RU2782564C2 - Phosphorus-containing molecular sieve, its production and use - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: inventions relate to phosphorus-containing molecular sieves, their production and use. A phosphorus-containing molecular sieve having a faujasite structure is described for use in hydrocracking of initial hydrocarbon materials, having a phosphorus content per oxide from 0.3 wt.% to 5 wt.%, a pore volume from 0.2 ml/g to 0.95 ml/g, and the ratio of the content of Brensted acid centers and the content of Lewis acid centers from 3.4 to 9.5, while the molecular sieve has a structural spectrum of NMR ²⁷Al, which is a ratio of I₆₀ w.f./I_-1 w.f., which is from 5 to 40, and the ratio of L_-1 w.f./I_±6 w.f., which is from 0.4 to 2. A method for the production of the above-described molecular sieve is described. A hydrocracking catalyst including the above-described phosphorus-containing molecular sieve, and its production method are described.

EFFECT: increase in the activity of a hydrocracking catalyst.

22 cl, 4 tbl, 8 ex, 1 dwg

Description

Cross-reference to related applications

The present application claims the priority of Patent Application No. 201711046549.4 entitled "Phosphorus-Containing Molecular Sieve, Its Production and Use" filed by the Applicant on October 31, 2017 with the PRC Patent Office, and Patent Application No. 201711048395.2 entitled "Hydrocracking Catalyst, Its Production and Use" and filed by the Applicant on October 31, 2017 with the PRC Patent Office, 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, in particular, to a phosphorus-containing molecular sieve, its production and use.

State of the art of the present invention

Industrial hydrocracking feedstocks contain fractions having boiling points in the range of 350 to 540°C, such as vacuum gas oil, which contains large amounts of polycyclic aromatic hydrocarbons and cycloalkanes. The study shows that in the high conversion zone through hydrocracking, the content of aromatic hydrocarbons in the heavy fraction decreases and the content of naphthenic hydrocarbons increases, and thus the degree of ring opening is an effective means of improving the quality of the oil tailings and increasing the smoke point of aviation kerosene. However, since the β-bond in cycloalkanes is oriented in the vertical direction of the unfilled p-orbital of the cycloalkane-derived carbonium ion, they cannot easily form a coplanar conformation, and thus higher acidity is required for ring-opening of cycloalkanes. Molecular sieves have a relatively higher acidity and are widely used for hydrocracking reactions. However, conventional HY molecular sieves have an unstable structure and undergo frame dealumination during the preparation and use of catalysts. Non-framework aluminum formed during molecular sieve production is typically low in acidity and can shield Brønsted acid sites, resulting in poor catalyst performance. The structure of the molecular sieves can be stabilized by over-stabilization during hydrothermal treatment, the introduction of the second component, etc., and the second input component usually contains a rare earth component and a phosphorus component. Phosphorus can form a higher molecular weight phosphorus aluminum oxide complex with non-framework aluminum removed from the molecular sieve during the calcination process. Said complex has increased thermal stability and is beneficial in preventing dealuminization of the framework, whereby it can partially act as rare earth components.

PRC Patent Application Publication No. CN 1279130 A discloses a method for producing a phosphorus-containing Y-type molecular sieve, which includes subjecting a P-NH ₄ NaY molecular sieve having a phosphorus content of 0.5 to 5 mass% (in terms of P) to hydrothermal calcination. ₂ O ₅ ), Na ₂ O content from 0.5 to 6 wt.% and a crystal lattice constant from 2.460 to 2.475 nm, at a temperature of from 450 to 700 ° C for 0.5 to 4 h in an atmosphere of 100% steam in an oven for calcination; the impact of liquid-phase dealumination and the addition of SiO ₂ on the calcined product; and then filtering and washing to obtain a phosphorus-containing Y-type ultra-stable molecular sieve.

PRC Patent Application Publication No. CN1727280 A discloses a phosphorus-containing molecular sieve containing 85 to 99.9 wt.% of molecular sieve and about 0.1 to 15 wt.% of phosphorus in terms of P ₂ O ₅ . In the ³¹ P NMR spectrum in the molecular sieve magic angle rotation (MAS) mode, the percentage of the peak area with a chemical shift of 0±1.0 ppm and the total peak area is less than 1%. The preparation of the molecular sieve includes the following steps: introducing phosphorus into the molecular sieve and washing the molecular sieve with an aqueous solution containing an acid, the acid being one or more acids selected from the group consisting of water-soluble organic acids and inorganic acids, the acid content being from 0.0001 to 10.0 mol/l, and the washing temperature is from room temperature to 95°C.

In the prior art, phosphorus-containing molecular sieves are typically post-treated to further increase the stability and acidity of the molecular sieves. Methods for this post-treatment typically include heat treatment and acid leaching.

Currently used heat treatment methods for molecular sieves typically include heat treatment and hydrothermal treatment, both of which allow a certain amount of unstable aluminum compounds to be removed, whereby the stability of the molecular sieve can be improved. The silica in the molecular sieve can form hydrated silicon compounds at high temperature under hydrothermal conditions, which improves the mobility of hydrated silicon compounds, and as a result, the reaction energy barrier difference of 10 to 30 kJ/mol between silicon removal and aluminum removal can be overcome, and a balance between dealumination and silicon incorporation can be achieved. Finally, the framework structure of the molecular sieve can be more fully maintained. The introduction of water in the hydrothermal treatment can be carried out in two modes, which are the introduction of steam during calcination and the release of water through autogenous calcination of the material. In two regimes, since the temperature exceeds the vaporization temperature of water under applied pressure conditions, a three-phase reaction occurs in the reaction system involving gas, liquid and solid phases, and thus the silicon removal reaction can exhibit microscopic heterogeneity. In addition, the vapor pressure greatly increases due to the effect of volumetric expansion when converting a liquid into a gas, which causes the reaction of the molecular sieve material in the reaction system during the production of the molecular sieve. For this reason, the degree of reaction of the molecular sieve may exhibit considerable heterogeneity depending on the atmosphere at the microscopic level, and the final distribution of framework aluminum in the molecular sieve becomes non-uniform, thereby reducing its reactivity.

Although certain phosphorus-containing molecular sieves and methods for their preparation are known in the art, there is still a need for phosphorus-containing molecular sieves that exhibit increased activity in the hydrocracking reaction and selectivity in the ring-opening reaction when used in hydrocracking catalysts, as well as methods for producing such molecular sieves.

Brief summary of the present invention

It is an object of the present application to provide a phosphorus-containing molecular sieve having a specific combination of characteristics, in particular a high ratio of Bronsted acid sites to Lewis acid sites, with which other specific characteristics are combined such that the molecular sieve can exhibit enhanced activity. in the hydrocracking reaction and selectivity in the ring-opening reaction when it is used in the preparation of a hydrocracking catalyst, as well as to suggest the preparation and use of this molecular sieve. Another object of the present application is to provide a hydrocracking catalyst containing a phosphorus-containing molecular sieve according to the present application, as well as the preparation and use of this catalyst.

To solve the above problem, according to an aspect of the present application, a phosphorus-containing molecular sieve is provided, having a phosphorus content of from about 0.3 wt.% to about 5 wt.% in terms of oxide, a pore volume of from about 0.2 ml / g to about 0.95 ml/g, and a ratio of Bronsted acid sites to Lewis acid sites of about 2 to about 10.

Preferably, the structural ²⁷ Al NMR spectrum of the phosphorus-containing molecular sieve has an I ratio of _{60 ppm.} /I _{-1 ppm} , ranging from about 5 to about 40, and the ratio I _{-1 ppm.} /I _{±6 ppm} , ranging from about 0.4 to about 2.

According to another aspect of the present application, a method for producing a phosphorus-containing molecular sieve is provided, comprising the following steps:

i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is in the range of from about 14:1 to about 5:1;

iii) subjecting the resulting molecular sieve slurry to an acid leach; and

iv) recovering the solid product,

wherein the acid leach in step (iii) is carried out as follows: adding the acid solution to the molecular sieve slurry at a substantially constant rate at a temperature of from about 40° C. to about 95° C., while adding the acid solution at a rate of from about 0 05 mol/h to about 10 mol/h in terms of H ⁺ in relation to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for from about 0.5 h to about 20 h, and the ratio the weight of the acid in the acid solution and the dry weight of the phosphorus-containing molecular sieve starting material range from about 0.01:1 to about 0.6:1.

Preferably, the phosphorus-containing molecular sieve feedstock has a phosphorus content of from about 0.1 wt.% to about 15 wt.%, and a sodium content of from about 0.5 wt.% to about 4.5 wt.% in terms of oxides and relative to the dry weight of the source material of the phosphorus-containing molecular sieve.

The phosphorus-containing molecular sieve starting material is preferably a Y-type phosphorus-containing molecular sieve having a lattice constant of 2.425 to 2.470 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.

Preferably, the phosphorus-containing molecular sieve feedstock is present in particulate form, and the phosphorus-containing molecular sieve feedstock having a particle size of from about 1 mm to about 500 mm is from about 10% to about 100% by weight of the total weight of the phosphorus-containing molecular sieve feedstock, wherein the particle size is the diameter of a sphere circumscribed around the particle.

According to a further aspect of the present application, there is provided a phosphorus-containing molecular sieve obtainable by the process for producing a phosphorus-containing molecular sieve according to the present application.

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

the carrier contains a phosphorus-containing molecular sieve according to the present invention and a refractory inorganic oxide, and the mass ratio of the phosphorus-containing molecular sieve and refractory inorganic oxide is from about 0.03:1 to about 20:1; the first metal is a Group VIB metal; and the second metal is a Group VIII metal.

Preferably, the refractory inorganic oxide is selected from the group consisting of alumina, silica, amorphous silica and alumina double oxides, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and combinations thereof; the first metal is molybdenum and/or tungsten; the second metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

According to a further aspect of the present application, the use of the phosphorus-containing molecular sieve of the present application in the preparation of hydrocracking catalysts is provided.

According to a further aspect of the present application, there is provided a process for preparing a hydrocracking catalyst, comprising the steps of contacting the carrier with an impregnating solution containing a parent metal compound to effect impregnation, and also drying the material obtained after impregnation, wherein:

the carrier contains a phosphorus-containing molecular sieve according to the present application and a refractory inorganic oxide, the parent metal compound contains the parent compound of the first metal and the parent compound of the second metal, the first metal is a group VIB metal, and the second metal is a group VIII metal;

preferably, the method further comprises the steps of mixing a phosphorus-containing molecular sieve and a refractory inorganic oxide with a peptizing agent and optionally a lubricant, and then shaping, drying and calcining to obtain a carrier.

Preferably, the first metal parent compound is selected from the group consisting of first metal inorganic acids, first metal inorganic salts, first metal organometallic compounds, and combinations thereof; wherein the inorganic salt is preferably selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; the organic fragment in the organometallic compound of the first metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups and combinations thereof;

the parent compound of the second metal is selected from the group consisting of inorganic acids of the second metal, inorganic salts of the second metal, organometallic compounds of the second metal, and combinations thereof; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; the organic moiety in the organometallic compound of the second metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof.

According to a further aspect of the present application, the use of a phosphorus-containing molecular sieve according to the present application or a hydrocracking catalyst according to the present application in the hydrocracking of hydrocarbon feedstocks is provided.

According to a further aspect of the present application, a process for hydrocracking a hydrocarbon feedstock is provided, comprising the step of hydrocracking the hydrocarbon feedstock in the presence of a phosphorus-containing molecular sieve according to the present application or a hydrocracking catalyst according to the present application.

According to the present application, the phosphorus-containing molecular sieve raw material is subjected to special processing to obtain a phosphorus-containing molecular sieve having excellent performance, and the phosphorus-containing molecular sieve has a specific combination of characteristics, in particular, a high ratio of Bronsted acid sites to Lewis acid sites, with which other specific characteristics. Compared to existing phosphorus-containing molecular sieves, the phosphorus-containing molecular sieve of the present application exhibits increased activity in the hydrocracking reaction and selectivity in the ring-opening reaction when used in the preparation of hydrocracking catalysts. Accordingly, a hydrocracking catalyst prepared from a phosphorus-containing molecular sieve exhibits improved hydrocracking reaction activity and ring-opening reaction selectivity when used in hydrocracking reactions.

Other characteristics and advantages of the present application will be detailed below in the detailed disclosure section.

Brief description of the figures

The drawing, which forms part of the present description, is provided to assist in the understanding of the present application and should not be construed as limiting. The present application may be construed with reference to the figure in combination with the embodiments that are described hereinafter. A drawing is given where:

in fig. 1 shows the ²⁷ Al NMR structural spectrum of the molecular sieves prepared in Examples I-1 to I-3 and Comparative Examples I-1 to I-4.

Detailed disclosure of the present invention

Hereinafter, the present application will be described in detail with reference to its embodiments and accompanying figures. It should be noted that the embodiments of the present application are presented solely for the purpose of illustration and are not intended to be restrictive in any way.

Any specific numerical value, including the end points of the numerical range described in the context of this application, is not limited to the corresponding exact value, but should be construed as further covering all values in the vicinity of the aforementioned exact value. In addition, with respect to any numerical range described herein, arbitrary combinations may be made between the end points of the range, between each end point and any particular value within the range, or between any two particular values within the range, to obtain one or more new numerical ranges, and one or more of the above new numerical ranges should also be considered as specifically described in this application.

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

In the context of this application, in addition to the specifically declared objects, any object or objects that are not mentioned are considered the same as objects known in the art, without any change. In addition, any of the embodiments described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus obtained should be considered as part of the original disclosure or the original description of this application. and should not be considered as a new subject that has not been disclosed or contemplated herein, unless it is obvious and clear to those skilled in the art that such a combination is unreasonable.

Unless otherwise noted, all pressures given in this document are gauge pressures.

Unless otherwise stated, all particle sizes given herein refer to the diameter of a sphere circumscribing the particle.

As used herein, the term "phosphorus-containing molecular sieve starting material" means a phosphorus-containing molecular sieve used as a starting material. According to the present application, when a phosphorus-containing molecular sieve raw material is used, phosphorus-aluminum compounds on the outside of the molecular sieve framework can improve the stability of the molecular sieve framework, and as a result, the performance of the molecular sieve is further improved.

As used herein, the term "substantially constant rate" means the substantially continuous addition of the acid solution to the molecular sieve slurry at a substantially constant rate until the weight of the added amount of acid in the acid solution reaches a predetermined value, the term "substantially continuous addition" means continuous addition until completion of the addition, or addition carried out several times with interruptions, each time the addition is carried out in a continuous manner. By adding the acid in a substantially continuous manner, the addition of the acid and the acid leaching reaction can be carried out simultaneously, and the acid can be added at a slower rate, which makes the dealumination process more moderate and thus is favorable for improving the performance of the molecular sieve.

In particular, in the context of this application, the expression "add the acid solution to the molecular sieve slurry at a substantially constant rate" refers to the case where the acid solution is continuously added to the molecular sieve slurry at a substantially constant rate until a predetermined amount of acid solution is added. at once; and also extends to the case where the acid solution is added to the molecular sieve slurry several times, where the acid solution is continuously added at a substantially constant rate each time during the addition, and the resulting mixture can be subjected to an isothermal reaction (i.e., reaction at a constant temperature) for a period of time each time an acid is added, and then the next addition of acid can be carried out until a predetermined amount of acid solution has been added. The rate of addition of the acid solution during each addition may be the same or different and is independently from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h .

All patent and non-patent documents cited herein, including, without limitation, manuals, journal articles, and similar documents, are incorporated herein by reference in their entirety.

According to the first aspect of the present application, a phosphorus-containing molecular sieve having a phosphorus content of from about 0.3 wt.% to about 5 wt.%, preferably from about 0.4 wt.% to about 2.0 wt.% in terms of oxide, a pore volume of from about 0.2 ml/g to about 0.95 ml/g, preferably from about 0.25 ml/g to about 0.60 ml/g, and the ratio of Bronsted acid sites to acid Lewis centers from about 2 to about 10, preferably from about 3.4 to about 9.5.

The phosphorus-containing molecular sieve according to the present application has an increased ratio of Bronsted acid sites to Lewis acid sites. In particular, the phosphorus-containing molecular sieve according to the present application retains not only a high ratio of framework aluminum to non-framework aluminum, but also a certain amount of non-framework aluminum, for example, in a position with a chemical shift from -4 ppm. up to -6 ppm or chemical shift from 3 ppm up to 7 ppm In particular, the molecular sieve has a structural ^27Al NMR spectrum in which the ratio of the peak height of framework aluminum at 60±1 ppm is and non-framework aluminum peak heights at -1±1 ppm, i.e. ratio I _{60 ppm} /I _{-1 ppm} is from about 5 to about 40, preferably from about 10.0 to about 39; and there are two distinct non-frame aluminum characteristic peaks, with one of these peaks occurring at -1±1 ppm and the other peak occurring at -5.5±2 ppm. or from 3 to 7 ppm The height ratio of these two characteristic peaks, i.e. ratio I _{-1 ppm} /I _{±6 ppm} is from about 0.4 to about 2, preferably from about 0.8 to about 2, and I _{±6 ppm.} is the height of the higher of these peaks observed at -5.5±2 ppm. and from 3 to 7 ppm

According to a preferred embodiment of the present application, the phosphorus-containing molecular sieve has a crystal lattice constant of 2.425 to 2.470 nm, preferably 2.430 to 2.458 nm, and a specific surface area of about 250 to 850 m ² /g, preferably about 400 to 750 m ² /g.

According to a preferred embodiment of the present application, the phosphorus-containing molecular sieve is a molecular sieve having a faujasite structure, preferably a Y-type molecular sieve, more preferably a molecular sieve selected from the group consisting of NaY, HNaY, REY, USY molecular sieves and combinations thereof.

According to a preferred embodiment of the present application, the cationic positions of the phosphorus-containing molecular sieve are occupied by one or more types of ions from sodium ions, ammonium ions, and hydrogen ions.

According to a particularly preferred embodiment of the present application, the phosphorus-containing molecular sieve is produced by a process comprising the following steps:

i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is in the range of from about 14:1 to about 5:1;

iii) subjecting the resulting molecular sieve slurry to an acid leach; and

iv) recovering the solid product,

wherein the acid leaching in step (iii) is carried out as follows: adding the acid solution to the molecular sieve slurry at a substantially constant rate at a temperature of from about 40°C to about 95°C, preferably from about 50°C to about 85°C, wherein the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for from about 0.5 h to about 20 h, preferably from about 0.5 h to about 15 h, and the ratio of the weight of acid in the acid solution to the dry weight the source material of the phosphorus-containing molecular sieve is from about 0.01:1 to about 0.6:1.

According to a further preferred embodiment, the starting material of the phosphorus-containing molecular sieve may be a faujasite molecular sieve, and is preferably a Y-type phosphorus-containing molecular sieve, which may have a lattice constant of 2.425 to 2.470 nm, preferably 2.440 to 2.470 nm, specific a surface area of from about 250 to 750 m ² /g, preferably from about 400 to 700 m ² /g, and a pore volume of from about 0.2 ml/g to about 0.95 ml/g, preferably from about 0.2 ml/g to about 0.5 ml/g. In addition, the selected Y-type molecular sieve can vary widely, provided that the starting material of the phosphorus-containing molecular sieve satisfies the above requirements. For example, the Y-type molecular sieve may be selected from the group consisting of NaY molecular sieve, HNaY (Y-type hydrogen molecular sieve), REY (Y-type rare earth molecular sieve), USY (Y-type ultra stable molecular sieve), and the like. The cationic positions of the phosphorus-containing Y-type molecular sieve may be occupied by one or more of sodium ions, ammonium ions, and hydrogen ions; or, alternatively, the sodium, ammonium, and hydrogen ions in the molecular sieve may 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 raw material of the phosphorus-containing molecular sieve may be a commercial product, and it may also be produced by any method described in the related art, such as the USY molecular sieve production method disclosed in PRC Patent Application Publication No. CN 1350886 A, or the production method molecular sieve PUSY disclosed in PRC Patent Application Publication No. CN1727280 A, and the like, which will not be described in detail herein.

According to a further preferred embodiment, the phosphorus-containing molecular sieve feedstock has a water content of from about 10% by weight to about 40% by weight. Phosphorus-containing molecular sieve feedstocks having such a water content can be obtained by adding water to the molecular sieve feedstock, suspending, and then filtering and drying. In addition, the phosphorus-containing molecular sieve feedstock is preferably present in particulate form, and the phosphorus-containing molecular sieve feedstock having a particle size of about 1 mm to about 500 mm can be from about 10 wt.% to about 100 wt.%, preferably from about 30 wt.% to about 100 wt.% of the total weight of the source material of the phosphorus-containing molecular sieve. Further, a phosphorus-containing molecular sieve starting material having a particle size of from about 5 mm to about 100 mm may comprise from about 30 wt.% to about 100 wt.% of the total weight of the phosphorus-containing molecular sieve starting material. The use of a phosphorus-containing molecular sieve starting material with the above-described particle size in a hydrothermal treatment can significantly improve the mass transfer efficiency of the hydrothermal treatment, reduce material loss, and improve operational stability. The particle size of the molecular sieve raw material can be controlled by a conventional method known in the art, such as a screening method, a belt extrusion method, a rolling ball method, and the like.

According to a further preferred embodiment, the hydrothermal treatment in step (i) is carried out in the presence of steam, preferably in the presence of 30% to 100% steam, under the following conditions: temperature is from about 350 to 700° C., pressure is from about 0.1 to 2 MPa, and the duration of the hydrothermal treatment is approximately 0.5 to 10 hours.

According to a further preferred embodiment, the molecular sieve slurry is prepared in step (ii) by forming a slurry of the hydrothermally treated molecular sieve material with water, wherein the expression "forming a slurry with water" has the meaning well known to those skilled in the art and the mass ratio of water in the slurry molecular sieve obtained after suspension, and the dry weight of the source material of the phosphorus-containing molecular sieve may be in the range from about 14:1 to about 5:1.

In some further preferred embodiments, in step (iii), the acid solution is added once to the molecular sieve slurry at a substantially constant rate, i. is added continuously at a given rate until all the acid solution has been added, and then the resulting product is subjected to an isothermal reaction, i.e. reactions at constant temperature.

In some other further preferred embodiments, in order to improve material utilization and reduce waste generation, the acid solution is added several times, wherein the acid solution is continuously added to the molecular sieve slurry at a predetermined rate, each time during the addition, the resulting product is subjected to an isothermal reaction for a period of time. after each addition, and then the next addition of acid is carried out until the specified amount of acid solution is completely added. For example, the acid solution may be added 2 to 10 times, and the acid solution may be added at a substantially constant rate ranging from about 0.05 mol/hr to about 10 mol/hr, preferably from about 0.2 mol/hr to about 3.0 mol/h each time in terms of H ⁺ in relation to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction for a period of time after each addition, so that the total duration of the isothermal reaction is approximately from 0, 5 to 20 hours, preferably from about 0.5 to 15 hours. When the acid solution is added several times, the weight ratio of the acid in the acid solution to the dry weight of the phosphorus-containing molecular sieve starting material is preferably from about 0.01:1 to about 0.3:1.

According to a further preferred embodiment, the acid solution may have an acid concentration of from about 0.01 mol/L to about 15.0 mol/L, preferably from about 0.02 mol/L to about 5.0 mol/L, and a pH from about 0.01 to about 3. The acid may be a conventional inorganic acid and/or organic acid, and, for example, it may be selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof.

According to a further preferred embodiment, in step (iii), the ammonium salt can also be added to the molecular sieve slurry during the addition of the acid solution. For example, the ammonium salt may be selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium sulfate, and combinations thereof. Preferably, the weight ratio of the ammonium salt to the dry weight of the phosphorus-containing molecular sieve feedstock may range from about 0.1:1 to about 2.0:1. The ammonium salt may be added to the molecular sieve slurry separately from the acid solution, or the ammonium salt and acid may be made into an aqueous solution in a desired amount and then added to the molecular sieve slurry in the form of an aqueous solution.

According to a further preferred embodiment, after step (iv), the recovered solid is washed with water and dried to obtain a phosphorus-containing molecular sieve. Washing with water and drying are conventional steps in the preparation of molecular sieves, and there is no particular limitation in this regard in this application. For example, drying can be carried out by oven drying, mesh belt drying, rotary oven heating, and the like, and the drying can be carried out under the following conditions: the temperature is about 50 to 350°C, preferably about 70 to 200°C; the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

According to a particularly preferred embodiment of the present application, the phosphorus-containing molecular sieve can be obtained by a method comprising the following steps:

i) subjecting the phosphorus-containing molecular sieve starting material to hydrothermal treatment in the presence of steam, preferably in the presence of 30 to 100% steam, at a temperature of about 350 to 700° C. and a pressure of about 0.1 to 2 MPa, for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material;

ii) forming a slurry of the hydrothermally treated molecular sieve material with water to form a molecular sieve slurry, wherein the weight ratio of the water in the molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1;

iii) heating the molecular sieve slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, and then holding at that temperature and adding the acid solution to the molecular sieve slurry at a substantially constant rate, wherein the weight ratio of the acid is in the acid solution and the dry weight of the starting material of phosphorus-containing molecular sieve is in the range from about 0.01:1 to about 0.6 1 in terms of H ⁺ in relation to 1 l of molecular sieve suspension, while the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 to 3.0 mol/h, and the resulting product is subjected to an isothermal reaction for from about 0.5 h to about 20 h, preferably in for about 0.5 to 15 hours after completion of the addition of the acid; and

iv) recovering the solid product.

According to the second aspect of the present application, a method for producing a phosphorus-containing molecular sieve is provided, comprising the following steps:

i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is in the range of from about 14:1 to about 5:1;

iii) subjecting the resulting molecular sieve slurry to an acid leach; and

iv) recovering the solid product,

wherein the acid leaching in step (iii) is carried out as follows: adding the acid solution to the molecular sieve slurry at a substantially constant rate at a temperature of from about 40°C to about 95°C, preferably from about 50°C to about 85°C, wherein the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for from about 0.5 h to about 20 h, preferably for from about 0.5 h to about 15 h, and the ratio of the mass of acid in the acid solution and dry weight of the source material of the phosphorus-containing molecular sieve is from about 0.01:1 to about 0.6:1.

According to a preferred embodiment, the starting material of the phosphorus-containing molecular sieve may be a faujasite molecular sieve, and it is preferably a Y-type phosphorus-containing molecular sieve, which may have a lattice constant of 2.425 to 2.470 nm, preferably 2.440 to 2.470 nm, a specific surface area of from about 250 to 750 m ² /g, preferably from about 400 to 700 m ² /g, and a pore volume of from about 0.2 ml/g to about 0.95 ml/g, preferably from about 0.2 ml/g to about 0.5 ml/g. In addition, the selected Y-type molecular sieve can vary widely, provided that the starting material of the phosphorus-containing molecular sieve satisfies the above requirements. For example, the Y-type molecular sieve may be selected from the group consisting of NaY molecular sieve, HNaY (Y-type hydrogen molecular sieve), REY (Y-type rare earth molecular sieve), USY (Y-type ultra stable molecular sieve), and the like. The cationic positions of the phosphorus-containing Y-type molecular sieve may be occupied by one or more of sodium ions, ammonium ions, and hydrogen ions; or, alternatively, the sodium, ammonium, and hydrogen ions in the molecular sieve may 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 raw material of the phosphorus-containing molecular sieve may be a commercial product, and it may also be produced by any method described in the related art, such as the USY molecular sieve production method disclosed in PRC Patent Application Publication No. CN 1350886 A, or the production method molecular sieve PUSY disclosed in PRC Patent Application Publication No. CN 1727280 A, and the like, which will not be described in detail herein.

According to a preferred embodiment, the phosphorus-containing molecular sieve feedstock has a water content of from about 10 wt.% to about 40 wt.%. Phosphorus-containing molecular sieve feedstocks having such a water content can be obtained by adding water to the molecular sieve feedstock, suspending, and then filtering and drying. In addition, the phosphorus-containing molecular sieve feedstock is preferably present in particulate form, and the phosphorus-containing molecular sieve feedstock having a particle size of about 1 mm to about 500 mm can be from about 10 wt.% to about 100 wt.%, preferably from about 30 wt.% to about 100 wt.% of the total weight of the source material of the phosphorus-containing molecular sieve. Further, a phosphorus-containing molecular sieve starting material having a particle size of from about 5 mm to about 100 mm may comprise from about 30 wt.% to about 100 wt.% of the total weight of the phosphorus-containing molecular sieve starting material. The use of a phosphorus-containing molecular sieve starting material with the above-described particle size in a hydrothermal treatment can significantly improve the mass transfer efficiency of the hydrothermal treatment, reduce material loss, and improve operational stability. The particle size of the molecular sieve raw material can be controlled by a conventional method known in the art, such as a screening method, a belt extrusion method, a rolling ball method, and the like.

According to a preferred embodiment, the hydrothermal treatment in step (i) is carried out in the presence of steam, preferably in the presence of 30% to 100% steam, under the following conditions: temperature is from about 350 to 700° C., pressure is from about 0.1 to 2 MPa, and the duration of the hydrothermal treatment is approximately 0.5 to 10 hours.

In a preferred embodiment, the molecular sieve slurry is prepared in step (ii) by forming a slurry of the hydrothermally treated molecular sieve material with water, wherein the aforementioned "forming a slurry with water" has a meaning well known to those skilled in the art and the weight ratio of water in the slurry molecular sieve obtained after suspension, and the dry weight of the source material of the phosphorus-containing molecular sieve may be from about 14:1 to about 5:1.

In some embodiments, in step (iii), the acid solution is added once to the molecular sieve slurry at a substantially constant rate, i. is added continuously at a predetermined rate until all the acid solution has been added, and then the resulting product is subjected to an isothermal reaction.

In some other embodiments, in order to improve material utilization and reduce waste generation, the acid solution is added several times, wherein the acid solution is continuously added to the molecular sieve slurry at a predetermined rate each time during the addition, the resulting product undergoes an isothermal reaction for a period of time after each addition, and then the next addition of acid is carried out until the specified amount of acid solution is completely added. For example, the acid solution may be added 2 to 10 times, and the acid solution may be added at a substantially constant rate ranging from about 0.05 mol/hr to about 10 mol/hr, preferably from about 0.2 mol/hr to about 3.0 mol/h each time in terms of H ⁺ in relation to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction for a period of time after each addition, so that the total duration of the isothermal reaction is approximately from 0, 5 to 20 hours, preferably from about 0.5 to 15 hours. When the acid solution is added several times, the weight ratio of the acid in the acid solution to the dry weight of the phosphorus-containing molecular sieve starting material is preferably from about 0.01:1 to about 0.3:1.

In a preferred embodiment, the acid solution may have an acid concentration of from about 0.01 mol/L to about 15.0 mol/L, preferably from about 0.02 mol/L to about 5.0 mol/L, and a pH of about 0.01 to about 3. The acid may be a conventional inorganic acid and/or organic acid and, for example, may be selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof.

According to a preferred embodiment of the present application, the method may further comprise in step (iii) adding an ammonium salt to the molecular sieve slurry during addition of the acid solution. For example, the ammonium salt may be selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium sulfate, and combinations thereof. Preferably, the weight ratio of the ammonium salt to the dry weight of the phosphorus-containing molecular sieve feedstock may range from about 0.1:1 to about 2.0:1. The ammonium salt may be added to the molecular sieve slurry separately from the acid solution, or the ammonium salt and the acid may be made into an aqueous solution in a desired amount and then added to the molecular sieve slurry in the form of an aqueous solution.

According to a preferred embodiment of the present application, the method may further comprise, after step (iv), subjecting the recovered solid to washing with water and drying to obtain a phosphorus-containing molecular sieve. Washing with water and drying are conventional steps in the preparation of molecular sieves, and there is no particular limitation in this regard in this application. For example, drying can be carried out by oven drying, mesh belt drying, rotary oven heating, and the like, and the drying can be carried out under the following conditions: the temperature is about 50 to 350°C, preferably about 70 to 200°C; the drying time is about 1 to 24 hours, preferably about 2 to 6 hours.

According to a particularly preferred embodiment of the present application, the method comprises the following steps:

i) subjecting the phosphorus-containing molecular sieve starting material to hydrothermal treatment in the presence of steam, preferably in the presence of 30 to 100% steam, at a temperature of about 350 to 700° C. and a pressure of about 0.1 to 2 MPa, for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve material;

ii) forming a slurry of the hydrothermally treated molecular sieve material with water to form a molecular sieve slurry, wherein the weight ratio of the water in the molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1;

iii) heating the molecular sieve slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, and then holding at that temperature and adding the acid solution to the molecular sieve slurry at a substantially constant rate, wherein the weight ratio of the acid is in acid solution and dry weight starting material of phosphorus-containing molecular sieve is in the range from about 0.01: 1 to about 0.6: 1 in terms of H ⁺ in relation to 1 l of molecular sieve suspension, while the acid solution is added at a rate, from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 to 3.0 mol/h, and the resulting product is subjected to an isothermal reaction for about 0.5 h to about 20 h, preferably about 0.5 to 15 hours after completion of the acid addition; and iv) recovering the solid product.

According to a third aspect of the present application, there is provided a phosphorus-containing molecular sieve obtainable by the process for producing a phosphorus-containing molecular sieve according to the present application.

By processing the phosphorus-containing molecular sieve raw material in a special way, a phosphorus-containing molecular sieve with excellent performance can be obtained, which exhibits enhanced activity in the hydrocracking reaction and selectivity in the ring-opening reaction when it is used in the production of hydrocracking catalysts.

The phosphorus-containing molecular sieve of the present application is suitable for use in a variety of catalysts exhibiting acid catalytic activity in reactions such as catalytic cracking, hydroisomerization, alkylation, hydrocracking, and the like, and it is particularly suitable for hydrocracking hydrocarbon feedstocks to obtain a hydrocarbon fraction having a lower boiling point and a lower molecular weight.

According to the fourth aspect of the present application, a hydrocracking catalyst is provided containing from about 45 wt.% to about 90 wt.%, preferably from about 55 wt.% to about 85 wt.% of the carrier, calculated on dry matter and in relation to the weight of the catalyst, from about 1 wt.% to about 40 wt.%, preferably from about 12 wt.% to about 35 wt.% component of the first metal in terms of metal oxide and from about 1 wt.% to about 15 wt.%, preferably from about 2 wt.% to about 10 wt.% component of the second metal in terms of metal oxide, and:

the carrier contains a phosphorus-containing molecular sieve according to the present application, which is described above, and a refractory inorganic oxide, and the mass ratio of the phosphorus-containing molecular sieve and refractory inorganic oxide is from about 0.03: 1 to about 20:1, preferably from about 0.03: 1 up to about 6:1; the first metal is a Group VIB metal; and the second metal is a Group VIII metal.

In the hydrocracking catalyst according to the present application, the refractory inorganic oxide can improve the strength of the catalyst, as well as improve and control the physicochemical properties of the catalyst, for example, improve the pore structure of the catalyst. A refractory inorganic oxide suitable for use in the present application contains inorganic oxides commonly used in hydrogenation catalyst supports such as alumina, silica, amorphous silicon and alumina double oxides, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, oxide boron, cadmium oxide, and the like. In some preferred embodiments, the refractory inorganic oxide may be alumina, including hydrargillite such as gibbsite, bayerite, nordstrandite, and diaspore monohydrate such as boehmite, diaspore, pseudoboehmite. In other embodiments, the refractory inorganic oxide may be other types or combinations.

According to a preferred embodiment, the first metal may be molybdenum and/or tungsten; and the second metal may be selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

According to the fifth aspect of the present application, the use of a phosphorus-containing molecular sieve according to the present invention in the preparation of a hydrocracking catalyst is provided.

According to the sixth aspect of the present application, there is provided a process for preparing a hydrocracking catalyst, comprising the steps of contacting an impregnating carrier with an impregnating solution containing a starting metal compound and drying the material obtained after impregnation, wherein:

the carrier contains a phosphorus-containing molecular sieve according to the present application and a refractory inorganic oxide, as described above, and preferably the weight ratio of phosphorus-containing molecular sieve and refractory inorganic oxide is from about 0.03:1 to about 20:1, preferably from about 0.03:1 up to about 6:1; and

the metal parent compound comprises a first metal parent compound and a second metal parent compound, wherein the first metal is a Group VIB metal and the second metal is a Group VIII metal.

According to the present application, contacting the carrier with the impregnation solution and impregnation can be carried out according to any method known in the art, such as the method described in PRC Patent Application Publication No. a Group VIII metal component and an organic additive to the catalyst carrier, wherein the addition of the Group VIB metal component, the Group VIII metal component and the organic additive to the catalyst carrier is carried out by any of the following methods:

first method: contacting the catalyst support with the first solution and then with the second solution, or contacting the catalyst support with the second solution and then with the first solution, the first solution containing a group VIB metal component compound and a group VIII metal component compound, the second solution contains a Group VIB metal component compound, but lacks any Group VIII metal component compound, and the first solution and/or the second solution contains an organic additive;

second method: contacting the catalyst support with a third solution and then with a fourth solution, or contacting the catalyst support with a fourth solution and then with a third solution, wherein the third solution contains a group VIB metal component compound, the fourth solution contains a group VIII metal component compound and an organic excipient, but lacking any Group VIB metal component compound, and the third solution may or may not contain a Group VIII metal component compound and an organic additive,

moreover, after each introduction into contact, the catalyst carrier obtained after contact is heated.

The support used in the catalyst according to the present application can be obtained by a method well known to those skilled in the art, and there is no particular limitation in this regard in this application. For example, the carrier can be obtained by mixing a phosphorus-containing Y-type molecular sieve, a refractory inorganic oxide, a solvent, and optionally an auxiliary substance, followed by shaping and drying. The molding can be carried out by various conventional methods such as tableting method, rolling ball method or belt extrusion method. The solvent may be a solvent commonly used in the process of molding catalysts. When an extrusion method is used, an appropriate amount of an aid is preferably added to facilitate molding.

Preferably, the carrier can be obtained by a method comprising the following steps: mixing a phosphorus-containing Y-type molecular sieve, a refractory inorganic oxide, a peptizing agent, and optionally a lubricant, and then shaping, drying, and calcining to obtain a carrier. The peptizing agent may be an acid-containing solution or a base-containing solution, wherein the acid may be selected from the group consisting of organic acids and inorganic acids known to those skilled in the art, and combinations thereof such as phosphoric acid, sulfuric acid, nitric acid. , hydrochloric acid, acetic acid, tungsten-containing and/or molybdenum-containing heteropolyacids, citric acid, tartaric acid, formic acid and combinations thereof, and cations such as ammonium, iron, cobalt, nickel and aluminum ions can also be added to the solution, which contribute to maintaining the acidity of the acid-containing solution; and the base-containing solution may contain at least one of ammonia, organic amines, and urea.

The shape of the carrier is not specifically limited according to the present application, and may be spherical, plate, hollow plate, block shape, etc., and the plate-shaped carrier may be a multi-leaf clover, such as three-leaf clover, four-leaf clover, or corresponding variants.

According to an alternative embodiment of the present application, the carrier can be prepared according to the method described in PRC Patent Application Publication No. CN 107029779 A, which includes: (1) mixing a phosphorus-containing Y-type molecular sieve with a refractory inorganic oxide, a peptizing agent, a lubricant, and water to obtain a mixture, and the components are used in such quantities that the ratio of the molar amount of the peptizing agent in the mixture and the mass of powdered substances is from 0.28×10 ^-4 mol/g to 4.8×10 ^-4 mol/g, and the ratio the mass of water and the molar amount of the peptizing agent is from 2.0×10 ³ g/mol to 30×10 ³ g/mol, and the mass of powdered substances is the total mass of the Y-type phosphorus-containing molecular sieve and the refractory inorganic oxide, and the molar amount of the peptizing agent is the number of moles of H protons in the peptizing agent; the lubricant is one or two substances from sesbania powder and graphite; and (2) mixing, shaping, drying and calcining the mixture obtained in step (1) to obtain a support.

According to the present application, the parent metal compound comprises a parent compound of a first metal and a parent compound of a second metal, wherein the parent compound of the first metal is a soluble compound containing the first metal, including inorganic acids of the first metal, inorganic salts of the first metal, organometallic compounds of the first metal, and combinations thereof; wherein the inorganic salt may be selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; the organic fragment in the organometallic compound of the first metal may be selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof. For example, when the first metal is molybdenum, the parent compound of the first metal may be selected from the group consisting of molybdic acid, paramolybdic acid, molybdate, paramolybdate, and combinations thereof; when the first metal is tungsten, the parent compound of the first metal may be selected from the group consisting of tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, ethyl metatungstate, and combinations thereof. The second metal parent compound is a soluble second metal containing compound, including second metal inorganic acids, second metal inorganic salts, second metal organometallic compounds, and combinations thereof; wherein the inorganic salt may be selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; the organic fragment in the organometallic compound of the second metal may be selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof.

According to the present application, the impregnating solution may also contain an organic additive, and the concentration of the organic additive may be from about 2 to 300 g/l. The organic additive may be an oxygen-containing organic compound and/or a nitrogen-containing organic compound. For example, the oxygenated organic compound may be selected from the group consisting of ethylene glycol, glycerin, polyethylene glycol (which may have a molecular weight of 200 to 1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1,2- cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, and combinations thereof; the nitrogen-containing organic compound may be selected from the group consisting of ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ammonium ethylenediaminetetraacetate, and combinations thereof.

In the process for producing a hydrocracking catalyst according to the present application, the contacting and impregnating temperature is not particularly limited, and may be any temperature that can be reached for the impregnating solution. The duration of the impregnation is also not particularly limited, provided that a desired amount of the active metal component starting compound can be introduced into the catalyst carrier. In general, the higher the impregnation temperature and the higher the concentration of the impregnation solution, the shorter the time required to reach the same weight of impregnant added (i.e., the difference between the weight of catalyst support after impregnation and the weight of catalyst support before impregnation); and vice versa. Where the desired amount of impregnant and impregnation conditions are determined, one skilled in the art can readily select the appropriate impregnation duration based on the description herein. The impregnation method is not specifically limited according to the present application, and the impregnation may be saturation impregnation or supersaturation impregnation. The impregnation medium is not particularly limited, and the impregnation may be carried out in a sealed environment or in an open environment according to conventional methods known in the art, and during the impregnation, the loss of aqueous solvent may or may not be compensated. During impregnation, various gases such as air, nitrogen, steam, etc. may be introduced, or no new component may be introduced.

In the process for producing the hydrocracking catalyst of the present application, the conditions for drying the impregnated material are not particularly limited, and various drying conditions commonly used in the art can be adopted, for example, conditions in which the temperature is about 80 to 350°C, preferably about 100 to 300°C, and the drying time is from about 0.5 to 24 hours, preferably from about 1 to 12 hours.

The method for producing a hydrocracking catalyst according to the present application may further include the step of drying the contacted material and subsequent calcination, wherein calcination is a conventional step for obtaining catalysts and is not specifically limited in the present application. The calcination can be carried out, for example, under the following conditions: the temperature is about 350 to 600°C, preferably 400 to 550°C; the duration of the calcination is approximately 0.2 to 12 hours, preferably 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 various other reactions, and is particularly suitable for hydrocracking hydrocarbon feedstocks to produce a hydrocarbon fraction having a lower boiling point and a lower molecular weight.

According to the seventh aspect of the present application, the use of the phosphorus-containing molecular sieve or hydrocracking catalyst of the present application in the hydrocracking of hydrocarbon feedstocks is provided.

According to an eighth aspect of the present application, there is provided a process for hydrocracking a hydrocarbon feedstock, comprising the step of hydrocracking the hydrocarbon feedstock in the presence of a phosphorus-containing molecular sieve or a hydrocracking catalyst according to the present application.

Suitable hydrocarbon feedstocks for use in the present application may be a variety of heavy mineral oils or synthetic oils or appropriate mixed distillates such as straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, vacuum deasphalted residues, coking distillates. , catalytic cracking distillates, shale oils, tar sands oils, liquefied coal oils (coal processing liquid fuels), etc. In particular, the hydrocracking catalyst of the present application is suitable for hydrocracking heavy and low grade distillate oils to produce a middle distillate having a distillation temperature in the range of 149 to 371°C, in particular 180 to 370°C.

According to the present application, the hydrocracking reaction can be carried out in any reaction device that allows the hydrocarbon feedstock to come into contact and react in the presence of a catalyst under hydrogenation reaction conditions, for example, in one or more of the traditional hydrocracking devices, such as fixed bed reactors, reactors moving bed reactors, fluidized bed reactors, fluidized bed reactors and suspended bed reactors.

According to the present application, the hydrocracking reaction can be carried out under conventional hydrocracking reaction conditions. For example, the hydrocracking reaction can be carried out under the following conditions: the reaction temperature is about 200 to 650°C, preferably about 300 to 510°C, the reaction pressure is about 3 to 24 MPa, preferably about 4 to 15 MPa, hour the liquid space velocity is from about 0.1 to 10 h ^-1 , preferably from about 0.2 to 5 h ^-1 , and the volume ratio of hydrogen to oil is from about 100 to 5000 Nm ³ /m ³ , preferably from about 200 to 1000 Nm ³ /m ³ .

In the hydrocracking reaction, the hydrocracking catalyst of the present application may be used alone or in combination with a hydrocracking catalyst having a different composition.

In certain preferred embodiments, some of the hydrocracking reaction product may then be returned to the reactor inlet in such a manner as to increase the yield of the desired product.

According to a preferred embodiment of the present application, the hydrocracking process may further comprise the step of subjecting the hydrocracking catalyst to presulfonation using sulfur, hydrogen sulfide, or a sulfur-containing feed at a temperature of from about 140 to 370° C. in the presence of hydrogen to convert the catalyst to the sulfide form prior to its application in the hydrocracking reaction. This presulfonation can be carried out outside the reactor or at the site of the catalyst inside the reactor.

According to the preferred embodiment, the following technical solutions are proposed in this application:

A1. A phosphorus-containing molecular sieve, characterized in that the molecular sieve has a mass content of phosphorus of from about 0.3 to 5% in terms of oxide, a pore volume of from about 0.2 ml/g to about 0.95 ml/g, and a Bronsted acid site to Lewis acid site ratio of about 2 to about 10.

A2. The phosphorus-containing molecular sieve of claim A1, wherein the molecular sieve has a ²⁷ Al NMR structural spectrum representing a ratio of 1:60 _ppm. /I _{-1 ppm} , ranging from about 5 to about 40, and the ratio I _{-1 ppm.} /I _{±6 ppm} , ranging from about 0.4 to about 2.

A3. A method for producing a phosphorus-containing molecular sieve according to claim A1 or A2, including:

a) subjecting the phosphorus-containing molecular sieve starting material to hydrothermal treatment at a temperature of about 350 to 700° C. and a pressure of about 0.1 to 2 MPa for about 0.5 to 10 hours in the presence of steam to obtaining a hydrothermally treated molecular sieve material, wherein the phosphorus-containing molecular sieve starting material has a phosphorus content of from about 0.1 wt.% to about 15 wt.%, and a sodium content of from about 0.5 wt.% to about 4, 5 wt.% in terms of oxide and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) forming a slurry of the hydrothermally treated molecular sieve material obtained in step (a) with water to obtain a molecular sieve slurry, heating the molecular sieve slurry to a temperature of from about 40° C. to about 95° C., then holding at the temperature and continuously adding acid solution to a molecular sieve slurry, wherein the ratio of the weight of the acid in the acid solution to the dry weight of the phosphorus-containing molecular sieve starting material is from about 0.01:1 to about 0.6:1, calculated as H ⁺ , relative to 1 liter of the molecular sieve suspension , while the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, reacting at a constant temperature for from about 0.5 h to about 20 h after completion of the addition of the acid and recovering the solid product .

A4. The method of claim A3, wherein in step (a) the phosphorus-containing molecular sieve starting material is a Y-type phosphorus-containing molecular sieve having a crystal lattice constant of 2.425 to 2.470 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.

A5. The method according to item A4, in which in stage (a) the source material of the phosphorus-containing molecular sieve has a water content of approximately 10 to 40 wt.%; the phosphorus-containing molecular sieve starting material is present in particulate form, wherein the phosphorus-containing molecular sieve starting material having a particle size of about 1 to 500 mm is about 10 to 100 wt.% of the total mass of the phosphorus-containing molecular sieve starting material, and the size particle is the diameter of a sphere circumscribing the particle.

A6. The method of claim A5, wherein the phosphorus-containing molecular sieve starting material having a particle size of about 1 to 500 mm is from about 30 to 100 wt% of the total weight of the phosphorus-containing molecular sieve starting material.

A7. The method of claim A6, wherein the phosphorus-containing molecular sieve starting material having a particle size of about 5 to 100 mm is about 30 wt% to about 100 wt% of the total weight of the phosphorus-containing molecular sieve starting material.

A8. The method of claim A3, wherein in step (b) the weight ratio of the water in the molecular sieve slurry obtained after slurry to the dry weight of the phosphorus-containing molecular sieve starting material is from about 14:1 to about 5:1.

A9. The method of claim A3, wherein the method further comprises in step (b) adding an ammonium salt selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium sulfate, and combinations thereof, to the molecular sieve slurry during addition of the acid solution, wherein the ratio the weight of the ammonium salt and the dry weight of the starting material of the phosphorus-containing molecular sieve is in the range from about 0.1:1 to about 2.0:1.

A10. The method of claim 3, wherein in step (b) the acid solution has an acid concentration of about 0.01 mol/l to about 15.0 mol/l and the acid is selected from the group consisting of phosphoric acid, sulfuric acid , nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof.

A11. The method of claim A3, the method further comprising recovering a solid product, then washing with water and drying to obtain a phosphorus-containing molecular sieve, the drying being 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.

A12. The use of a phosphorus-containing molecular sieve according to paragraph A1 or A2 in the hydrocracking of hydrocarbon feedstocks.

A13. The use of claim A12, wherein the hydrocarbon feedstock is selected from the group consisting of straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillates, catalytic cracking distillates, shale oils, tar sands oils , liquefied coal oils and combinations thereof; and

hydrocracking 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 reaction pressure 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 10 h ^-1 , preferably from about 0.2 to 5 h ^-1 ; the volume ratio of hydrogen to oil is about 100 to 5000 Nm ³ /m ³ , preferably about 200 to 1000 Nm ³ /m ³ .

B1. Hydrocracking catalyst, characterized in that the catalyst contains from about 45 to 90 wt.% of the carrier in terms of dry matter; from about 1 to 40 wt.% component of the first metal in terms of metal oxide; and from about 1 to 15 wt.% component of the second metal in terms of metal oxide in relation to the dry weight of the catalyst;

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

wherein the phosphorus-containing Y-type molecular sieve has a phosphorus content of from about 0.3 wt.% to about 5 wt.%, in terms of oxide, a pore volume of from about 0.2 ml/g to about 0.95 ml /g, and the ratio of the content of the acid sites of Bronsted and the content of the acid sites of Lewis, comprising from about 2 to about 10 when measured by infrared method using pyridine.

B2. The catalyst according to item B1, and the catalyst contains from about 55 to 85 wt.% carrier in terms of dry matter; from about 12 to 35 wt.% component of the first metal in terms of metal oxide; and from about 2 to 10 wt.% component of the second metal in terms of metal oxide in relation to the dry weight of the catalyst; and

the weight ratio of the phosphorus-containing Y-type molecular sieve to the refractory inorganic oxide is from about 0.03:1 to about 6:1.

B3. The catalyst according to item B1 or B2, in which the phosphorus-containing molecular sieve type Y has a structural NMR spectrum ²⁷ Al, representing the ratio I _{60 ppm.} /I _{-1 ppm} , which is approximately from 5 to 40, and the ratio L _{-1 ppm.} /I _{±6 ppm} , which is approximately from 0.4 to 2.

B4. The catalyst of claim B1 or B2, wherein the phosphorus-containing Y-type molecular sieve is produced by a process comprising:

a) subjecting the phosphorus-containing molecular sieve starting material to hydrothermal treatment at a temperature of about 350 to 700° C. and a pressure of about 0.1 to 2 MPa for about 0.5 to 10 hours in the presence of steam to obtaining a hydrothermally treated molecular sieve material; wherein the phosphorus-containing molecular sieve feedstock has a phosphorus content of from about 0.1 wt.% to about 15 wt.%, and a sodium content of about 0.5 wt.% to about 4.5 wt.% in terms of oxide and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve;

b) forming a slurry of the hydrothermally treated molecular sieve material obtained in step (a) with water to form a molecular sieve slurry, heating the molecular sieve slurry to a temperature of about 40° C. to about 95° C., maintaining at that temperature, and continuously adding acid solution to a molecular sieve slurry, wherein the ratio of the weight of the acid in the acid solution to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 0.01:1 to about 0.6:1, based on H ⁺ , relative to 1 liter of the molecular sieve slurry and the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, reacting at a constant temperature for about 0.5 h to about 20 h after completion of the acid addition, and recovering a solid product.

B5. The catalyst of claim B4, wherein in step (a) the phosphorus-containing molecular sieve feedstock is a Y-type phosphorus-containing molecular sieve having a crystal lattice constant of 2.425 to 2.47 nm, a specific surface area of approximately 250 to 750 ^m2 / g, and a pore volume of about 0.2 to 0.95 ml/g.

B6. The catalyst of claim B5, wherein in step (a) the phosphorus-containing molecular sieve feedstock has a water content of about 10 to 40% by weight;

The phosphorus-containing molecular sieve starting material is present in particulate form, wherein the phosphorus-containing molecular sieve starting material having a particle size of 1 to 500 mm is about 10 to 100 wt% of the total mass of the phosphorus-containing molecular sieve starting material, wherein the particle size is the diameter of a sphere described around the particle.

B7. The catalyst of claim B6, wherein the phosphorus-containing molecular sieve feedstock having a particle size of 1 to 500 mm is about 30 to 100% by weight of the total weight of the phosphorus-containing molecular sieve feedstock;

a phosphorus-containing molecular sieve starting material having a particle size of 5 to 100 mm is preferably from about 30 wt% to about 100 wt% of the total weight of the phosphorus-containing molecular sieve starting material.

B8. The catalyst of claim B4, wherein in step (b) the weight ratio of the water in the molecular sieve slurry obtained after slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1.

B9. The catalyst of claim B4, wherein the preparation of a phosphorus-containing type Y molecular sieve further comprises, in step (b), adding an ammonium salt selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium sulfate, and combinations thereof, to the molecular sieve slurry during addition of the solution acid, and the ratio of the weight of the ammonium salt to the dry weight of the source material of the phosphorus-containing molecular sieve is from about 0.1:1 to about 2.0:1.

AT 10 O'CLOCK. The catalyst of claim B4, wherein in step (b) the acid solution has an acid concentration of about 0.01 to 15.0 mol/l and the acid is selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof.

AT 11. The catalyst of claim B4, wherein the preparation of a phosphorus-containing Y-type molecular sieve further comprises recovering a solid product, then washing with water and drying to obtain a phosphorus-containing molecular sieve; and 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.

B12. The catalyst of claim B1, wherein the refractory inorganic oxide is selected from the group consisting of alumina, zirconium dioxide, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and combinations thereof; the first metal is molybdenum and/or tungsten; and the second metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

B13. A method for producing a hydrocracking catalyst according to any one of paragraphs. B1-B12, characterized in that the method includes bringing the impregnating carrier into contact with an impregnating solution containing the initial metal compound, and drying the material obtained after impregnation.

B14. The method of claim B13, wherein the method further comprises mixing a phosphorus-containing Y-type molecular sieve, a refractory inorganic oxide, a peptizing agent, and optionally a lubricant, and then shaping, drying, and calcining to form a carrier.

B15. The method of claim B13, wherein the metal parent compound comprises a first metal parent compound and a second metal parent compound, wherein the first metal parent compound is selected from the group consisting of first metal inorganic acids, first metal inorganic salts, first metal organometallic compounds, and combinations thereof ; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the first metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof;

the parent compound of the second metal is selected from the group consisting of inorganic acids of the second metal, inorganic salts of the second metal, organometallic compounds of the second metal, and combinations thereof; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the second metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof.

B16. The method according to item B13, in which the impregnating solution further comprises an organic additive; and the concentration of the organic additive is about 2 to 300 g/l; wherein the organic additive is selected from the group consisting of ethylene glycol, glycerin, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ammonium ethylenediaminetetraacetate, and combinations thereof.

B17. The method according to claim B13, wherein the drying is carried out under the following conditions: the temperature is from about 80 to 350°C, and the drying time is from about 0.5 to 24 hours.

B18. The method of claim B13, wherein the method further comprises the step of drying the contacted material and subsequent calcination, and 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.

B19. The use of a hydrocracking catalyst according to any one of paragraphs. B1-12 in the hydrocracking of hydrocarbon feedstocks.

B20. The use of claim B19, wherein the hydrocarbon feedstock is selected from the group consisting of straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, vacuum deasphalted residues, coking distillates, catalytic cracking distillates, shale oils, tar sands oils liquefied coal oils and combinations thereof;

hydrocracking 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 reaction pressure 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 10 h ^-1 , preferably from about 0.2 to 5 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to 5000 Nm ³ /m ³ , preferably about 200 to 1000 Nm ³ /m ³ .

C1. A phosphorus-containing molecular sieve having a phosphorus content of about 0.3 to 5% by weight, preferably about 0.4 to 2.0% by weight, based on oxide, and a pore volume of about 0.2 to 0 95 ml/g, preferably from about 0.25 to 0.60 ml/g, and a ratio of Bronsted acid sites to Lewis acid sites of about 2 to 10, preferably about 3.4 to 9.5.

C2. The phosphorus-containing molecular sieve of claim C1, wherein the molecular sieve represents a ²⁷ Al NMR structural spectrum having an I ratio of _{60 ppm.} /I _{-1 ppm} , comprising from about 5 to about 40, preferably from about 10.0 to about 39, and the ratio I _{-1 ppm.} /I _{±6 ppm} , ranging from about 0.4 to about 2.

C3. A phosphorus-containing molecular sieve according to any one of the preceding claims, wherein the molecular sieve has a lattice constant of 2.425 to 2.470 nm, preferably 2.430 to 2.458 nm, and a specific surface area of about 250 to 850 m ² /g, preferably about 400 to 750 m ² /g.

C4. A phosphorus-containing molecular sieve according to any one of the preceding claims, wherein the molecular sieve has a faujasite structure and is preferably a Y-type molecular sieve, more preferably a molecular sieve selected from the group consisting of NaY, HNaY, REY, USY molecular sieves and combinations thereof.

C5. A phosphorus-containing molecular sieve according to any one of the preceding claims, wherein the cationic positions of the molecular sieve are occupied by one or more types of sodium ions, ammonium ions, and hydrogen ions.

C6. A phosphorus-containing molecular sieve according to any one of the preceding claims, wherein the molecular sieve is produced by a method comprising:

i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1;

iii) subjecting the resulting molecular sieve slurry to an acid leach; and

iv) recovering the solid product,

wherein the acid leaching in step (iii) is carried out as follows: adding the acid solution to the molecular sieve slurry at a substantially constant rate at a temperature of from about 40°C to about 95°C, preferably from about 50°C to about 85°C, wherein the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for from about 0.5 h to about 20 h, preferably for from about 0.5 h to about 15 h, and the ratio of the mass of acid in the acid solution and dry weight of the source material of the phosphorus-containing molecular sieve is from about 0.01:1 to about 0.6:1.

C7. A method for producing a phosphorus-containing molecular sieve, comprising the following steps:

i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1;

iii) subjecting the resulting molecular sieve slurry to an acid leach; and

iv) recovering the solid product,

wherein the acid leaching in step (iii) is carried out as follows: adding the acid solution to the molecular sieve slurry at a substantially constant rate at a temperature of from about 40°C to about 95°C, preferably from about 50°C to about 85°C, wherein the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for from about 0.5 h to about 20 h, preferably from about 0.5 h to about 15 h, and the ratio of the weight of acid in the acid solution to the dry weight the source material of the phosphorus-containing molecular sieve is from about 0.01:1 to about 0.6:1.

C8. The method of claim C7 wherein the phosphorus-containing molecular sieve feedstock has a phosphorus content of about 0.1 to 15 wt. 0.5 to 4.5 wt.%, preferably from about 1.0 to 4.0 wt.% in terms of oxides and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve.

C9. The method according to any one of paragraphs. C7-C8, wherein the phosphorus-containing molecular sieve starting material is a Y-type phosphorus-containing molecular sieve having a lattice constant of 2.425 to 2.470 nm, preferably 2.440 to 2.470 nm, a specific surface area of about 250 to 750 ^m2 /g, preferably about 400 to 700 m ² /g, and a pore volume of about 0.2 to 0.95 ml/g, preferably about 0.2 to 0.5 ml/g.

C10. The method according to any one of paragraphs. C7-C9, in which the source material of the phosphorus-containing molecular sieve has a water content of approximately 10 to 40 wt.%.

C11. The method according to any one of paragraphs. C7-C10, wherein the phosphorus-containing molecular sieve starting material is present in particulate form, and the phosphorus-containing molecular sieve starting material having a particle size of about 1 to 500 mm is about 10 to 100 wt%, preferably about 30 to 100 wt.% of the total weight of the source material of the phosphorus-containing molecular sieve, and the particle size is the diameter of the sphere circumscribed around the particle; preferably, the phosphorus-containing molecular sieve starting material having a particle size of about 5 to 100 mm is from about 30 wt.% to about 100 wt.% of the total weight of the phosphorus-containing molecular sieve starting material.

C12. The method according to any one of paragraphs. C7-C11, in which the hydrothermal treatment in step (i) is carried out in the presence of steam, preferably in the presence of 30 to 100% steam, under the following conditions: temperature is from about 350 to 700° C., pressure is from about 0.1 up to 2 MPa, and the duration of the hydrothermal treatment is approximately 0.5 to 10 hours.

C13. The method according to any one of paragraphs. C7-C12, further comprising in the acid leaching step (iii) adding an ammonium salt, preferably selected from the group consisting of ammonium nitrate, ammonium chloride, ammonium sulfate, and combinations thereof, to the molecular sieve suspension during the addition of the acid solution, and preferably the ratio the weight of the ammonium salt and the dry weight of the source material of the phosphorus-containing molecular sieve is from about 0.1:1 to about 2.0:1.

C14. The method according to any one of paragraphs. C7-C13, wherein the acid solution used in the acid leach in step (iii) has an acid concentration of about 0.01 to 15.0 mol/l, preferably about 0.02 to 5.0 mol/l and the acid is selected from the group consisting of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof.

C15. The method according to any one of paragraphs. C7-C14, further comprising after step (iv) washing the obtained solid product with water and drying to obtain a phosphorus-containing molecular sieve; moreover, 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.

C16. The method according to any one of paragraphs. C7-C15, in which the addition of the acid solution in the acid leach in step (iii) is carried out several times, preferably 2 to 10 times, wherein the acid solution is added at a substantially constant rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 mol/h to about 3.0 mol/h in terms of H ⁺ in relation to 1 l of molecular sieve suspension each time during the addition, and after each addition, the resulting product is subjected to an isothermal reaction in for such a period of time that the total duration of the isothermal reaction is from about 0.5 to 20 hours, preferably from about 0.5 to 15 hours; and preferably the acid solution is added several times, the ratio of the weight of the acid in the acid solution to the dry weight of the starting material of the phosphorus-containing molecular sieve is from about 0.01:1 to about 0.3:1.

C17. The method according to any one of paragraphs. C7-C16, including the following stages:

i) subjecting the phosphorus-containing molecular sieve starting material to hydrothermal treatment in the presence of steam, preferably in the presence of 30 to 100% steam, at a temperature of about 350 to 700° C. and a pressure of about 0.1 to 2 MPa, for about 0.5 to 10 hours to obtain a hydrothermally treated molecular sieve;

ii) forming a hydrothermally treated molecular sieve slurry with water to form a molecular sieve slurry, wherein the weight ratio of the water in the molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is from about 14:1 to about 5:1;

iii) heating the molecular sieve slurry to a temperature of about 40 to 95°C, preferably about 50 to 85°C, holding at that temperature, and adding the acid solution to the molecular sieve slurry at a substantially constant rate, wherein the weight ratio of the acid in the solution is acid and dry weight of the source material of phosphorus-containing molecular sieve is in the range from about 0.01: 1 to about 0.6: 1 in terms of H ⁺ in relation to 1 liter of molecular sieve suspension, while the acid solution is added at a rate of from about 0.05 mol/h to about 10 mol/h, preferably from about 0.2 to 3.0 mol/h, and the resulting product is subjected to an isothermal reaction for about 0.5 h to about 20 h, preferably for about 0.5 to 15 hours after completion of the acid addition; and

iv) recovering the solid product.

C18. Phosphorus-containing molecular sieve, obtained by the method according to any one of paragraphs. C7-C17.

C19. Hydrocracking catalyst containing from about 45 wt.% to about 90 wt.%, preferably from about 55 wt.% to about 85 wt.% of the carrier in terms of dry matter and in relation to the weight of the catalyst, from about 1 wt.% to about 40 wt.%, preferably from about 12 wt.% to about 35 wt.% component of the first metal in terms of metal oxide, and from about 1 wt.% to about 15 wt.%, preferably from about 2 wt.% to about 10 wt.% component of the second metal in terms of metal oxide, and:

the carrier contains a phosphorus-containing molecular sieve according to any one of paragraphs. C1-C6 and C18 and a refractory inorganic oxide, wherein the weight ratio of the phosphorus-containing molecular sieve to the refractory inorganic oxide is from about 0.03:1 to about 20:1, preferably from about 0.03:1 to about 6:1; the first metal is a Group VIB metal; and the second metal is a Group VIII metal.

C20. The catalyst of claim C19 wherein the refractory inorganic oxide is selected from the group consisting of alumina, silica, amorphous silica and alumina double oxides, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and combinations thereof ; the first metal is molybdenum and/or tungsten; and the second metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

C21. A method for producing a hydrocracking catalyst according to any one of paragraphs. C19-C20, which includes the steps of bringing the impregnation carrier into contact with the impregnating solution, which contains the original metal compound, and drying the material obtained after impregnation, wherein:

the carrier contains a phosphorus-containing molecular sieve according to any one of paragraphs. C1-C6 and C18 and a refractory inorganic oxide, and preferably the weight ratio of the phosphorus-containing molecular sieve to the refractory inorganic oxide is from about 0.03:1 to about 20:1, preferably from about 0.03: to about 6:1; and

the metal parent compound comprises a first metal parent compound and a second metal parent compound, wherein the first metal is a Group VIB metal and the second metal is a Group VIII metal.

C22. The method according to p. C21, further comprising the following steps: mixing a phosphorus-containing molecular sieve and a refractory inorganic oxide with a peptizing agent and optionally with a lubricant, and then shaping, drying and calcining to obtain a carrier.

C23. The method according to paragraphs. C21 or C22, wherein the first metal parent compound is selected from the group consisting of first metal inorganic acids, first metal inorganic salts, first metal organometallic compounds, and combinations thereof; wherein the inorganic salt is preferably selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the first metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof; and

the parent compound of the second metal is selected from the group consisting of inorganic acids of the second metal, inorganic salts of the second metal, organometallic compounds of the second metal, and combinations thereof; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the second metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof.

C24. The method according to any one of paragraphs. C21-C23, wherein the impregnation solution further comprises an organic additive at a concentration of about 2 to 300 g/l, and the organic additive is preferably selected from the group consisting of ethylene glycol, glycerin, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid , oxalic acid, nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ammonium ethylenediaminetetraacetate, and combinations thereof.

C25. The method according to any one of paragraphs. C21-C24, in which the material obtained after impregnation is dried under the following conditions: the temperature is from about 80 to 350°C, preferably from 100 to 300°C, and the drying time is from about 0.5 to 24 hours, preferably about from 1 to 12 noon

C26. The method according to any one of paragraphs. C21-C25, further comprising the step of calcining the dried material under the following conditions: the temperature is from about 350 to 600°C, and the calcination time is from about 0.2 to 12 hours.

C27. The use of a phosphorus-containing molecular sieve according to any one of paragraphs. C1-C6 and C18 in the preparation of a hydrocracking catalyst suitable for use in the hydrocracking of hydrocarbon feedstocks.

C28. The use of a phosphorus-containing molecular sieve according to any one of paragraphs. C1-C6 and C18 or a hydrocracking catalyst according to any one of paragraphs. С19-С20 in hydrocracking of initial hydrocarbon materials.

C29. The use of claim C27 or 28, wherein the hydrocarbon feedstock is selected from the group consisting of straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillates, catalytic cracking distillates, shale oils, oils tar sands, liquefied coal oils and combinations thereof.

C30. The use according to claim C27 or C28, in which the hydrocracking 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 reaction pressure 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 10 h ^-1 , preferably from about 0.2 to 5 h ^-1 ; and the volume ratio of hydrogen to oil is about 100 to 5000 Nm ³ /m ³ , preferably about 200 to 1000 Nm ³ /m ³ .

C31. A method for hydrocracking a hydrocarbon feedstock, comprising the step of hydrocracking a hydrocarbon feedstock in the presence of a phosphorus-containing molecular sieve according to any one of claims C1-C6 and C18 or a hydrocracking catalyst according to any one of paragraphs. C19 and C20.

C32. The process of claim C31, wherein the hydrocarbon feedstock is selected from the group consisting of straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillates, catalytic cracking distillates, shale oils, tar sands oils , liquefied coal oils and combinations thereof.

C33. The method according to p. C31 or C32, in which the hydrocracking 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 reaction pressure 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 10 h ^-1 , preferably from about 0.2 to 5 h - ¹ ; and the volume ratio of hydrogen to oil is about 100 to 5000 Nm ³ /m ³ , preferably about 200 to 1000 Nm ³ /m ³ .

Examples

The present application will be further illustrated by the examples provided herein below and are not intended to be limiting in any way.

Instruments and devices

In the following Examples and Comparative Examples, the pore volume and the specific surface area of the molecular sieve were measured using the static low temperature adsorption capacity method (the method according to the PRC national standard GB/T5816-1995) using the ASAP 2400 automatic adsorption apparatus from Micromeritics Instrument Corporation (USA). In particular, the measurements included evacuation and degassing at 250° C. and 1.33 Pa for 4 hours, contact with nitrogen used as adsorbate at -196° C. until static adsorption equilibrium was reached; calculating the amount of nitrogen adsorbed on the adsorbent based on the difference between the incoming amount of nitrogen gas and the amount of nitrogen gas remaining in the gas phase after adsorption, calculating the pore size distribution using the Barret-Joyner-Halenda (BJH) equation, and calculating the specific surface area and pore volume using the Brunauer-Emmett-Teller (BET) equation.

In the following examples and comparative examples, the molecular sieve lattice constant was measured using a D5005 X-ray diffractometer from Siemens (Germany) and a method according to PRC Petrochemical Industrial Standard SH/T03 39-92. The measurements were carried out under the following conditions: copper target, Kα radiation, solid detector, X-ray tube voltage 40 kV, X-ray tube current 40 mA, stepped scanning with a step width of 0.02°, a pretreatment time of 2 s, and a scan range from 5° to 70 °.

In the following examples and comparative examples, the phosphorus content and the sodium content of the molecular sieve were measured using a 3271E X-ray fluorescence spectrometer from Rigaku Industrial Corporation (Japan). In particular, to carry out measurements, a tablet was obtained by pressing a powdered sample, the intensity of the spectral line of each element was determined using a scintillation counter and a proportional counter using a rhodium target, a laser voltage of 50 kV and a laser current of 50 mA, and quantitative and semi-quantitative analysis of the content of the element was carried out by the method with using an external standard.

In the following examples and comparative examples, the ratio of Bronsted acid sites to Lewis acid sites of the molecular sieve was measured using a Bio-Rad IFS-3000 infrared spectrometer. In particular, to carry out measurements, a molecular sieve sample was crushed, an independent sheet was pressed from it, the surface density of which was approximately 10 mg/cm ² , an independent sheet was placed in the local storage of an infrared spectrometer, and the surface was cleaned at a temperature of 350 ° C in a vacuum of 10 ^-3 Pa for 2 hours, saturated pyridine vapor was introduced after cooling to room temperature, adsorption was carried out for 15 minutes until equilibrium was reached, desorption was carried out in vacuum for 30 minutes at 350°C, and the vibrational spectrum of adsorbed pyridine was measured after cooling to room temperature. The scanning range was from 1400 cm ^-1 to 1700 cm ^-1 . The content of Brønsted acid sites was determined as the ratio of the infrared absorption value for the band at 1540±5 cm ^-1 and the mass and area of the sample in the form of a sheet [the infrared absorption value per unit area and unit mass of the sample, expressed as AB⋅(cm ² ⋅d) ^-1 ]. The content of Lewis acid sites was determined as the ratio of the infrared absorption value for the strip at 1450±5 cm ^-1 and the mass and area of the sample in the form of a sheet [the infrared absorption value per unit area and unit mass of the sample, expressed as AL⋅(cm ² ⋅d) ^-1 ]. The AB/AL ratio was defined as the ratio of the Bronsted acid site content to the Lewis acid site content of the zeolite molecular sieve.

In the following examples and comparative examples, the ^27Al NMR structural spectrum of the molecular sieve was analyzed using a UNITYLINOVA 300M nuclear magnetic resonance spectrometer from Varian in magic angle rotation mode, where the ^27Al NMR resonant frequency was 78.162 MHz, the rotation speed was 3000 Hz, the repetition time delay was 0.5 s, sampling time was 0.020 s, pulse width was 1.6 µs, spectral width was 54.7 kHz, data acquisition was performed at 2000 points, accumulation number was 800, and test temperature was room temperature.

Options

The parameters shown in the following examples and comparative examples were calculated as follows:

Yield of molecular sieve (%) = dry weight of molecular sieve produced/dry weight of raw molecular sieve material before hydrothermal treatment ×100%.

Feedstock conversion rate (%) = (weight of fraction with initial boiling point above 350°C in original oil - mass of fraction with initial boiling point above 350°C in obtained oil) / mass of fraction with initial boiling point above 350°C in original oil ×100%.

Preparation of molecular sieves

Examples I-1 to I-3 below are examples of the production of phosphorus-containing molecular sieves according to the present application, and comparative examples I-1 to I-4 are examples of the production of molecular sieves not according to the present application.

Example I-1

To 300 g of NaY molecular sieve (supplied as NaY by Changling subsidiary of Sinopec Catalyst Co., Ltd. and having a crystal lattice constant of 2.468 nm, specific surface area of 680 m ² /g, pore volume of 0.30 ml/g, content of Na ₂ O 13.0 wt.% and the content of A ₂ O ₃ 22 wt.%), was added an aqueous solution of 2.0 mol/l (NH ₄ ) ₂ HPO ₄ , suspended, and the total amount of water was 1000 ml, and then filtered. The resulting filter cake was treated with the above method three times and then dried at 100° C. for 1 hour to obtain a phosphorus-containing molecular sieve starting material which had a crystal lattice constant of 2.468 nm, a specific surface area of 590 m ² /g, a pore volume of 0, 37 ml/g, P ₂ O ₅ content 4.8 wt.% and Na ₂ O content 3.5 wt.%.

Put 100 g of phosphorus-containing molecular sieve raw material into the hydrothermal treatment apparatus, 100% steam was introduced, the temperature was raised to 450°C, the apparatus pressure was set to 0.8 MPa, the hydrothermal treatment was carried out under constant conditions for 8 hours, and then the hydrothermally treated molecular sieve material was recovered.

100 ml of an aqueous solution of hydrochloric acid and ammonium chloride was prepared using hydrochloric acid, ammonium chloride and a raw material of phosphorus-containing molecular sieve (based on dry matter) in a mass ratio of 0.2:0.4:1, resulting in a concentration of hydrochloric acid in the aqueous solution was 0.05 mol/l, and the concentration of ammonium chloride in the aqueous solution was 0.07 mol/l.

To 50 g (dry basis) of the hydrothermally treated molecular sieve material, 500 ml of deionized water was added, mixed and suspended, obtaining a suspension of molecular sieve, which was then heated to 80°C. The resulting aqueous solution of hydrochloric acid and ammonium chloride was added to the molecular sieve slurry at a constant rate of 2 mol/h in terms of H ⁺ in relation to 1 l of molecular sieve slurry in three portions, the resulting product was reacted for 4 hours at a constant temperature each time after adding acid, then filtered, and the next addition of acid to the filter cake was carried out in the same way. After the final addition of acid and 4 hours of subsequent reaction, the solid product was recovered and dried at 180°C for 3 hours, obtaining a phosphorus-containing Y-1 molecular sieve having a crystal lattice constant of 2.436 nm, a specific surface area of 634 m ² /g, the content of Na ₂ O 0.42 wt.% and the content of Al ₂ O ₃ 18.7 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in Figure 1 and other properties are shown in Table 1.

Example I-2

To 300 g of PSRY molecular sieve (supplied as PSRY by Changling subsidiary of Sinopec Catalyst Co., Ltd. and having a crystal lattice constant of 2.456 nm, specific surface area of 620 m ² /g, pore volume of 0.39 ml/g, content of Na ₂ O 2.2 wt.%, the content of P ₂ O ₅ 1.5 wt.% and the content of Al ₂ O ₃ 18 wt.%) was added deionized water and suspended, and the total amount of water was 1000 ml, filtered and dried at 70 ° C for 2 hours to obtain a phosphorus-containing molecular sieve starting material with a water content of 35% by weight.

The phosphorus-containing molecular sieve feedstock was crushed, sieved to a fraction of 5 to 20 mesh (with particles having an approximate particle size of 1 to 500 mm accounting for 70% by weight of the total weight of the phosphorus-containing molecular sieve feedstock), placed in a hydrothermal processing, introduced 100% steam, the temperature was raised to 580°C, the pressure in the device was set at 0.4 MPa, the hydrothermal treatment was carried out for 2 hours under constant conditions, and the hydrothermally treated molecular sieve material was recovered.

250 ml of an aqueous solution of sulfuric acid was prepared using sulfuric acid and a raw material of phosphorus-containing molecular sieve (based on dry matter) in a mass ratio of 0.02:1, resulting in a concentration of sulfuric acid in an aqueous solution of 0.2 mol/L.

To 50 g (dry basis) of the hydrothermally treated molecular sieve material, 500 ml of deionized water was added, mixed and suspended, obtaining a suspension of molecular sieve, which was then heated to 80°C. The resulting aqueous sulfuric acid solution was added to the molecular sieve suspension at a constant rate of 0.5 mol/h, in terms of H ⁺ with respect to 1 l of the molecular sieve suspension in three portions, the resulting product was reacted for 2 hours at a constant temperature each time after adding acid, then filtered, and the next addition of acid to the filter cake was carried out in the same way. After the final addition of acid and 2 hours of subsequent reaction, the solid product was recovered and dried at 100°C for 8 hours, obtaining a phosphorus-containing Y-2 molecular sieve having a crystal lattice constant of 2.447 nm, specific surface area of 684 m ² /g, Na ₂ content O 0.08 wt.% and the content of Al ₂ O ₃ 14.4 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in Figure 1 and other properties are shown in Table 1.

Example I-3

The phosphorus-containing molecular sieve was prepared as described in Example I-2, except that the starting material of the phosphorus-containing molecular sieve was crushed and sieved to obtain a fraction of 5 to 20 mesh (whereas particles having an approximate particle size of 5 to 100 mm were 70 wt.% of the total weight of the source material of the phosphorus-containing molecular sieve), and then the hydrothermal treatment and subsequent operations were carried out as described in example 1-2, obtaining a phosphorus-containing molecular sieve Y-3 having a crystal lattice constant of 2.438 nm, a specific surface area of 733 m ² / g, the content of Na ₂ O 0.08 wt.%) and the content of Al ₂ O ₃ 8.1 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in FIG. 1, and other properties are presented in table 1.

Comparative Example I-1

The phosphorus-containing molecular sieve in this comparative example was PSRY molecular sieve, which is described in Example I-2, and was obtained by the method for producing phosphorus-containing zeolites, which is described in PRC Publication No. CN 1088407 C. Specifically, the phosphorus-containing compound was directly mixed with the zeolite raw material in a mass ratio of 0.2 and heated at 520°C for at least 0.1 h under sealed conditions, the resulting product was washed with deionized water until the detection of acid residue ions ceased, and then the phosphorus-containing zeolite, designated RY-1. The zeolite had a lattice constant of 2.456 nm, a specific surface area of 620 m ² /g, a Na ₂ O content of 2.53 wt%, and an Al ₂ O ₃ content of 20.7 wt%. The ^27Al NMR structural spectrum of the molecular sieve is shown in FIG. 1 and other properties are shown in Table 1. Comparative Example I-2

100 g of a phosphorus-free molecular sieve HY (supplied under the name HY by Changling Branch of Sinopec Catalyst Co., Ltd. and having a crystal lattice constant 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 0.3 wt.% and the content of Al ₂ O ₃ 22 wt.%), injected 100% steam, the temperature was raised to 450°C, the pressure in the device was set at 0.8 MPa, the hydrothermal treatment was carried out under constant conditions for 8 hours, and the hydrothermally treated molecular sieve material was recovered.

50 ml of an aqueous solution of hydrochloric acid and ammonium chloride was prepared using hydrochloric acid, ammonium chloride and molecular sieve starting material in a mass ratio of 0.08 1.5 1, resulting in the concentration of hydrochloric acid in the aqueous solution was 0.1 mol/l, and the concentration of ammonium chloride in the aqueous solution was 0.14 mol/l.

To 50 g (dry basis) of the hydrothermally treated molecular sieve material was added 500 ml of deionized water, mixed and suspended, obtaining a suspension of molecular sieve, which was then heated to 80°C. The resulting aqueous solution of hydrochloric acid and ammonium chloride was added to the molecular sieve slurry at a constant rate of 2 mol/h in terms of H ⁺ in relation to 1 l of molecular sieve slurry in three portions, the resulting product was reacted for 4 hours at a constant temperature each time after adding acid, then filtered, and the next addition of acid to the filter cake was carried out in the same way. After the final addition of acid and 4 hours of subsequent reaction, the solid product was recovered and dried at 180° C. for 3 hours, obtaining an RY-2 molecular sieve having a crystal lattice constant of 2.434 nm, specific surface area of 694 m ² /g, content of Na ₂ O 0.08 wt.% and the content of Al ₂ O ₃ 10.2 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in FIG. 1, and other properties are presented in table 1.

Comparative Example I-3

To 300 g of PSRY molecular sieve (same as in Example 1-2) was added 600 ml of an aqueous solution of NH ₄ Cl having a concentration of 0.5 mol/l, and deionized water was used for suspension, and the total amount of water was 1000 ml. The resulting product was heated to 90°C, subjected to ammonium ion exchange for 3 h, then filtered, washed twice with deionized water, and the filter cake was heated at 600°C and atmospheric pressure for 4 h.

300 ml of an aqueous solution of hydrochloric acid and ammonium chloride was prepared using hydrochloric acid, ammonium chloride and a raw material of a phosphorus-containing molecular sieve in a mass ratio of 0.5:0.36:1, resulting in a concentration of hydrochloric acid in an aqueous solution of 0.6 mol /l, and the concentration of ammonium chloride in an aqueous solution was 0.3 mol/l.

To 50 g (dry basis) of treated molecular sieve material was added 500 ml of deionized water, mixed and suspended, obtaining a suspension of molecular sieve, which was then heated to 80°C. The resulting aqueous solution of hydrochloric acid and ammonium chloride was added to the molecular sieve slurry at a constant rate of 2 mol/h in terms of H ⁺ in relation to 1 l of molecular sieve slurry in three portions, the resulting product was reacted for 4 hours at a constant temperature each time after adding acid, then filtered, and the next addition of acid to the filter cake was carried out in the same way. After the final addition of acid and 4 hours of subsequent reaction, the solid product was recovered and dried at 180°C for 3 hours, obtaining a phosphorus-containing RY-3 molecular sieve having a crystal lattice constant of 2.427 nm, specific surface area of 608 m ² /g, Na ₂ content O 0.12 wt.% and the content of Al ₂ O ₃ 7.8 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in Figure 1 and other properties are shown in Table 1.

Comparative Example I-4

To 300 g of PSRY molecular sieve (same as in Example 1-2) was added deionized water and suspended, and the total amount of water was 1000 ml, filtered and dried at 70°C for 2 hours, obtaining a starting material of phosphorus-containing molecular sieve with water content 65%.

The resulting phosphorus-containing molecular sieve raw material was placed in a hydrothermal treatment apparatus, the temperature was raised to 580° C., the pressure in the apparatus was set to 0.4 MPa, hydrothermal treatment was carried out for 2 hours under constant conditions, and the hydrothermally treated molecular sieve material was recovered.

500 ml of an aqueous solution of sulfuric acid was prepared using sulfuric acid and a raw material of a phosphorus-containing molecular sieve in a mass ratio of 0.8:1, resulting in a concentration of sulfuric acid in an aqueous solution of 0.2 mol/l.

To 50 g (dry basis) of the hydrothermally treated molecular sieve material was added 500 ml of deionized water, mixed and suspended, obtaining a molecular sieve suspension, which was then heated to 80°C. The resulting aqueous sulfuric acid solution was added to the molecular sieve suspension in three portions. When adding each time, the solution was directly poured into suspension, the resulting product was reacted for 2 hours at a constant temperature, then filtered, and the next addition of acid to the filter cake was carried out in the same way. After the final addition of acid and 2 hours of subsequent reaction, the solid product was recovered and dried at 100°C for 8 hours, obtaining a phosphorus-containing RY-4 molecular sieve having a crystal lattice constant of 2.432 nm, specific surface area of 485 m ² /g, Na ₂ content O 0.12 wt.% and the content of Al ₂ O ₃ 4.6 wt.%. The ^27Al NMR structural spectrum of the molecular sieve is shown in FIG. 1, and other properties are presented in table 1.

As can be seen in Table 1, the phosphorus-containing molecular sieve according to the present application has a specific combination of characteristics, in particular, an increased ratio of Bronsted acid sites to Lewis acid sites and a reduced ratio of I _-1ppm. /I _{±6 ppm} , and the method for producing a phosphorus-containing molecular sieve according to the present application can improve the yield of the molecular sieve by controlling the particle size of the raw material of the phosphorus-containing molecular sieve. Preparation of catalysts

The following examples II-1 to II-5 are examples of the production of hydrocracking catalysts according to the present application, and comparative examples II-1 to II-4 are examples of the production of hydrocracking catalysts that do not correspond to the present application.

Example II-1

583.3 g of PB90 pseudoboehmite powder (supplied by Changling Branch of Sinopec Catalyst Co., Ltd. and having a pore volume of 0.9 ml/g and a water content of 28 mass%), 98.8 g of Y-1 molecular sieve ( with a water content of 19 wt.%) and 18 g of sesbania powder, 580 ml of an aqueous solution containing 18 ml of 65-68 wt.% nitric acid (supplied by Beijing Chemical Reagents) was added and extruded to obtain a trefoil-shaped plate with a diameter 1.6 mm. The trefoil-shaped plate was dried at 120° C. and calcined at 600° C. for 3 hours to obtain CS-1 support.

After cooling to room temperature, 100 g of CS-1 support was impregnated using 80 ml of an aqueous solution containing 52 g of ammonium metatungstate (having a tungsten oxide content of 82 mass% and supplied by Sichuan Zigong Cemented Carbide Plant), 8.7 g of basic nickel carbonate (having a nickel oxide content of 51 mass% and supplied by Jiangsu Yixing Xuchi Chemical Co., Ltd.) and 10.5 g of citric acid as an impregnating solution, and dried at 120° C. for 10 hours to obtain a hydrocracking catalyst of the composition which is presented in table 2.

Examples II-2 and II-3

Catalysts were prepared as described in Example II-1, except that the molecular sieves used were Y-2 and Y-3, respectively. The compositions of the obtained catalysts are presented in table 2.

Example II-4

178 g of SB pseudoboehmite powder (supplied under the trade name SB powder by the Sasol Company and having a dry matter content of 0.72) and 31.6 g of HY molecular sieve (supplied under the trade name HY by the Changling subsidiary of Sinopec Catalyst Co., Ltd. and having dry matter content 0.76), 10 g of Y-2 molecular sieve (water content 19 wt%) and 2.2 g of sesbania powder were added and mixed evenly. 200 ml of an aqueous solution containing 2 ml of 65-68 wt% nitric acid (supplied by Beijing Chemical Reagents) was added, extruded into a trefoil-shaped plate with a circumcircle diameter of 1.6 mm, dried at 120°C, and calcined at 550 °C for 3 h to obtain the carrier CS-4.

After cooling to room temperature, 100 g of the CS-4 carrier was impregnated using 90 ml of an aqueous solution containing 24.1 g of ammonium heptamolybdate (supplied by Tianjin Sifang Chemical Development Co., Ltd. and having a molybdenum oxide content of 82 mass%), dried at 120° C. for 10 hours, and then impregnated using 50 ml of an aqueous solution containing 46.2 g of nickel nitrate (supplied by Jiangsu Yixing Xuchi Chemical Co., Ltd. and having a nickel oxide content of 25.6 mass%) , dried at 90°C for 5 hours and calcined at 420°C for 3 hours to obtain a hydrocracking catalyst whose composition is shown in Table 2.

Example II-5

67.6 g of PB100 pseudoboehmite powder (supplied by Changling Branch of Sinopec Catalyst Co., Ltd. and having a pore volume of 1.05 ml/g and a water content of 29 mass%), 138 g of Y-3 molecular sieve (content of water 19 wt%), and 6.2 g of sesbania powder, 144 ml of an aqueous solution containing 20 g of carbamide (Beijing Chemical Reagents) was added to obtain a trefoil-shaped plate with a circumscribed circle diameter of 1.6 mm, dried at 120°C and calcined at 600°C for 3 h to obtain a support CS-5.

After cooling to room temperature, 100 g of the support was impregnated using 85 ml of an aqueous solution containing 39.2 g of ammonium metatungstate (supplied by Sichuan Zigong Cemented Carbide Plant and having a tungsten oxide content of 91 mass%), 20.56 g of nickel nitrate (supplied by Jiangsu Yixing Xuchi Chemical Co., Ltd. and having a nickel oxide content of 25.6%) and 0.26 g of ethylene glycol, and dried at 180° C. for 3 hours to obtain a hydrocracking catalyst whose composition is shown in Table 2.

Comparative Examples II-1 to II-4

Catalysts were prepared as described in Example II-1, except that the molecular sieves used were RY-1, RY-2, RY-3, and RY-4, respectively. The compositions of the obtained catalysts are presented in table 2.

Application example

This application example was used to evaluate the hydrocracking catalytic activity of the catalysts prepared in Examples II-1 to II-5 and the catalysts prepared in Comparative Examples II-1 to II-4. The oil feedstock used was secondary vacuum gas oil, which was produced from Arabian light crude oil, and whose physical and chemical properties are shown in Table 3.

In this application example, the catalysts were evaluated as follows: the catalyst was pulverized to obtain particles having a diameter of 2 to 3 mm, 20 ml of the catalyst was charged into a 30 ml fixed bed reactor, and before the reaction, the catalyst was first sulfonated with kerosene containing 2 wt.% carbon disulphide , under a hydrogen atmosphere according to the procedure described below, and then the oil starting material was used as the reaction oil.

The sulfonation procedure was carried out as follows: the reactor was heated to 150°C, vulcanized oil was introduced, and the reaction mixture was kept at this temperature for 1 hour; heated to 230°C at 60°C/h, stabilized for 2 hours, then heated to 360°C at 60°C/h and stabilized for 6 hours. was set as follows, and the reaction system was stabilized for at least 20 hours.

The hydrocracking reaction was carried out under the following conditions: the reaction temperature was 365° C., the hydrogen partial pressure was 6.4 MPa, the liquid hourly space velocity (LHSV) was 1 h ⁻¹ , and the hydrogen to oil volume ratio was 800 Nm ³ /m ³ . The results are presented in table 4.

As can be seen in Table 4, the increase in catalytic activity of hydrocracking catalysts containing phosphorus-containing molecular sieve according to the present application is approximately 7.9 to 63.4% compared to hydrocracking catalysts containing molecular sieve obtained by conventional methods, under the same conditions. reactions.

Preferred embodiments of the present application are described in detail with reference to the accompanying figures. However, the present application is not limited to these embodiments, and various modifications can be made without departing from the spirit of the present application. Such modifications are also within the scope of the present application.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without conflict, and in order to avoid unnecessary repetition, these possible combinations have not been described separately herein.

In addition, arbitrary combinations of embodiments of the present application can also be made, and these combinations should be considered as part of the disclosure of the present application, provided that they do not deviate from the idea of the present application.

Claims (42)

1. A phosphorus-containing molecular sieve having a faujasite structure for use in hydrocracking of hydrocarbon feedstocks, having a phosphorus content in terms of oxide of 0.3 wt.% to 5 wt.%, a pore volume of 0.2 ml / g to 0.95 ml/g, and a ratio of Brønsted acid sites to Lewis acid sites of 3.4 to 9.5, wherein the molecular sieve has a structural ²⁷ Al NMR spectrum representing a ratio of I ₆₀ ppm. /I _-1 ppm, ranging from 5 to 40, and the ratio L _{-1 ppm.} /I _{±6 ppm} , ranging from 0.4 to 2. 2. Phosphorus-containing molecular sieve according to claim 1, wherein the phosphorus-containing molecular sieve has a phosphorus content in terms of oxide from 0.4 wt.% to 2.0 wt.%, a pore volume is from 0.25 ml / g to 0.60 ml/g and has a structural NMR spectrum ²⁷ Al, representing the ratio of I _{60 ppm} /I _{-1 ppm.} , ranging from 10.0 to 39, and the ratio I _-1m.d. /I _±6ppm , ranging from 0.4 to 2. 3. Phosphorus-containing molecular sieve according to any one of the preceding paragraphs, and the molecular sieve has a crystal lattice constant of from 2.425 to 2.470 nm, a specific surface area of 250 to 850 m ² /g; and the molecular sieve is a Y-type molecular sieve. 4. Phosphorus-containing molecular sieve according to any one of the preceding paragraphs, and the molecular sieve has a crystal lattice constant of 2.430 to 2.458 nm, a specific surface area of 400 to 750 m ² /g; and a molecular sieve selected from the group consisting of NaY, HNaY, REY, USY molecular sieves and combinations thereof. 5. A phosphorus-containing molecular sieve according to any one of the preceding claims, wherein the molecular sieve is produced by a method comprising: i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve having the structure of faujasite; ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is in the range of 14:1 to 5:1; iii) subjecting the resulting molecular sieve slurry to an acid leach; and iv) recovering the solid product, wherein the acid leaching in step (iii) is carried out as follows: the acid solution is added to the molecular sieve suspension at a constant rate at a temperature of 40° C. to 95° C., the acid solution is added at a rate of 0.05 mol/ h to 10 mol/h, in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for 0.5 h to 20 h, and the mass ratio of the acid in the acid solution and dry weight of the source material of the phosphorus-containing molecular sieve is in the range from 0.01:1 to 0.6:1. 6. The phosphorus-containing molecular sieve according to claim 5, wherein the acid leaching in step (iii) is carried out as follows: the acid solution is added to the molecular sieve suspension at a constant rate at a temperature of 50°C to 85°C, while the acid solution is added at a rate of 0.2 mol/h to 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for 0.5 h to 15 hours, and the ratio of the weight of the acid in the acid solution and the dry weight of the source material of the phosphorus-containing molecular sieve is in the range from 0.01:1 to 0.6:1. 7. A method for producing a phosphorus-containing molecular sieve according to claim 1, including the following steps: i) the effect of hydrothermal treatment on the source material of the phosphorus-containing molecular sieve having the structure of faujasite; ii) forming a hydrothermally treated molecular sieve slurry, wherein the ratio of the weight of water in the resulting molecular sieve slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is in the range of 14:1 to 5:1; iii) subjecting the resulting molecular sieve slurry to an acid leach; and iv) recovering the solid product, wherein the acid leaching in step (iii) is carried out as follows: the acid solution is added to the molecular sieve suspension at a constant rate at a temperature of 40° C. to 95° C., the acid solution is added at a rate of 0.05 mol/ h to 10 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for 0.5 h to 20 h, and the mass ratio of the acid in the acid solution and dry the weight of the starting material of the phosphorus-containing molecular sieve is in the range from 0.01:1 to 0.6:1. 8. The method according to claim 7, in which the acid leach in step (iii) is carried out as follows: adding the acid solution to the molecular sieve suspension at a constant rate at a temperature of from 50°C to 85°C, while the acid solution is added with a rate of 0.2 mol/h to 3.0 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension, and the resulting product is subjected to an isothermal reaction after completion of the addition of acid for 0.5 h to 15 h, and the ratio of the weight of the acid in the acid solution and the dry weight of the source material of the phosphorus-containing molecular sieve is in the range from 0.01:1 to 0.6:1. 9. The method according to claim 7 or 8, wherein the phosphorus-containing molecular sieve starting material has a phosphorus content of 0.1 wt% to 15 wt% and a sodium content of 0.5 wt% to 4, 5 wt.%, in terms of oxides and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve. 10. The method according to claim 7 or 8, wherein the phosphorus-containing molecular sieve starting material has a phosphorus content of 0.2 wt.% to 5.0 wt.%, and a sodium content of 1.0 wt.% to 4.0 wt.% in terms of oxides and in relation to the dry weight of the source material of the phosphorus-containing molecular sieve; and the starting material of the phosphorus-containing molecular sieve has a water content of 10 wt.% to 40 wt.%. 11. The method according to any one of paragraphs. 7-10, wherein the phosphorus-containing molecular sieve starting material is a Y-type phosphorus-containing molecular sieve having a lattice constant of 2.425 to 2.470 nm, a specific surface area of 250 m ² /g to 750 m ² /g, and a pore volume of 0.2 ml/g to 0.95 ml/g. 12. The method according to any one of paragraphs. 7-11, wherein the phosphorus-containing molecular sieve starting material is present in particulate form, and the phosphorus-containing molecular sieve starting material having a particle size of 5 to 100 mm is 30 wt.% to 100 wt.% of the total mass of the phosphorus-containing starting material. molecular sieve. 13. The method according to any one of paragraphs. 7-12, in which the hydrothermal treatment in step (i) is carried out in the presence of 30 to 100% steam under the following conditions: the temperature is from 350°C to 700°C, the pressure is from 0.1 MPa to 2 MPa, and the duration of the hydrothermal processing is from 0.5 h to 10 h. 14. The method according to any one of paragraphs. 7-12, wherein the acid solution used in the acid leaching in step (iii) has an acid concentration of 0.01 mol/L to 15.0 mol/L, and the acid is selected from the group which is phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and combinations thereof. 15. The method according to any one of paragraphs. 7-14, wherein in the acid leaching in step (iii), the acid solution is added 2 to 10 times, and the acid solution is added at a constant rate of 0.05 mol/h to 10 mol/h in terms of H ⁺ with respect to 1 l of molecular sieve suspension during the time of each addition, and the resulting product is subjected to an isothermal reaction after each addition for such a period of time that the total duration of the isothermal reaction is from 0.5 hour to 20 hours; and when the ratio of the weight of the acid in the acid solution to the dry weight of the phosphorus-containing molecular sieve starting material is in the range of 0.01:1 to 0.3:1. 16. Hydrocracking catalyst containing in terms of dry matter and in relation to the mass of the catalyst from 45 wt.% to 90 wt.% of the carrier, from 1 wt.% to 40 wt.% of the component of the first metal in terms of metal oxide and from 1 wt.% up to 15 wt.% component of the second metal in terms of metal oxide, and: the carrier contains a phosphorus-containing molecular sieve according to any one of paragraphs. 1-6 and a refractory inorganic oxide, wherein the weight ratio of the phosphorus-containing molecular sieve and the refractory inorganic oxide is from 0.03:1 to 20:1; the first metal of the first metal component is a Group VIB metal; and the second metal of the second metal component is a Group VIII metal. 17. The catalyst according to claim 16, wherein the refractory inorganic oxide is selected from the group consisting of alumina, silicon dioxide, amorphous silicon and aluminum double oxides, zirconia, magnesium oxide, thorium dioxide, beryllium oxide, boron oxide, cadmium oxide, and their combinations; the first metal of the first metal component is molybdenum and/or tungsten; and the second metal of the second metal component is selected from the group consisting of iron, nickel, cobalt, and combinations thereof. 18. A method for producing a hydrocracking catalyst, comprising the steps of bringing the impregnation carrier into contact with an impregnating solution containing the original metal compound, and drying the material obtained after impregnation, wherein: the carrier contains a phosphorus-containing molecular sieve according to any one of paragraphs. 1-6 and a refractory inorganic oxide, and the mass ratio of the phosphorus-containing molecular sieve and the refractory inorganic oxide is from 0.03:1 to 20:1; and the parent metal compound comprises a parent compound of a first metal and a parent compound of a second metal, wherein the first metal of the first metal component is a Group VIB metal and the second metal of the second metal component is a Group VIII metal. 19. The method according to claim 18, further comprising the following steps: mixing a phosphorus-containing molecular sieve and a refractory inorganic oxide with a peptizing agent, and then shaping, drying and calcining to obtain a carrier. 20. The method of claim 18 or 19, wherein the first metal starting compound is selected from the group consisting of first metal inorganic acids, first metal inorganic salts, first metal organometallic compounds, and combinations thereof; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the first metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof; and the parent compound of the second metal is selected from the group consisting of inorganic acids of the second metal, inorganic salts of the second metal, organometallic compounds of the second metal, and combinations thereof; wherein the inorganic salt is selected from the group consisting of nitrates, carbonates, hydroxycarbonates, hypophosphites, phosphates, sulfates, chlorides, and combinations thereof; and the organic fragment in the organometallic compound of the second metal is selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether, alkyl groups, and combinations thereof. 21. The use of a phosphorus-containing molecular sieve according to any one of paragraphs. 1-6 or a hydrocracking catalyst according to any one of paragraphs. 16, 17 in the hydrocracking of hydrocarbon feedstocks. 22. Use according to claim 21 wherein the hydrocarbon feedstock is selected from the group consisting of straight run gas oils, vacuum gas oils, demetallized oils, atmospheric distillation residues, deasphalted vacuum distillation residues, coking distillates, catalytic cracking distillates, shale oils, oils tar sands, liquefied coal oils and combinations thereof; and hydrocracking conditions include: a reaction temperature of 200 to 650°C; a reaction pressure of 3 to 24 MPa; hourly space velocity of the liquid, ranging from 0.1 to 10 h ^-1 ; volume ratio of hydrogen and oil, ranging from 100 to 5000 Nm ³ /m ³ .

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