CN111097506A

CN111097506A - Hydrocracking catalyst containing composite molecular sieve and silicon-aluminum, and preparation method and application thereof

Info

Publication number: CN111097506A
Application number: CN201811259948.3A
Authority: CN
Inventors: 毛以朝; 龙湘云; 张润强; 赵阳; 赵广乐
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-10-26
Filing date: 2018-10-26
Publication date: 2020-05-05
Anticipated expiration: 2038-10-26
Also published as: CN111097506B

Abstract

The present disclosure relates to a hydrocracking catalyst, a preparation method and an application thereof, wherein the catalyst comprises a carrier of 45-90 wt% calculated by dry weight of the catalyst, a first metal component of 1-40 wt% calculated by metal oxide, and a second metal component of 1-15 wt% calculated by metal oxide; the carrier comprises a phosphorus-containing high-silicon molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, wherein in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a first strong peak is 5.9-6.9 degrees, the diffraction angle position of a second strong peak is 10.0-11.0 degrees, and the diffraction angle position of a third strong peak is 15.6-16.7 degrees. The catalyst has high hydrocracking reaction activity and high nitrogen stability.

Description

Hydrocracking catalyst containing composite molecular sieve and silicon-aluminum, and preparation method and application thereof

Technical Field

The disclosure relates to a hydrocracking catalyst, a preparation method and an application thereof.

Background

Commercial hydrocracking feeds include heavy, inferior fractions such as VGO, containing significant amounts of polycyclic aromatic hydrocarbons and naphthenes, as well as significant amounts of nitrogen-containing compounds. Conventional hydrocracking feed nitrogen mass percentages are generally between 0.1 and 0.2. However, secondary processing of oil refining such as coking, solvent deasphalting, etc. often produces large amounts of nitrogen-containing compounds, often with nitrogen contents exceeding 0.3%, and some even reaching 0.6%, which makes it difficult to remove the nitrogen contents to 10-100ppm levels that conventional molecular sieve type hydrocracking catalysts can endure after using conventional refining catalysts. Amorphous silica-alumina or silica-containing alumina having weak acidity is generally used as an acidic component as a main acidic component of the high nitrogen content hydrocracking catalyst.

The prior art invention generally uses a solution of silicon oxide and aluminum oxide in salt to synthesize weakly acidic silicon aluminum at low pH, and also uses a method of grafting aluminum oxide on a silicon oxide precursor or grafting aluminum oxide on a silicon oxide precursor, and forming silicon aluminum tetrahedron by further reaction, thereby generating acidity in the sample.

ZL97121663.0 discloses a hydrocracking catalyst especially suitable for producing middle distillate, which comprises amorphous silica-alumina component and small-pore alumina adhesive, wherein the content of amorphous silica-alumina is 30-60 wt%, at least one VIB group element and at least one VIII group element, the total content of hydrogenated metal oxides is 20-35 wt%, and the balance is small-pore alumina adhesive, and is characterized in that the specific surface of the catalyst is 150-300 m-²The volume of the pores is 0.25-0.50 ml/g, the pore size of the pores is 60-90%, and the infrared acidity is 0.30-0.50 mmol/g.

Although the methods can generate certain acidity, the materials are short-range ordered and difficult to achieve long-range ordered due to the existence of a large amount of non-framework six-coordinate aluminum in the obtained samples in order to keep the structure of the matrix stable in the synthesis process.

Disclosure of Invention

The aim of the disclosure is to provide a hydrocracking catalyst, a preparation method and an application thereof, wherein the catalyst has higher hydrocracking reaction activity and nitrogen resistance stability.

To achieve the above object, a first aspect of the present disclosure: providing a hydrocracking catalyst, wherein the catalyst comprises 45-90 wt% of a carrier, 1-40 wt% of a first metal component and 1-15 wt% of a second metal component, wherein the carrier is calculated by the weight of the carrier on a dry basis, the first metal component is calculated by metal oxide, and the second metal component is calculated by the weight of the metal oxide;

the carrier comprises a phosphorus-containing high-silicon molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, wherein the weight ratio of the phosphorus-containing high-silicon molecular sieve to the Y-type molecular sieve to the weakly acidic silicon aluminum to the aluminum oxide is 1: (0.03-20): (0.03-20): (0.05-15); the first metal component is a metal component selected from metals of a VIB group; the second metal component is a metal component selected from group VIII metals;

the phosphorus-containing high-silicon molecular sieve has the pore volume of 0.20-0.50 mL/g and the specific surface area of 260-600 m²The phosphorus-containing high-silicon molecular sieve comprises, by weight, 90-99.8% of silicon, 0.1-9.0% of aluminum and 0.01-2.5% of phosphorus, wherein the percentages by weight are calculated by oxides and based on the dry weight of the molecular sieve; in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a first intensity peak is 5.9-6.9 degrees, the diffraction angle position of a second intensity peak is 10.0-11.0 degrees, and the diffraction angle position of a third intensity peak is 15.6-16.7 degrees.

Optionally, in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a first intensity peak is 6.1-6.8 °, the diffraction angle position of a second intensity peak is 10.2-10.7 °, and the diffraction angle position of a third intensity peak is 15.8-16.5 °.

Optionally, the phosphorus-containing high silicon molecular sieveIn XRD spectrum of (1), I₁/I_{23.5～24.5°}Is 3.0 to 11.0, I₂/I_{23.5～24.5°}Is 2.9 to 7.0, I₃/I_{23.5～24.5°}1.0 to 4.0, wherein I₁Is the peak height of the first strong peak, I₂Is the peak height of the second strong peak, I₃Is the peak height of the third strong peak, I_{23.5～24.5°}The peak height of the diffraction angle peak at a diffraction angle position of 23.5 to 24.5 degrees.

Optionally, in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a fourth intensity peak is 20.4-21.6 degrees, and the diffraction angle position of a fifth intensity peak is 11.8-12.8 degrees.

Optionally, in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a fourth intensity peak is 20.8-21.4 degrees, and the diffraction angle position of a fifth intensity peak is 12.1-12.6 degrees; and/or the presence of a gas in the gas,

I₄/I_{23.5～24.5°}1.0 to 4.0, I₅/I_{23.5～24.5°}1.0 to 2.0, wherein I₄Is the peak height of the fourth strong peak, I₅Is the peak height of the fifth strong peak, I_{23.5～24.5°}The diffraction angle peak has a diffraction angle position of 23.5 to 24.5 degrees.

Alternatively, the phosphorus-containing high-silicon molecular sieve is prepared by a method comprising the following steps:

a. carrying out hydro-thermal treatment on a phosphorus-containing molecular sieve raw material for 0.5-10 h at the temperature of 350-700 ℃ and the pressure of 0.1-2 MPa in the presence of steam to obtain a hydro-thermally treated molecular sieve material; calculated by oxide and based on the dry weight of the phosphorus-containing molecular sieve raw material, the phosphorus content of the phosphorus-containing molecular sieve raw material is 0.1-15 wt%, and the sodium content is 0.5-4.5 wt%;

b. b, adding water into the molecular sieve material subjected to the hydrothermal treatment obtained in the step a, pulping to obtain first slurry, heating the first slurry to 40-95 ℃, keeping the temperature, adding a first acid solution into the first slurry, wherein the adding amount of the first acid solution enables the pH value of the first slurry subjected to acid addition to be 2.5-4, carrying out constant temperature reaction for 0.5-20 h, and collecting a first solid product;

c. b, adding water into the first solid product obtained in the step b, pulping to obtain second slurry, heating the second slurry to 40-95 ℃, keeping the temperature, continuously adding a second acid solution into the second slurry, wherein the adding amount of the second acid solution enables the pH value of the acid-added second slurry to be 1.0-2.0, reacting at constant temperature for 0.5-20 h, and collecting a second solid product.

Optionally, in the step a, the phosphorus-containing molecular sieve is a phosphorus-containing Y-type molecular sieve, the unit cell constant of the phosphorus-containing Y-type molecular sieve is 2.425-2.47 nm, and the specific surface area is 250-750 m²The pore volume is 0.2-0.95 mL/g.

Optionally, in the step b, the ratio of the weight of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is (14-5): 1.

optionally, in step c, the ratio of the weight of water in the second slurry to the dry weight of the phosphorus-containing molecular sieve raw material is (0.5-20): 1.

optionally, in step c, the second acid solution is added in a manner that: taking 1L of the second slurry as a reference, and taking H as the reference⁺The second acid solution is added to the second slurry at a rate of 0.05 to 10 moles/hour.

Optionally, in the step b, the acid concentration of the first acid solution is 0.01-15.0 mol/L, and the acid in the first acid solution is at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid; and/or the presence of a gas in the gas,

in the step c, the acid concentration of the second acid solution is 0.01-15.0 mol/L, and the acid in the second acid solution is at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid.

Optionally, the step of preparing the phosphorus-containing high silicon molecular sieve further comprises: collecting the second product, then washing with water and drying to obtain a high-silicon phosphorus-containing molecular sieve; and/or, the drying conditions are as follows: the temperature is 50-350 ℃, and preferably 70-200 ℃; the time is 1-24 h, preferably 2-6 h.

Optionally, the acidity value of the infrared B acid of the weakly acidic silicon aluminum is 0.01-0.1 mmol/g, the silicon content calculated by silicon dioxide is 20-60 wt%, and the pore volume is 0.5-1.0 mL/g; preferably, the weak acid silicon aluminum is silicon-containing aluminum oxide and/or amorphous silicon aluminum;

and/or the unit cell constant of the Y-type molecular sieve is 2.465-2.420 nm, and the specific surface area is 500-850 m²Per gram, the pore volume is 0.25-0.55 ml/g;

and/or the first metal component is a molybdenum component and/or a tungsten component; the second metal component is an iron component, a nickel component, or a cobalt component, or a combination of two or three thereof.

In a second aspect of the present disclosure: there is provided a process for preparing a hydrocracking catalyst according to the first aspect of the present disclosure, the process comprising: and contacting an impregnation liquid containing a first metal precursor and a second metal precursor with the carrier for impregnation.

Optionally, the method further comprises: mixing a high-silicon phosphorus-containing molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, and then molding, drying and roasting to obtain the carrier.

Optionally, the first metal precursor is an inorganic acid, an inorganic salt or an organic compound of a first metal; the inorganic salt is nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the first metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl; and/or the presence of a gas in the gas,

the second metal precursor is an inorganic acid, an inorganic salt or an organic compound of a second metal; the inorganic salt is nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the second metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl.

Optionally, the method further comprises the steps of drying and roasting the impregnated material; and/or the presence of a gas in the gas,

the drying conditions are as follows: the temperature is 80-350 ℃, and the time is 0.5-24 hours; and/or the presence of a gas in the gas,

the roasting conditions are as follows: the temperature is 350-600 ℃, and the time is 0.2-12 hours.

A third aspect of the disclosure: there is provided the use of a hydrocracking catalyst according to the first aspect of the present disclosure in a hydrocracking reaction of a hydrocarbon feedstock.

Optionally, the hydrocarbon feedstock is straight run gas oil, vacuum gas oil, demetallized oil, atmospheric residue oil, deasphalted vacuum residue oil, coker distillate oil, catalytically cracked distillate oil, shale oil, tar sand oil, or coal liquefaction oil, or a combination of two or three thereof; and/or the presence of a gas in the gas,

the conditions of the hydrocracking reaction are as follows: the reaction temperature is 200-650 ℃, preferably 300-510 ℃; the reaction pressure is 3-24 MPa, preferably 4-15 MPa; the liquid hourly space velocity is 0.1-50 h^-1Preferably 0.2 to 30 hours^-1(ii) a The volume ratio of the hydrogen to the oil is 100-5000.

According to the technical scheme, the phosphorus-containing molecular sieve is adopted to carry out special hydrothermal treatment and two-step acid pickling treatment on the raw material to prepare the phosphorus-containing high-silicon molecular sieve with novel structural characteristics, and the hydrocracking catalyst prepared by adopting the phosphorus-containing high-silicon molecular sieve has higher hydrocracking activity and nitrogen stability resistance.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

FIG. 1 is an XRD spectrum of the molecular sieves prepared in preparation examples 1 to 2 and preparation comparative examples 1 to 3.

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The first aspect of the disclosure: provided is a hydrocracking catalyst, which is characterized by comprising 45-90 wt% of a carrier, 1-40 wt% of a first metal component and 1-15 wt% of a second metal component, wherein the first metal component is calculated by metal oxide, and the second metal component is calculated by metal oxide, and the first metal component and the second metal component are calculated by metal oxide, and the second metal component is calculated by metal oxide. The carrier comprises a phosphorus-containing high-silicon molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, wherein the weight ratio of the phosphorus-containing high-silicon molecular sieve to the Y-type molecular sieve to the weakly acidic silicon aluminum to the aluminum oxide is 1: (0.03-20): (0.03-20): (0.05-15). The first metal component is a metal component selected from a group VIB metal; the second metal component is a metal component selected from group VIII metals.

In the hydrocracking catalyst disclosed by the disclosure, the phosphorus-containing high-silicon molecular sieve serving as a carrier component has special performance, so that the hydrocracking catalyst has higher hydrocracking activity and nitrogen resistance stability. The phosphorus-containing high-silicon molecular sieve has the pore volume of 0.20-0.50 mL/g and the specific surface area of 260-600 m²The phosphorus-containing high-silicon molecular sieve comprises, by weight of oxides and based on the dry basis weight of the molecular sieve, 90-99.8% of silicon, 0.1-9.0% of aluminum and 0.01-2.5% of phosphorus; in addition, the phosphorus-containing high-silicon molecular sieve can also contain a small amount of sodium, and the sodium content of the molecular sieve can be 0.01-1.0 wt% in terms of oxides and on the basis of the dry weight of the molecular sieve.

According to the present disclosure, the phosphorus-containing high silicon molecular sieve has different structural characteristics from conventional silicon-aluminum materials. Specifically, in an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of a first intensity peak is 5.9-6.9 degrees, and preferably 6.1-6.8 degrees; the diffraction angle position of the second strong peak is 10.0-11.0 degrees, preferably 10.2-10.7 degrees; the diffraction angle of the third intensity peak is 15.6 to 16.7 degrees, preferably 15.8 to 16.5 degrees. It is well known to those skilled in the art that in the structural analysis of a substance by X-ray diffraction (XRD), the D value (interplanar spacing) can be generally calculated from the wavelength and diffraction angle, and the initial identification of the phase is performed based on the features of the strongest three diffraction peaks, i.e., the first, second and third intensity peaks in the present disclosure. The concept of the three strong peaks can also be found in "Yi Yuan root Prudo" research method of heterogeneous catalyst [ M ]. Beijing: chemical industry Press, 1988.P140-170 ". Wherein, the diffraction angle position refers to the 2 theta angle value of the highest value of diffraction peak in the XRD spectrogram.

Further, in the XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, I₁/I_{23.5～24.5°}Can be 3.0 to 11.0, I₂/I_{23.5～24.5°}Can be 2.9 to 7.0, I₃/I_{23.5～24.5°}Can be 1.0 to 4.0, wherein I₁Is the peak height of the first strong peak, I₂Is the peak height of the second strong peak, I₃Is the peak height of the third strong peak, I_{23.5～24.5°}The peak height of the diffraction angle peak with the diffraction angle position of 23.5-24.5 degrees.

Further, in the XRD spectrogram of the phosphorus-containing high-silicon molecular sieve, the diffraction angle position of the fourth strong peak can be 20.4-21.6 degrees, preferably 20.8-21.4 degrees, and the diffraction angle position of the fifth strong peak can be 11.8-12.8 degrees, preferably 12.1-12.6 degrees. Further, I₄/I_{23.5～24.5°}Can be 1.0-4.0, I₅/I_{23.5～24.5°}Can be 1.0-2.0, wherein, I₄Is the peak height of the fourth strong peak, I₅Is the peak height of the fifth strong peak, I_{23.5～24.5°}The peak height of the diffraction angle peak with the diffraction angle position of 23.5-24.5 degrees. The concept of the fourth strong peak and the fifth strong peak can be understood according to the description of the three strong peaks, and will not be described herein.

The phosphorus-containing high-silicon molecular sieve is prepared by carrying out special hydrothermal treatment and two-step acid washing treatment on a phosphorus-containing molecular sieve raw material. Specifically, the phosphorus-containing high-silicon molecular sieve is prepared by a method comprising the following steps:

According to the present disclosure, in step a, the phosphorus-containing molecular sieve raw material refers to a phosphorus-containing molecular sieve. The method adopts the phosphorus-containing molecular sieve as a raw material, and phosphorus aluminum species outside the molecular sieve framework can improve the framework stability of the molecular sieve, so that the performance of the molecular sieve is further improved. The structure of the phosphorus-containing molecular sieve raw material can be an octahedral zeolite molecular sieve structure, preferably a phosphorus-containing Y-type molecular sieve, the unit cell constant of the phosphorus-containing molecular sieve raw material can be 2.425-2.47 nm, and the specific surface area of the phosphorus-containing molecular sieve raw material can be 250-750 m²The pore volume may be 0.2 to 0.95 mL/g. Further, the specific selection of the Y-type molecular sieve may be widely varied as long as the phosphorus-containing molecular sieve raw material satisfies the above conditions, and for example, the Y-type molecular sieve may be selected from NaY, HNaY (hydrogen Y-type molecular sieve), REY (rare earth Y-type molecular sieve), USY (ultra stable Y-type molecular sieve), and the like. The cation position of the phosphorus-containing Y-type molecular sieve can be occupied by one or more of sodium ions, ammonium ions and hydrogen ions; alternatively, the sodium, ammonium and hydrogen ions may be replaced by other ions, either before or after the molecular sieve is introduced with phosphorus, by conventional ion exchange. What is needed isThe phosphorus-containing molecular sieve raw material can be a commercial product, and can also be prepared by any conventional technology, for example, a method for preparing USY disclosed in a patent ZL00123139.1, a method for preparing PUSY disclosed in a patent ZL200410071122.6 and the like can be adopted, and the details of the disclosure are not repeated.

The meaning of said water addition beating in step b and step c is well known to the person skilled in the art in light of the present disclosure. In the step b, the ratio of the weight of water in the first slurry obtained after pulping to the dry basis weight of the phosphorus-containing molecular sieve raw material can be (14-5): 1. in the step c, the ratio of the weight of water in the second slurry to the dry weight of the phosphorus-containing molecular sieve raw material may be (0.5-20): 1.

according to the present disclosure, in the step b, the first slurry is preferably heated to 50 to 85 ℃, and then the temperature is maintained and the first acid solution is continuously added to the first slurry until the pH value of the first slurry after the acid addition reaches the required value. The amount of the first acid solution added can vary widely according to the nature of the phosphorus-containing molecular sieve feedstock and the hydrothermal treatment conditions of step a, and it will be understood by those skilled in the art that the amount of the first acid solution added is reasonable as long as the pH of the acidified first slurry meets the above suitable range. The rate of addition of the first acid solution is not particularly limited and may vary over a wide range.

According to the disclosure, in the step b, the operation of adding the first acid solution may be performed multiple times (for example, 1 to 5 times), and after each time of adding the acid, the reaction may be performed at a constant temperature for a period of time, and then the next time of adding the acid is continued until the pH value of the first slurry after adding the acid reaches a required range. The acid concentration of the first acid solution can be 0.1-15.0 mol/L, and the pH value can be 0.01-3. The acid in the first acid solution may be a conventional inorganic acid and/or organic or acid, and may be, for example, at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid.

According to the present disclosure, in step c, the second slurry is preferably heated to 50-85 ℃, then maintained at temperature and continuouslyAdding a second acid solution to the second slurry until the pH of the acid-added second slurry reaches a desired level. The second acid solution may be added in a manner that: based on 1L of the second slurry, taking H as reference⁺And adding the second acid solution into the second slurry at a speed of 0.05-10 mol/h. Thus, the acid adding speed is slower in the step c, so that the dealumination process is more moderate, and the performance of the molecular sieve is favorably improved.

According to the disclosure, in the step c, the operation of adding the second acid solution may be performed multiple times (for example, 1 to 5 times), and after each time of adding the acid, the reaction may be performed at a constant temperature for a period of time, and then the next time of adding the acid is continued until the pH value of the second slurry after adding the acid reaches a required range. The acid concentration of the second acid solution can be 0.1-15.0 mol/L, and the pH value can be 0.01-3. The acid in the second acid solution may be a conventional inorganic acid and/or organic or acid, and may be, for example, at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid. The second acid solution may be the same as or different from the first acid solution in terms of kind and concentration, and is preferably the same acid solution.

According to the present disclosure, the preparation steps of the phosphorus-containing high silicon molecular sieve may further include: and collecting the second product, and then washing and drying to obtain the phosphorus-containing high-silicon molecular sieve. The washing and drying are conventional steps for preparing a molecular sieve, and the present disclosure is not particularly limited. For example, the drying may be performed by using an oven, a mesh belt, a converter, or the like, and the drying conditions may be: the temperature is 50-350 ℃, and preferably 70-200 ℃; the time is 1-24 h, preferably 2-6 h.

According to the present disclosure, the Y-type molecular sieve may be selected from HY (hydrogen Y-type molecular sieve), REY (rare earth Y-type molecular sieve), PY (phosphorus-containing Y-type molecular sieve), USY (ultrastable Y-type molecular sieve), PUSY (phosphorus-containing USY, including PHY, REUSY), preferably USY, PUSY, and further preferably PUSY. The unit cell constant of the second Y-type molecular sieve can be 2.465-2.420 nm, and the specific surface area can be 500-850 m²In grams, the pore volume may be0.25 to 0.55 ml/g. The second Y-type molecular sieve can be a commercially available product, or can be prepared by any conventional method, for example, the method for preparing USY disclosed in patent ZL00123139.1, or the method for preparing PUSY disclosed in patent ZL 200410071122.6.

According to the disclosure, the acidity value of the infrared B acid of the weakly acidic silicon aluminum can be 0.01 to 0.1mmol/g, the silicon content of the weakly acidic silicon aluminum as a reference and calculated by silicon dioxide can be 20 to 60 wt%, and the pore volume can be 0.5 to 1.0 mL/g. The weakly acidic silicon aluminum is, for example, silicon-containing alumina and/or amorphous silicon aluminum. The present disclosure is not particularly limited with respect to the source of the weakly acidic silica-alumina.

In accordance with the present disclosure, the alumina may include gibbsite such as gibbsite (gibbsite), bayerite (bayeritenordstrandite), and diaspore such as boehmite (boehmite, diasporic, pseudoboehmite). The source of alumina is not particularly limited in this disclosure provided that it sufficiently meets the requirements of the present disclosure, and may be, for example, commercially available or prepared by any conventional method, such as pseudoboehmite prepared by the neutralization of aluminum sulfate and sodium metaaluminate as disclosed in patent CN 100999328B.

According to the present disclosure, preferably, the first metal is a molybdenum component and/or a tungsten component; the second metal component is an iron component, a nickel component, or a cobalt component, or a combination of two or three thereof.

In a second aspect of the present disclosure: there is provided a process for preparing a hydrocracking catalyst according to the first aspect of the present disclosure, the process comprising: and contacting an impregnation liquid containing a first metal precursor and a second metal precursor with the carrier for impregnation. The contact impregnation method of the impregnation liquid and the carrier can adopt any method known in the art, such as a method disclosed in patent CN200810241082.3 which comprises loading a group VIB metal component, a group VIII metal component and an organic additive on a catalyst carrier.

Methods for preparing the carrier are well known to those skilled in the art, and the present disclosure is not particularly limited. For example, the method may further comprise: mixing a high-silicon phosphorus-containing molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, and then molding and drying to obtain the carrier. The molding method can adopt various conventional methods, such as tabletting molding, rolling ball molding or extrusion molding.

The shape of the carrier is not particularly required in the present disclosure, and may be spherical, strip-shaped, hollow strip-shaped, spherical, block-shaped, etc., and the strip-shaped carrier may be cloverleaf, clover, etc., and variations thereof.

According to the present disclosure, the first metal precursor is a soluble compound containing the first metal, including at least one of an inorganic acid of the first metal, an inorganic salt of the first metal, and a first metal organic compound; the inorganic salt may be at least one selected from the group consisting of nitrate, carbonate, hydroxycarbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the first metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl. For example, when the first metal is molybdenum, the first metal precursor may be at least one selected from molybdic acid, paramolybdic acid, molybdate, paramolybdate, and the like; when the first metal is tungsten, the first metal precursor may be at least one selected from the group consisting of tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstate. The second metal precursor is a soluble compound containing the second metal and comprises at least one of inorganic acid of the second metal, inorganic salt of the second metal and organic compound of the second metal; the inorganic salt may be at least one selected from the group consisting of nitrate, carbonate, hydroxycarbonate, hypophosphite, phosphate, sulfate and chloride; the organic substituent in the second metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl.

According to the present disclosure, the impregnation fluid may further contain an organic additive; the concentration of the organic additive can be 2-300 g/L. The organic additive is an oxygen-containing organic compound and/or a nitrogen-containing organic compound. Specifically, the oxygen-containing organic compound may be at least one selected from the group consisting of ethylene glycol, glycerol, polyethylene glycol (molecular weight may be 200 to 1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid; the nitrogen-containing organic compound may be at least one selected from the group consisting of ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid and ammonium ethylenediaminetetraacetate.

In the method for producing a hydrocracking catalyst of the present disclosure, the contacting temperature is not particularly limited, and may be various temperatures that the impregnation solution can reach. The time for the impregnation is also not particularly limited as long as the catalyst carrier can be supported with the desired amount of the metal active component precursor. In general, the higher the impregnation temperature, the higher the impregnation solution concentration, and the shorter the time required to achieve the same impregnation amount (i.e., the weight difference between the catalyst support after impregnation and before impregnation); and vice versa. When the desired amount of impregnation and conditions are determined, one skilled in the art can readily select an appropriate impregnation time based on the teachings of the present disclosure. The present disclosure does not specifically require an impregnation method, which may be either a saturated impregnation or a supersaturated impregnation. The impregnation may be carried out under a sealed condition or in an open environment according to a conventional method in the art, and the loss of the aqueous solvent may or may not be replenished during the impregnation. Various gases, such as air, nitrogen, water vapor, etc., may be introduced during the impregnation process, or any new components may not be introduced.

The method for preparing a hydrocracking catalyst according to the present disclosure may further include a step of drying and calcining the impregnated resultant material, which is a conventional step for preparing a catalyst, and the present disclosure is not particularly limited. For example, the drying conditions may be: the temperature is 80-350 ℃, preferably 100-300 ℃, and the time is 0.5-24 hours, preferably 1-12 hours. The roasting conditions can be as follows: the temperature is 350-600 ℃, and preferably 400-550 ℃; the time is 0.2 to 12 hours, preferably 1 to 10 hours.

The hydrocracking catalyst provided by the disclosure can be used as various acid catalytic catalysts in catalytic cracking, hydroisomerization, alkylation, hydrocracking and other reactions, and is particularly suitable for hydrocracking hydrocarbon raw materials to produce hydrocarbon fractions with lower boiling points and lower molecular weights. Accordingly, the third aspect of the present disclosure: there is provided the use of a hydrocracking catalyst according to the first aspect of the present disclosure in a hydrocracking reaction of a hydrocarbon feedstock.

The hydrocarbon feedstock may be various heavy mineral oils or synthetic oils or their mixed distillates, such as straight run gas oil (straight run gas oil), vacuum gas oil (vacuum gas oil), demetalized oils (demetalized oils), atmospheric residues (atmospheric residues), deasphalted vacuum residues (deasphalted vacuum residues), coker distillates (coker distillates), catalytic cracker distillates (cat cracker distillates), shale oils (shell oils), tar sand oils (tar sand oils), coal liquefied oils (coal liquids), etc. In particular, the catalyst provided by the disclosure is particularly suitable for hydrocracking heavy and poor distillate oil to produce a hydrocracking process of middle distillate oil with a distillation range of 149-371 ℃, especially 180-370 ℃.

In the application of the hydrocracking catalyst provided by the present disclosure in the hydrocracking reaction of the hydrocarbon feedstock, the hydrocracking catalyst is preferably presulfided with sulfur, hydrogen sulfide or a sulfur-containing feedstock at a temperature of 140-370 ℃ in the presence of hydrogen before the hydrocracking catalyst is used, and the presulfiding can be performed outside the reactor or in-situ sulfiding can be performed inside the reactor to convert the hydrocracking catalyst into a sulfide type.

The catalyst provided by the present disclosure can be used under conventional hydrocracking process conditions when used for distillate oil hydrocracking, for example, the hydrocracking reaction conditions are as follows: the reaction temperature is 200-650 ℃, preferably 300-510 ℃; the reaction pressure is 3-24 MPa, preferably 4-15 MPa; the liquid hourly space velocity is 0.1-50 h^-1Preferably 0.2 to 30 hours^-1(ii) a The volume ratio of the hydrogen to the oil is 100-5000.

The hydrocracking reaction apparatus may be any reaction apparatus sufficient to allow the hydrocarbon feedstock to react with the catalyst under hydrogenation reaction conditions, and may be, for example, a fixed bed reactor, a moving bed reactor, an ebullating bed reactor or a slurry bed reactor.

The present disclosure is further illustrated by the following examples, but is not limited thereto.

The pore volume and the specific surface area of the molecular sieve are measured by a static low-temperature adsorption capacity method (by adopting a national standard GB/T5816-1995 method) by adopting an ASAP 2400 model automatic adsorption instrument of American micromeritics instruments, and the specific method comprises the following steps: vacuumizing and degassing at 250 deg.C and 1.33Pa for 4 hr, contacting with nitrogen as adsorbate at-196 deg.C, and statically reaching adsorption balance; the nitrogen adsorption amount of the adsorbent is calculated according to the difference between the nitrogen gas inflow and the gas phase remained after adsorption, then the pore size distribution is calculated by using a BJH formula, and the specific surface area and the pore volume are calculated by using a BET formula.

The crystal structure of the molecular sieve is determined by an X-ray diffractometer D5005 of Siemens Germany, and the method is in an industry standard SH/T0339-92. The experimental conditions are as follows: cu target, Ka radiation, solid detector, tube voltage 40kV, tube current 40mA, step scanning, step width of 0.02 degrees, prefabrication time of 2s, and scanning range of 5-70 degrees. The diffraction angle position refers to the 2 theta angle value of the highest peak value of the diffraction peak.

The silicon content, aluminum content, phosphorus content and sodium content of the molecular sieve are measured by a 3271E type X-ray fluorescence spectrometer of Nippon science and Motor industry Co., Ltd, and the measuring method comprises the following steps: tabletting and forming a powder sample, carrying out rhodium target, detecting the spectral line intensity of each element by a scintillation counter and a proportional counter under the laser voltage of 50kV and the laser current of 50mA, and carrying out quantitative and semi-quantitative analysis on the element content by an external standard method.

Preparation examples 1 to 2 are provided to illustrate the preparation method of the phosphorus-containing high-silicon molecular sieve of the present disclosure.

Preparation of example 1

Taking RY molecular sieve (produced by China petrochemical catalyst Chang Ling division, the unit cell constant is 2.456nm, and the specific surface isArea 672m²Per g, pore volume of 0.357mL/g, Na₂O content 1.44 wt.%, P₂O₅Content 1.37 wt%) was put into a hydrothermal kettle, 100% steam was introduced, and the molecular sieve material after hydrothermal treatment was taken out after hydrothermal treatment at 560 ℃ and 0.8MPa for 3 hours.

Taking 50g (dry basis) of the obtained molecular sieve material subjected to the hydrothermal treatment, adding 500mL of deionized water, stirring and pulping to obtain first slurry, heating the first slurry to 80 ℃, adding 2.0mol/L of sulfuric acid solution, stopping adding acid when the pH value of the first slurry after acid addition is detected to be 2.8, then reacting at constant temperature for 4h, and filtering to obtain 40g of first solid product.

And adding 400mL of deionized water into the first solid product, stirring and pulping to obtain second slurry, and heating the second slurry to 80 ℃. Based on 1L of the second slurry, H⁺Adding 2mol/L sulfuric acid solution into the second slurry at a speed of 5mol/h, stopping adding acid when the pH value of the second slurry after acid addition is detected to be 1.4, then reacting at a constant temperature for 3h, filtering, collecting a second solid product, and drying at 180 ℃ for 3h to obtain the phosphorus-containing silicon-aluminum molecular sieve Y-1, wherein an XRD spectrogram of the phosphorus-containing silicon-aluminum molecular sieve Y-1 is shown in figure 1, and can be seen, wherein the diffraction angle position of a first strong peak is 6.1-6.8 degrees, the diffraction angle position of a second strong peak is 10.2-10.7 degrees, the diffraction angle position of a third strong peak is 15.8-16.5 degrees, the diffraction angle position of a fourth strong peak is 20.8-21.4 degrees, and the diffraction angle position of a fifth strong peak is 12.1-12.6 degrees. Other properties are shown in table 1.

Preparation of example 2

A high silicon molecular sieve was prepared as in preparative example 1, except that the second acid solution was added at a rate of 15 mol/h. The prepared molecular sieve Y-2 has an XRD spectrogram shown in figure 1, and can be seen, wherein the diffraction angle position of a first intensity peak is 6.1-6.8 degrees, the diffraction angle position of a second intensity peak is 10.2-10.7 degrees, the diffraction angle position of a third intensity peak is 15.8-16.5 degrees, the diffraction angle position of a fourth intensity peak is 20.8-21.4 degrees, and the diffraction angle position of a fifth intensity peak is 12.1-12.6 degrees. Other properties are shown in table 1.

Comparative examples 1-3 are prepared to illustrate the preparation of phosphorus-containing molecular sieves that are different from the present disclosure.

Preparation of comparative example 1

The molecular sieve of the preparation comparative example is a PSRY molecular sieve, the preparation method refers to CN1088407C example 1, the PSRY molecular sieve is named as DY-1, and an XRD spectrogram is shown in figure 1, wherein the diffraction angle position of a first intensity peak is 6.0-6.5 degrees, the diffraction angle position of a second intensity peak is 15.7-16.2 degrees, the diffraction angle position of a third intensity peak is 23.5-24.0 degrees, the diffraction angle position of a fourth intensity peak is 20.4-20.7 degrees, the diffraction angle position of a fifth intensity peak is 10.0-10.5 degrees, and the molecular sieve is different from the phosphorus-containing high-silicon molecular sieve of the preparation example 1. Other properties are shown in table 1.

Preparation of comparative example 2

Taking phosphorus-free HY molecular sieve (product name HY, crystal cell constant of 2.465nm, specific surface area of 580m, produced by Zhongshiedian catalyst Chang Ling division Co., Ltd.)²Per g, pore volume of 0.33mL/g, Na₂0.3 wt.% of O, Al₂O₃Content of 22 wt%) was put into a hydrothermal kettle, 100% steam was introduced, and the molecular sieve material after hydrothermal treatment was taken out after hydrothermal treatment at 500 ℃ and 2.0MPa for 1 hour.

Taking 80g (dry basis) of the obtained molecular sieve material subjected to hydrothermal treatment, adding 500mL of deionized water, stirring and pulping to obtain first slurry, heating the first slurry to 80 ℃, adding 1.0mol/L of sulfuric acid solution, stopping adding acid when the pH value of the first slurry after acid addition is detected to be 3.0, reacting at constant temperature for 4h, and performing

And adding 600mL of deionized water into the first solid product, stirring and pulping to obtain second slurry, and heating the second slurry to 80 ℃. Based on 1L of the second slurry, H⁺Adding 1.0mol/L phosphoric acid solution into the second slurry at a speed of 2mol/h, stopping adding acid when the pH value of the acid-added second slurry is detected, reacting at a constant temperature for 3h, filtering, collecting a second solid product, and drying at 180 ℃ for 3h to obtain the molecular sieve DY-2, wherein an XRD spectrogram of the molecular sieve DY-2 is shown in figure 1, and the diffraction angle position of a first strong peak is 5.5-6.2 degrees, the diffraction angle position of a second strong peak is 15.7-16.2 degrees, the diffraction angle position of a third strong peak is 10.0-10.5 degrees, the diffraction angle position of a fourth strong peak is 11.8-12.2 degrees, and the diffraction angle position of a fifth strong peak is 11.8-12.2 degreesThe diffraction angle of the diffraction grating is 20.3-20.7 degrees. Other properties are shown in table 1.

Preparation of comparative example 3

500g of RY molecular sieve (same as example 1) is taken and placed into a hydrothermal kettle, 100 percent of steam is introduced, and after hydrothermal treatment is carried out for 3 hours at 560 ℃ and 0.8MPa, the molecular sieve material after the hydrothermal treatment is taken out.

Taking 60g (dry basis) of the molecular sieve material subjected to the hydrothermal treatment, adding 500mL of deionized water, stirring and pulping to obtain first slurry, heating the first slurry to 90 ℃, adding 2.0mol/L of sulfuric acid solution, stopping adding acid when the pH value of the first slurry subjected to acid addition is detected to be 2.5, then reacting at a constant temperature for 4 hours, filtering to obtain 60g of a first solid product, and drying at 180 ℃ for 3 hours to obtain a molecular sieve DY-3, wherein an XRD (X-ray diffraction) spectrogram of the molecular sieve DY-3 is shown in figure 1, and as can be seen, the diffraction angle position of a first strong peak is 15.7-16.0 degrees, the diffraction angle position of a second strong peak is 6.0-6.5 degrees, the diffraction angle position of a third strong peak is 23.7-24.3 degrees, the diffraction angle position of a fourth strong peak is 11.5-12.0 degrees, and the diffraction angle position of a fifth strong peak is 10.0-10.5 degrees, which are different from the phosphorus-containing high-silicon molecular sieve prepared in example 1. Other properties are shown in table 1.

TABLE 1

Examples 1-6 are provided to illustrate methods of preparing hydrocracking catalysts provided by the present disclosure. Comparative examples 1-3 are presented to illustrate catalysts prepared using different molecular sieves than those of the present disclosure.

Example 1

65g Y-1 dry molecular sieve, 20g of pseudoboehmite (product of Zhongpetrochemical catalyst Changjingtie division, trade name PB90, dry basis 70 wt.%), 30g of LAY molecular sieve (product of Zhongpetrochemical catalyst Changjingtie catalyst factory, trade mark LAY, unit cell constant 2.458nm, specific surface area 682m²Per g, pore volume 0.39mL/g, dry basis 76 wt.%) with 80g of a weak acidSex silica-alumina (product name Sira-40, pore volume 0.88mL/g, specific surface 468m, Condea, Germany)²(g), the content of silicon dioxide is 40 percent by weight, the acidity value of the infrared B acid is 0.04mmol/g, the weight percent of a dry base is 76 percent), the mixture is extruded into a trilobal strip with the circumscribed circle diameter of 1.6 mm, the drying is carried out for 3h at 120 ℃, and the roasting is carried out for 3h at 600 ℃ to obtain the carrier CS-1. After cooling to room temperature, 100g of CS-1 carrier was immersed in 70mL of an aqueous solution containing 34.65 g of ammonium metatungstate (82 wt% tungsten oxide, product of the mitsui new photochemical reagent plant, 27.85 wt% nickel oxide) and 24.37 g of nickel nitrate, dried at 120 ℃ for 3 hours, and calcined at 480 ℃ for 4 hours to obtain the hydrocracking catalyst prepared in this example, the composition of which is shown in table 2.

Example 2

A catalyst was prepared as in example 1, except that Y-2 was used as the molecular sieve.

Example 3

138gY-1 dry molecular sieve, 12g of pseudoboehmite (product of Zhongpetrochemical catalyst Changjingtie division, trade name PB90, dry basis 70 wt.%), 11g of LAY molecular sieve (product of Zhongpetrochemical catalyst Changjingtie catalyst factory, trade mark LAY, unit cell constant 2.458nm, specific surface area 682m²Pore volume of 0.39mL/g, dry basis 76 wt%) and 11g of weakly acidic silica-alumina (product name Sira-40, pore volume of 0.88mL/g, specific surface 468m²(g), the content of silicon dioxide is 40 percent by weight, the acidity value of the infrared B acid is 0.04mmol/g, the weight percent of a dry base is 76 percent), the mixture is extruded into a trilobal strip with the circumscribed circle diameter of 1.6 mm, the drying is carried out for 3h at 120 ℃, and the roasting is carried out for 3h at 600 ℃ to obtain the carrier CS-3. After cooling to room temperature, 100g of CS-3 carrier was immersed in 45mL of an aqueous solution containing 13.86g of ammonium metatungstate (82 wt% tungsten oxide, product of the beijing new photochemical agent factory) and 8.16g of nickel nitrate (27.85 wt% nickel oxide, product of the beijing new photochemical agent factory), dried at 120 ℃ for 3 hours, and calcined at 480 ℃ for 4 hours to obtain the hydrocracking catalyst prepared in this example, the composition of which is shown in table 2.

Example 4

24.3g Y-1 dry basis molecular sieve, 11.6g pseudo-boehmite (medium petrochemical catalyst length)Trade name PB90 from Ringzhao corporation, dry basis 70 wt%), 160g LAY molecular sieve (product of Changling catalyst plant from Zhongpetrochemical catalyst division, trade name LAY, cell constant 2.458nm, and specific surface area 682m²Pore volume of 0.39mL/g, dry basis 76 wt%) and 10.7g of weakly acidic silica-alumina (product name Sira-40, pore volume of 0.88mL/g, specific surface 468m²(g), the content of silicon dioxide is 40 wt%, the acidity value of the infrared B acid is 0.04mmol/g, and the weight of a dry base is 76%), the mixture is extruded into a trilobal strip with the diameter of an outer circle of 1.6 mm, the trilobal strip is dried for 3h at the temperature of 120 ℃, and is roasted for 3h at the temperature of 600 ℃, and the carrier CS-4 is obtained. After cooling to room temperature, 100g of CS-5 carrier was immersed in 74g of 70mL of aqueous solution containing ammonium metatungstate (82 wt% tungsten oxide, product of beijing new photochemical reagent plant) and 43g of nickel nitrate (27.85 wt% nickel oxide, product of beijing new photochemical reagent plant), dried at 120 ℃ for 3 hours, and calcined at 480 ℃ for 4 hours to obtain the hydrocracking catalyst prepared in this example, the composition of which is shown in table 2.

Example 5

8g Y-1 dry-base molecular sieve, 162g of pseudoboehmite (product of Zhongpetrochemical catalyst ChangLing division, trade name PB90, dry base 70 wt.%), 10g of USY-5 molecular sieve (product of Zhongpetrochemical catalyst ChangLing catalyst factory, trade mark USY, unit cell constant 2.437nm, specific surface area 623m²0.39mL/g in pore volume and 75 wt% in dry basis) and 42.6g of weakly acidic silica-alumina (product name: Sira-40, pore volume 0.88mL/g, specific surface 468m, manufactured by Condea, Germany)²(g), the content of silicon dioxide is 40 percent by weight, the acidity value of the infrared B acid is 0.04mmol/g, the weight percent of a dry base is 76 percent), the mixture is extruded into a trilobal strip with the circumscribed circle diameter of 1.6 mm, the drying is carried out for 3h at 120 ℃, and the roasting is carried out for 3h at the temperature of 600 ℃, thus obtaining the carrier CS-5. After cooling to room temperature, 100g of CS-5 carrier was immersed in 69g of 80mL of aqueous solution containing ammonium metatungstate (82 wt% tungsten oxide, product of the beijing new photochemical reagent plant), 17g of nickel nitrate (27.85 wt% nickel oxide, product of the beijing new photochemical reagent plant), dried at 120 ℃ for 3 hours, and calcined at 480 ℃ for 4 hours, to obtain the hydrocracking catalyst prepared in this example, the composition of which is shown in table 2.

Example 6

65g Y-1 dry-base molecular sieve, 92.6g pseudoboehmite (product name PB90, dry base 70 wt.%), 20.3g USY-5 molecular sieve (product name USY, unit cell constant 2.437nm, specific surface area 623 m)²Pore volume of 0.39mL/g, dry basis 75 wt%) and 21.3g of weakly acidic silica-alumina (product name Sira-40, pore volume of 0.88mL/g, specific surface 468m²(g), the content of silicon dioxide is 40 wt%, the acidity value of the infrared B acid is 0.04mmol/g, and the weight of a dry base is 76%), the mixture is extruded into a trilobal strip with the diameter of an outer circle of 1.6 mm, the trilobal strip is dried for 3h at the temperature of 120 ℃, and is roasted for 3h at the temperature of 600 ℃, and the carrier CS-6 is obtained. After cooling to room temperature, 100g of the CS-6 carrier was immersed in 95mL of an aqueous solution containing 29g of molybdenum trioxide (produced by Taoyangjin Tokyo molybdenum Co., Ltd.), 67g of cobalt nitrate (produced by Beijing New photochemical reagent factory, cobalt oxide content 27.85 wt%), and 11.8g of phosphoric acid (produced by Beijing chemical reagent factory, purity 85%), dried at 120 ℃ for 3 hours, and calcined at 480 ℃ for 4 hours to obtain the hydrocracking catalyst prepared in the present example, the composition of which is shown in Table 2.

Comparative examples 1 to 3

A catalyst was prepared as in example 1, except that the molecular sieves used were DY-1, DY-2 and DY-3, respectively.

TABLE 2

Test examples

The test examples were used to test the catalytic activity of the catalysts of examples 1 to 3 and comparative examples 1 to 3 for hydrocracking reactions.

The hydrocracking activity of the catalyst is evaluated on a small fixed bed hydrocracking device by taking n-octane containing 5.61% of tetrahydronaphthalene and 0.29% of pyridine as a raw material, the catalyst loading is 0.2 ml, the reaction temperature is 320 ℃, the reaction pressure is 4.0MPa, the hydrogen-oil volume ratio is 3600, and the liquid hourly space velocity is 30h^-1The catalyst activity was expressed as the percentage of n-decane converted in the product composition after 4h of stabilization of the reaction feed and the results of the evaluation are shown in Table 3.

TABLE 3

Catalyst and process for preparing same	Conversion (%)
		Example 1	53.2
Example 2	52.7
		Example 3	76.3
Comparative example 1	42.3
		Comparative example 2	46.4
Comparative example 3	45.3

As can be seen from table 3, under the same comparative conditions, the catalyst containing the phosphorus-containing aluminosilicate molecular sieve provided by the present disclosure has the catalytic activity improved by more than about 5% under the high nitrogen condition, compared to the molecular sieve prepared by the prior method.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A hydrocracking catalyst, characterized in that the catalyst comprises 45 to 90 wt% of a carrier, 1 to 40 wt% of a first metal component calculated as a metal oxide, and 1 to 15 wt% of a second metal component calculated as a metal oxide, based on the dry weight of the catalyst;

the carrier comprises a phosphorus-containing high-silicon molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, wherein the weight ratio of the phosphorus-containing high-silicon molecular sieve to the Y-type molecular sieve to the weakly acidic silicon aluminum to the aluminum oxide is 1: (0.03-20): (0.03-20): (0.05-15); the first metal component is a metal component selected from a group VIB metal; the second metal component is a metal component selected from group VIII metals;

2. The catalyst according to claim 1, wherein the phosphorus-containing high-silicon molecular sieve has an XRD spectrum in which the diffraction angle position of the first intensity peak is 6.1-6.8 °, the diffraction angle position of the second intensity peak is 10.2-10.7 °, and the diffraction angle position of the third intensity peak is 15.8-16.5 °.

3. The catalyst of claim 1 or 2, wherein the phosphorus-containing high silicon molecular sieve has an XRD spectrum with I₁/I_{23.5～24.5°}Is 3.0 to 11.0, I₂/I_{23.5～24.5°}Is 2.9 to 7.0, I₃/I_{23.5～24.5°}1.0 to 4.0, wherein I₁Is the peak height of the first strong peak, I₂Is the peak height of the second strong peak, I₃Is the peak height of the third strong peak, I_{23.5～24.5°}The peak height of the diffraction angle peak with the diffraction angle position of 23.5-24.5 degrees.

4. The catalyst according to claim 1 or 2, wherein the phosphorus-containing high-silicon molecular sieve has an XRD spectrum in which the diffraction angle position of the fourth intensity peak is 20.4-21.6 ° and the diffraction angle position of the fifth intensity peak is 11.8-12.8 °.

5. The catalyst according to claim 4, wherein the phosphorus-containing high-silicon molecular sieve has an XRD spectrum with a diffraction angle position of a fourth intensity peak in the range of 20.8-21.4 ° and a diffraction angle position of a fifth intensity peak in the range of 12.1-12.6 °; and/or the presence of a gas in the gas,

I₄/I_{23.5～24.5°}1.0 to 4.0, I₅/I_{23.5～24.5°}1.0 to 2.0, wherein I₄Is the peak height of the fourth strong peak, I₅Is the peak height of the fifth strong peak, I_{23.5～24.5°}The peak height of the diffraction angle peak with the diffraction angle position of 23.5-24.5 degrees.

6. The catalyst of claim 1 or 2, wherein the phosphorous containing high silicon molecular sieve is prepared by a method comprising:

a. carrying out hydro-thermal treatment on a phosphorus-containing molecular sieve raw material for 0.5-10 h at the temperature of 350-700 ℃ and the pressure of 0.1-2 MPa in the presence of water vapor to obtain a hydro-thermally treated molecular sieve material; calculated by oxide and based on the dry weight of the phosphorus-containing molecular sieve raw material, the phosphorus content of the phosphorus-containing molecular sieve raw material is 0.1-15 wt%, and the sodium content is 0.5-4.5 wt%;

7. The catalyst of claim 6, wherein in the step a, the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, the unit cell constant of the phosphorus-containing Y-type molecular sieve is 2.425-2.47 nm, and the specific surface area is 250-750 m²The pore volume is 0.2 to 0.95 mL/g.

8. The catalyst of claim 6, wherein in the step b, the ratio of the weight of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is (14-5): 1.

9. the catalyst of claim 6, wherein in step c, the ratio of the weight of water in the second slurry to the dry weight of the phosphorus-containing molecular sieve feedstock is (0.5-20): 1.

10. the catalyst of claim 6, wherein in step c, the second acid solution is added by: based on 1L of the second slurry, taking H as reference⁺The second acid solution is added to the second slurry at a rate of 0.05 to 10 moles/hour.

11. The catalyst according to claim 6, wherein in the step b, the acid concentration of the first acid solution is 0.01-15.0 mol/L, and the acid in the first acid solution is at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid; and/or the presence of a gas in the gas,

12. The catalyst of claim 6, wherein the step of preparing the phosphorus-containing high silicon molecular sieve further comprises: collecting the second product, then washing with water and drying to obtain a high-silicon phosphorus-containing molecular sieve; and/or, the drying conditions are as follows: the temperature is 50-350 ℃, and preferably 70-200 ℃; the time is 1-24 h, preferably 2-6 h.

13. The catalyst according to claim 1, wherein the weakly acidic silicon aluminum has an infrared B acidity value of 0.01 to 0.1mmol/g, a silicon content of 20 to 60 wt% in terms of silicon dioxide, and a pore volume of 0.5 to 1.0 mL/g;

14. A process for preparing a hydrocracking catalyst according to any one of claims 1 to 13, characterized in that the process comprises: and contacting an impregnation liquid containing a first metal precursor and a second metal precursor with the carrier for impregnation.

15. The method of claim 14, wherein the method further comprises: mixing a high-silicon phosphorus-containing molecular sieve, a Y-type molecular sieve, weakly acidic silicon aluminum and aluminum oxide, and then molding, drying and roasting to obtain the carrier.

16. The method of claim 14, wherein the first metal precursor is an inorganic acid, an inorganic salt, or an organic compound of a first metal; the inorganic salt is nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the first metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl; and/or the presence of a gas in the gas,

the second metal precursor is inorganic acid of a second metal, inorganic salt of the second metal or a second metal organic compound; the inorganic salt is nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate or chloride; the organic substituent in the second metal organic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether and alkyl.

17. The method of claim 14, further comprising the steps of drying and calcining the impregnated material; and/or the presence of a gas in the gas,

18. Use of a hydrocracking catalyst according to any one of claims 1 to 13 in a hydrocracking reaction of a hydrocarbon feedstock.

19. The use according to claim 18, wherein the hydrocarbon feedstock is a straight run gas oil, a vacuum gas oil, a demetallized oil, an atmospheric residue, a deasphalted vacuum residue, a coker distillate, a catalytically cracked distillate, a shale oil, a tar sand oil, or a coal liquefaction oil, or a combination of two or three thereof; and/or the presence of a gas in the gas,