing a phosphorus-containing molecular sieve with a high content of silicon dioxide according to any one of paragraphs. 1-8 or a phosphorus-containing molecular sieve with a high content of silicon dioxide, obtained by the method according to any one of paragraphs. 9-15 with a refractory inorganic oxide to form a support; And ii) contacting the carrier with an impregnating solution containing a first metal precursor and a second metal precursor for impregnation, then drying and calcining the impregnated material. 19. The method of claim 18, wherein the first metal precursor is a first metal inorganic acid, a first metal inorganic salt, a first metal oxide, or a first metal organometallic compound; wherein the inorganic salt is at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the first metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group; and/or the second metal precursor is a second metal inorganic acid, a second metal inorganic salt, a second metal oxide, or a second metal organometallic compound; wherein the inorganic salt is at least one salt selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the second metal organometallic compound is at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group. 20. The method according to p. 18 or 19, according to which in stage (ii) the drying is carried out under the following conditions: the temperature is from 80 to 350°C and the drying time is from 0.5 to 24 hours; and/or the calcination is carried out under the following conditions: the temperature is from 350 to 600°C and the calcination time is from 0.2 to 12 hours. 21. The use of a hydrocracking catalyst according to any one of paragraphs. 16, 17 or hydrocracking catalyst obtained by the method according to any one of paragraphs. 18-20 in hydrocracking a hydrocarbon feed comprising the step of contacting said hydrocarbon feed with said hydrocracking catalyst. 22. The use of claim 21, wherein the hydrocarbon feedstock is selected from the group consisting of direct distillation gas oils, vacuum distillation gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillates, catalytically cracked distillates. , shale oils, oil sands oils, liquid coal gasification products and any combination thereof; and/or the hydrocracking reaction is carried out under the following conditions: the reaction temperature is from 200 to 650°C; the pressure in the reactor is from 3 to 24 MPa; the hourly space velocity of the liquid is from 0.1 to 50 h ^-1 ; and the volume ratio of hydrogen and oil is from 100 to 5000.

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