Phosphorus-containing high-silica molecular sieve, its preparation and application thereof

Abstract

A phosphorus-containing high-silicon molecular sieve, a preparation method therefor and an application thereof; in terms of oxides and by using the dry basic weight of the molecular sieve as a baseline, the molecular sieve comprises about 86.5-99.8% by weight of silicon, about 0.1-13.5% by weight of aluminum and about 0.01-6% by weight of phosphorus; the XRD spectrum of the molecular sieve has at least three diffraction peaks, the diffraction angle position of a first strong peak being at about 5.9-6.9°, the diffraction angle position of a second strong peak being at about 10.0-11.0°, and the diffraction angle position of a third strong peak being at about 15.6-16.7°. When the phosphorus-containing high-silicon molecular sieve is used to prepare a hydrocracking catalyst, the molecular sieve exhibits improved hydrocracking activity in the presence of a nitrogen-containing substance.

Description

Phosphorus-containing high-silica molecular sieves, their preparation methods and applications

[0001] Cross-references to related applications

[0002] This application claims priority to the applicant's patent application No. 201811259943.0, filed with the Chinese Patent Office on October 26, 2018, entitled "Phosphorus-containing high-silica molecular sieve and its preparation method and application", and the applicant's patent application No. 201811261400.2, filed with the Chinese Patent Office on October 26, 2018, entitled "Hydrocracking catalyst containing high-silica molecular sieve and its preparation method and application", the contents of which are hereby incorporated herein by reference in their entirety. Technical Field

[0003] This application relates to the technical fields of molecular sieves and hydrocracking, specifically to a phosphorus-containing high-silica molecular sieve, a hydrocracking catalyst containing the same, and their preparation methods and applications. Background Technology

[0004] Industrial hydrocracking feedstocks include heavy, low-grade fractions such as VGO, containing large amounts of polycyclic aromatic hydrocarbons (PAHs) and cycloalkanes, as well as significant amounts of nitrogen-containing compounds. The nitrogen content of conventional hydrocracking feedstocks is typically between 0.1% and 0.2% by mass. However, secondary refining processes such as coking and solvent deasphalting often generate large amounts of nitrogen-containing compounds, resulting in feedstocks with nitrogen contents often exceeding 0.3%, and sometimes even reaching 0.6%. This makes it difficult to remove nitrogen to the 10-100 ppm level that conventional molecular sieve-type hydrocracking catalysts can withstand after treatment with conventional refining catalysts. Typically, weakly acidic amorphous silica-alumina or silicon-containing alumina are used as the main acidic component in high-nitrogen-content hydrocracking catalysts.

[0005] Existing techniques typically employ salt solutions of silicon oxide and aluminum oxide at low pH values ​​to synthesize weakly acidic silicon-aluminum. Alternatively, alumina can be grafted onto a silicon oxide precursor or silicon oxide can be grafted onto an alumina precursor, and further reactions can be used to form silicon-aluminum tetrahedra, thereby generating acidity in the sample.

[0006] Chinese patent ZL97121663.0 discloses a hydrocracking catalyst particularly suitable for producing middle distillate oils, containing amorphous silica-alumina components, a porous alumina binder, at least one Group VIB element and at least one Group VIII element. The amorphous silica-alumina content is 30-60% by weight, the total content of hydrocracking metal oxides is 20-35% by weight, and the balance is a porous alumina binder. The catalyst is characterized by a specific surface area of ​​150-300 μm. 2 / g, pore volume is 0.25-0.50mg / g, pore size distribution of 4-15nm is 60-90%, and infrared acidity is 0.30-0.50mmol / g.

[0007] Although these methods can produce materials with a certain degree of acidity, in order to maintain the stability of the matrix structure during the synthesis process, the resulting products contain a large amount of non-framework six-coordinate aluminum, which makes the materials only short-range ordered and difficult to achieve long-range order.

[0008] Summary of the Invention

[0009] The purpose of this application is to provide a phosphorus-containing high-silica molecular sieve, a hydrocracking catalyst containing the same, a method for preparing the same, and applications thereof. When used to prepare a hydrocracking catalyst, the molecular sieve exhibits improved hydrocracking activity in the presence of nitrogen-containing substances.

[0010] To achieve the above objectives, this application provides a phosphorus-containing high-silicon molecular sieve, which, based on oxides and the dry weight of the molecular sieve, contains approximately 86.5-99.8% by weight of silicon, approximately 0.1-13.5% by weight of aluminum, and approximately 0.01-6% by weight of phosphorus.

[0011] The XRD pattern of the molecular sieve has at least three diffraction peaks, with the first strong peak located at a diffraction angle of approximately 5.9-6.9°, the second strong peak at approximately 10.0-11.0°, and the third strong peak at approximately 15.6-16.7°.

[0012] Preferably, the molecular sieve has a pore volume of about 0.20-0.50 mL / g and a specific surface area of ​​about 250-670 m². 2 / g.

[0013] On the other hand, this application provides a method for preparing phosphorus-containing high-silica molecular sieves, the method comprising the following steps:

[0014] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-8.0MPa, and in the presence of water vapor for about 0.5-10 hours to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-15% by weight, a sodium content of about 0.5-4.5% by weight, a silicon content of about 70-85% by weight, and an aluminum content of about 16.0-21.0% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0015] b) Add water to the hydrothermally treated molecular sieve material obtained in step a) to prepare a first slurry. Heat the first slurry to about 40-95°C, then maintain the temperature and add a first acid solution to the first slurry. The amount of the first acid solution added is such that the pH value of the resulting acid-added first slurry is about 2.3-4.0. Then react at a constant temperature for about 0.5-20 hours and collect the first solid product.

[0016] c) Add water to the first solid product obtained in step b) to make a second slurry, heat the second slurry to about 40-95°C, then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acid-added second slurry is about 0.8-2.0. Then react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0017] In another aspect, this application provides the application of the phosphorus-containing high-silicon molecular sieve according to this application in the hydrocracking reaction of hydrocarbon feedstocks, including contacting the hydrocarbon feedstock with a hydrocracking catalyst comprising the phosphorus-containing high-silicon molecular sieve.

[0018] In another aspect, this application provides a hydrocracking catalyst, which, based on the dry weight of the catalyst, comprises about 45-90% by weight of support, about 1-40% by weight of a first metal component based on metal oxides, and about 1-15% by weight of a second metal component based on metal oxides.

[0019] The carrier comprises a phosphorus-containing high-silica molecular sieve and a heat-resistant inorganic oxide, wherein the weight ratio of the phosphorus-containing high-silica molecular sieve to the heat-resistant inorganic oxide is approximately 0.03:1 to approximately 20:1.

[0020] Wherein, the first metal component contains a Group VIB metal, the second metal component contains a Group VIII metal, and the phosphorus-containing high-silicon molecular sieve is a phosphorus-containing high-silicon molecular sieve according to this application.

[0021] Furthermore, this application provides a method for preparing a hydrocracking catalyst, comprising the following steps:

[0022] A carrier is prepared by mixing a phosphorus-containing high-silica molecular sieve according to this application with a heat-resistant inorganic oxide; and

[0023] The carrier is impregnated by contacting an impregnation solution containing a first metal precursor and a second metal precursor.

[0024] In another aspect, this application provides the use of the hydrocracking catalyst according to this application in the hydrocracking reaction of hydrocarbon feedstocks, including contacting the hydrocarbon feedstock with the hydrocracking catalyst.

[0025] This application utilizes phosphorus-containing molecular sieve raw materials under specific conditions for hydrothermal treatment and a two-step acid washing process to prepare a phosphorus-containing high-silica molecular sieve with novel structural features. The phosphorus-containing high-silica molecular sieve of this application exhibits improved hydrocracking activity in the presence of nitrogen-containing substances when used to prepare hydrocracking catalysts. Correspondingly, the hydrocracking catalyst prepared using this phosphorus-containing high-silica molecular sieve also possesses improved hydrocracking activity.

[0026] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0027] The accompanying drawings are provided to further illustrate the present application and form part of the specification. They are used together with the following detailed description to explain the present application, but do not constitute a limitation thereof. In the drawings:

[0028] Figure 1 shows the XRD patterns of the molecular sieves prepared in Preparation Examples 1-2 and Comparative Examples 1-3. Detailed Implementation

[0029] The specific embodiments of this application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this application.

[0030] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0031] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0032] In this application, the dry basis weight of a substance refers to the weight of the solid product obtained by calcining the substance at 600°C for 3 hours. Except as expressly stated, any matters or issues not mentioned herein are directly applicable to those known in the art without any modification. Furthermore, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the resulting technical solutions or concepts are considered part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination clearly unreasonable.

[0033] All patent and non-patent literature mentioned in this article, including but not limited to textbooks and journal articles, are incorporated in full by way of citation.

[0034] In a first aspect, this application provides a phosphorus-containing high-silica molecular sieve, which, based on oxides and the dry weight of the molecular sieve, comprises about 86.5-99.8% by weight, preferably about 90-99.8% by weight, of silicon, about 0.1-13.5% by weight, preferably about 0.1-9.0% by weight, of aluminum, and about 0.01-6% by weight, preferably about 0.01-2.5% by weight of phosphorus. Optionally, the molecular sieve may also contain a small amount of sodium, which, based on oxides and the dry weight of the molecular sieve, may be about 0.01-1.0% by weight, for example, about 0.01-0.6% by weight.

[0035] In a preferred embodiment, the phosphorus-containing high-silica molecular sieve comprises about 90-99.8% by weight of silicon, about 0.1-9.0% by weight of aluminum, and about 0.01-2.5% by weight of phosphorus, based on oxides and the dry weight of the molecular sieve. Optionally, the molecular sieve may also contain about 0.01-1.0% by weight, for example about 0.01-0.6% by weight of sodium, based on oxides and the dry weight of the molecular sieve.

[0036] In a further preferred embodiment, the phosphorus-containing high-silica molecular sieve, based on oxides and on a dry basis, comprises about 95.0-99.0% by weight of silicon, about 0.5-5.0% by weight of aluminum, and about 0.1-1.0% by weight of phosphorus. Optionally, based on oxides and on a dry basis, the molecular sieve may also contain about 0.01-0.6% by weight of sodium.

[0037] In a preferred embodiment, the pore volume of the molecular sieve can be about 0.20-0.50 mL / g, preferably about 0.30-0.45 mL / g, for example about 0.33-0.42 mL / g; and / or, the specific surface area of ​​the molecular sieve can be about 250-670 m². 2 / g, preferably about 260-600m 2 / g, for example, about 400-600m 2 / g.

[0038] In a further preferred embodiment, the molecular sieve has a pore volume of approximately 0.20-0.50 mL / g and a specific surface area of ​​approximately 260-600 m². 2 / g.

[0039] According to this application, the molecular sieve has structural features different from conventional silicon-aluminum materials. Specifically, the XRD pattern of the molecular sieve has at least three diffraction peaks, wherein the diffraction angle of the first strong peak is located at approximately 5.9-6.9°, preferably at approximately 6.1-6.8°; the diffraction angle of the second strong peak is located at approximately 10.0-11.0°, preferably at approximately 10.2-10.7°; and the diffraction angle of the third strong peak is located at approximately 15.6-16.7°, preferably at approximately 15.8-16.5°, where the diffraction angle position refers to the 2θ angle value of the highest peak value in the XRD pattern.

[0040] In this application, the ordinal numbers “first,” “second,” and “third” in the descriptions of the first, second, and third strongest peaks represent the relative intensity order of the diffraction peaks determined by their peak height. The first strongest peak represents the diffraction peak with the highest peak height in the XRD pattern, the second strongest peak represents the diffraction peak with the second highest peak height in the XRD pattern, the third strongest peak represents the diffraction peak with the third highest peak height in the XRD pattern, and so on.

[0041] As is well known to those skilled in the art, when using X-ray diffraction (XRD) to analyze the structure of a material, the D-value (interplanar spacing) can usually be calculated from the wavelength and diffraction angle, and the phase can be preliminarily identified based on the characteristics of the three strongest diffraction peaks (i.e., the first, second, and third strongest peaks in this application). The concept of the aforementioned three strongest peaks can also be found in the reference "Research Methods for Heterogeneous Catalysts," edited by Yin Yuangen, Beijing: Chemical Industry Press, 1988, pp. 140-170.

[0042] In a preferred embodiment, in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5 It can be approximately 3.0-11.0, for example, approximately 4.0-10.5 or approximately 4.6-10.1; I2 / I 23.5-24.5 It can be approximately 2.5–8.0, for example, approximately 2.9–7.0 or approximately 3.0–6.4; I3 / I 23.5-24.5 It can be approximately 1.0-4.5, for example, approximately 1.5-4.0 or approximately 2.1-3.8; where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, I3 is the peak height of the third strong peak, and I... 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0043] In a further preferred embodiment, in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5 It can be approximately 3.0-11.0, I2 / I 23.5-24.5 It can be approximately 2.9-7.0, I3 / I 23.5-24.5It can be approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0044] In some further preferred embodiments, in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5 It can be approximately 4.0-10.5, I² / I. 23.5-24.5 It can be approximately 2.9-7.0, I3 / I 23.5-24.5 It can be approximately 1.5-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0045] In some further preferred embodiments, the XRD pattern of the molecular sieve has at least five diffraction peaks, wherein the diffraction angle position of the fourth strongest peak can be about 20.4-21.6°, preferably about 20.8-21.4°, and the diffraction angle position of the fifth strongest peak can be about 11.8-12.8°, preferably about 12.1-12.6°.

[0046] In a further preferred embodiment, I4 / I 23.5-24.5 It can be approximately 1.0-4.0, for example, approximately 1.1-3.0 or approximately 1.2-2.3, I5 / I 23.5-24.5 It can be approximately 1.0-2.0, for example, approximately 1.0-1.6 or approximately 1.0-1.2, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5 The value represents the peak height of the peak with a diffraction angle of approximately 23.5-24.5°. The concepts of the fourth and fifth strongest peaks can be understood based on the description of the three strongest peaks mentioned above, and will not be repeated here.

[0047] In some further preferred embodiments, I4 / I 23.5-24.5 It can be approximately 1.1-3.0, I5 / I. 23.5-24.5 It can be approximately 1.0-1.6, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0048] The phosphorus-containing high-silica molecular sieve of this application exhibits improved hydrocracking activity in the presence of nitrogen-containing substances when used to prepare hydrocracking catalysts.

[0049] In a second aspect, this application provides a method for preparing phosphorus-containing high-silica molecular sieves, the method comprising the following steps:

[0050] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-8.0MPa, and in the presence of water vapor for about 0.5-10 hours to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-15% by weight, a sodium content of about 0.5-4.5% by weight, a silicon content of about 70-85% by weight, and an aluminum content of about 16.0-21.0% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0051] b) The hydrothermally treated molecular sieve material obtained in step a) is mixed with water to prepare a first slurry. The first slurry is heated to approximately 40-95°C, and then, while maintaining the temperature, a first acid solution is added to the first slurry. The amount of the first acid solution added is such that the pH value of the resulting acid-added first slurry is approximately 2.3-4.0, preferably approximately 2.5-4.0. The mixture is then reacted at a constant temperature for approximately 0.5-20 hours, and the first solid product is collected.

[0052] c) Add water to the first solid product obtained in step b) to make a second slurry, heat the second slurry to about 40-95°C, then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acidified second slurry is about 0.8-2.0, preferably about 1.0-2.0. Then react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0053] In a preferred embodiment, the method for preparing phosphorus-containing high-silica molecular sieves includes the following steps:

[0054] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 400-650°C, for example, about 560°C, a pressure of about 0.5-5 MPa, for example, about 0.8 MPa, and in the presence of water vapor for about 1-7 hours, for example, about 3 hours, to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-6 wt%, for example, about 1.37 wt%, a sodium content of about 0.5-3.0 wt%, for example, about 1.44 wt%, a silicon content of about 70-80 wt%, for example, about 76.7 wt%, and an aluminum content of about 18.0-21.0 wt%, for example, about 20.5 wt%;

[0055] b) The hydrothermally treated molecular sieve material obtained in step a) is mixed with water to form a first slurry. The first slurry is heated to approximately 50-85°C, for example, approximately 80°C. The temperature is then maintained, and a first acid solution is added to the first slurry. The amount of the first acid solution added is such that the pH of the resulting acid-added first slurry is approximately 2.5-3.5, for example, approximately 2.8. The reaction is then carried out at a constant temperature for approximately 1-10 hours, for example, approximately 4 hours. The first solid product is then collected.

[0056] c) Add water to the first solid product obtained in step b) to make a second slurry, heat the second slurry to about 50-85°C, for example about 80°C, then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acidified second slurry is preferably about 1.0-1.8, for example about 1.4, and then react at a constant temperature for about 1-10 hours, for example about 3 hours, and collect the second solid product.

[0057] According to this application, in some embodiments, in step a), the phosphorus-containing molecular sieve raw material refers to a phosphorus-containing molecular sieve. This application uses a phosphorus-containing molecular sieve raw material, where the phosphorus and aluminum species outside the molecular sieve framework can improve the framework stability of the molecular sieve, thereby further improving the performance of the molecular sieve. The phosphorus-containing molecular sieve raw material may have an octahedral zeolite molecular sieve structure, preferably a phosphorus-containing Y-type molecular sieve, with a cell constant of approximately 2.425-2.47 nm, for example, approximately 2.456 nm, and a specific surface area of ​​approximately 250-750 m². 2 / g, for example, about 672m 2 / g, with a pore volume of approximately 0.2-0.95 mL / g, for example, approximately 0.357 mL / g.

[0058] Furthermore, the specific selection of the Y-type molecular sieve can vary within a wide range, as long as the phosphorus-containing molecular sieve raw material meets the above conditions. For example, the Y-type molecular sieve can be selected from NaY, HNaY (hydrogen Y-type molecular sieve), REY (rare earth Y-type molecular sieve), USY (ultra-stable Y-type molecular sieve), etc. The cation sites of the phosphorus-containing Y-type molecular sieve can be occupied by one or more of sodium ions, ammonium ions, and hydrogen ions; or, before or after the introduction of phosphorus into the molecular sieve, all or part of the sodium ions, ammonium ions, and hydrogen ions can be replaced by other ions through conventional ion exchange. The phosphorus-containing molecular sieve raw material can be a commercially available product or can be prepared using any existing technology. For example, it can be prepared using the method for preparing USY disclosed in Chinese Patent ZL00123139.1, or the method for preparing PUSY disclosed in Chinese Patent ZL200410071122.6, etc., which will not be elaborated further in this application.

[0059] According to this application, the meaning of adding water and pulping in steps b) and c) is well known to those skilled in the art. In some preferred embodiments, in step b), the weight ratio of water to the dry weight of the phosphorus-containing molecular sieve raw material in the first slurry obtained after pulping can be about 14:1 to about 5:1, for example, about 10:1; and / or in step c), the weight ratio of water to the dry weight of the phosphorus-containing molecular sieve raw material in the second slurry can be about 0.5:1 to about 20:1, for example, about 10:1.

[0060] According to this application, in some preferred embodiments, in step b), the first slurry is heated to approximately 50-85°C, for example, approximately 80°C, and then the temperature is maintained while a first acid solution is continuously added to the first slurry until the pH value of the first slurry after acid addition reaches the desired value. Depending on the properties of the phosphorus-containing molecular sieve raw material and the changes in the hydrothermal treatment conditions described in step a), the amount of the first acid solution added can vary considerably. Those skilled in the art will understand that any amount of the first acid solution added is desirable as long as it causes the pH value of the first slurry after acid addition to meet the aforementioned suitable range. The rate of addition of the first acid solution is not particularly limited and can vary within a wide range.

[0061] According to this application, in some preferred embodiments, in step b), the addition of the first acid solution can be performed multiple times (e.g., 1-5 times). After each addition of acid, the reaction can be carried out at a constant temperature for a period of time before the next addition of acid is performed, until the pH value of the first slurry after acid addition reaches the required range. The acid concentration of the first acid solution can be about 0.1-15.0 mol / L, preferably about 0.1-5.0 mol / L, for example about 2.0 mol / L, and the pH value can be about 0.01-3. The acid in the first acid solution can be a conventional inorganic acid and / or organic acid, 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, preferably selected from sulfuric acid and nitric acid.

[0062] According to this application, in some preferred embodiments, in step c), the second slurry is heated to approximately 50-85°C, for example, approximately 80°C, and then the temperature is maintained while a second acid solution is continuously added to the second slurry until the pH value of the second slurry after acid addition reaches the required value. The second acid solution can be added in the following manner: based on 1L of the second slurry, using H... + The second acid solution is added to the second slurry at a rate of about 0.05-15 mol / h, preferably about 0.05-10 mol / h, more preferably about 2-8 mol / h, for example about 5 mol / h. According to this application, using a slower acid addition rate in step c) allows for a gentler dealuminization process, which is beneficial for improving the performance of the molecular sieve.

[0063] According to this application, in some preferred embodiments, in step c), the addition of the second acid solution can be performed multiple times (e.g., 1-5 times). After each addition of acid, the reaction can be carried out at a constant temperature for a period of time before the next addition of acid is performed, until the pH value of the second slurry after acid addition reaches the required range. The acid concentration of the second acid solution can be about 0.1-15.0 mol / L, preferably about 0.1-5.0 mol / L, for example about 2.0 mol / L, and the pH value can be about 0.01-3. The acid in the second acid solution can be a conventional inorganic acid and / or organic acid, 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, preferably selected from sulfuric acid and nitric acid. The type and concentration of the second acid solution can be the same as or different from those of the first acid solution, but preferably the same acid solution.

[0064] According to this application, in some preferred embodiments, the method may further include: collecting the second solid product, then washing it with water and drying it to obtain the phosphorus-containing high-silica molecular sieve. The washing and drying are conventional steps in the preparation of molecular sieves, and this application does not impose any particular limitations. For example, the drying can be carried out using methods such as an oven, conveyor belt, or converter heating. The drying conditions can be: a temperature of approximately 50-350°C, preferably approximately 70-200°C, for example, approximately 180°C; and a time of approximately 1-24 hours, preferably approximately 2-6 hours, for example, approximately 3 hours.

[0065] This application uses phosphorus-containing molecular sieve raw materials for specific hydrothermal treatment and two-step acid washing to obtain phosphorus-containing high-silicon molecular sieves with novel structural features.

[0066] The phosphorus-containing high-silica molecular sieve provided in this application can be used as a catalyst for various acid catalysis reactions such as catalytic cracking, hydroisomerization, alkylation, and hydrocracking. It is particularly suitable for hydrocracking of hydrocarbon feedstocks to produce hydrocarbon fractions with lower boiling points and lower molecular weights.

[0067] Therefore, in a third aspect, this application provides the application of the phosphorus-containing high-silicon molecular sieve according to this application in the hydrocracking reaction of hydrocarbon feedstocks, including contacting the hydrocarbon feedstock with a hydrocracking catalyst comprising the phosphorus-containing high-silicon molecular sieve.

[0068] According to this application, the hydrocarbon feedstock can be various heavy mineral oils or synthetic oils, or their mixed distillate oils, such as straight run gas oil, vacuum gas oil, demetallized oils, atmospheric residue, deasphalted vacuum residue, coker distillates, catalytic cracking distillates, shale oil, tar sand oil, coal liquefaction oil, etc.

[0069] In particular, the phosphorus-containing high-silica molecular sieve catalyst based on this application is especially suitable for the hydrocracking of heavy and low-quality distillate oils to produce middle distillate oils with a distillation range of about 149-371°C, and especially about 180-370°C.

[0070] According to this application, the hydrocracking reaction can be one or more of the hydrocracking reactions carried out in conventional equipment such as fixed bed, fluidized bed, slurry bed, and suspension bed.

[0071] According to this application, the phosphorus-containing high-silica molecular sieve catalyst based on this application can be used under conventional hydrocracking process conditions when applied to distillate oil hydrocracking. For example, the hydrocracking reaction conditions can be: a reaction temperature of about 200-650°C, preferably about 300-510°C; a reaction pressure of about 3-24 MPa, preferably about 4-15 MPa; and a liquid hourly space velocity of about 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

[0072] In a fourth aspect, this application provides a hydrocracking catalyst comprising, on a dry weight basis, about 45-90 wt%, for example, about 60-90 wt%, of a support, about 1-40 wt%, for example, about 5-35 wt%, of a first metal component, and about 1-15 wt%, for example, about 2-12 wt%, of a second metal component, on a dry weight basis. The support comprises a phosphorus-containing high-silica molecular sieve according to this application and a heat-resistant inorganic oxide, wherein the weight ratio of the phosphorus-containing high-silica molecular sieve to the heat-resistant inorganic oxide is about 0.03:1 to about 20:1, for example, about 0.05:1 to about 19:1; the first metal component comprises a Group VIB metal; and the second metal component comprises a Group VIII metal.

[0073] According to this application, the use of the heat-resistant inorganic oxide can improve the strength of the catalyst and improve and modulate its physicochemical properties, such as improving the pore structure of the catalyst. In some embodiments, the heat-resistant inorganic oxide can be an inorganic oxide commonly used in hydrogenation catalyst supports, such as alumina, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, thorium oxide, beryllium oxide, boron oxide, and cadmium oxide. In a preferred embodiment of this application, the heat-resistant inorganic oxide is alumina, which may include gibbsite (such as gibbsite), bayerite-nordstrandite, and boehmite (such as boehmite, diaspor, pseudoboehmite).

[0074] According to this application, in a preferred embodiment, the first metal is selected from molybdenum, tungsten and any combination thereof; and / or, the second metal component is selected from iron, nickel, cobalt and any combination thereof.

[0075] In a fifth aspect, this application provides a method for preparing the hydrocracking catalyst of this application, the method comprising the following steps:

[0076] i) A carrier is prepared by mixing a phosphorus-containing high-silica molecular sieve according to this application with a heat-resistant inorganic oxide; and

[0077] ii) Impregnate the carrier by contacting the impregnation solution containing the first metal precursor and the second metal precursor.

[0078] In this application, the contact impregnation method between the impregnation liquid and the carrier can be any method known to those skilled in the art, such as the method disclosed in Chinese Patent ZL200810241082.3, which includes loading a Group VIB metal component, a Group VIII metal component and an organic additive onto the catalyst carrier.

[0079] The preparation method of the carrier is well known to those skilled in the art, and this application does not impose any particular limitations. For example, the method may include: mixing the phosphorus-containing high-silica molecular sieve according to this application with a heat-resistant inorganic oxide, then molding and drying it to obtain the carrier. The molding method can employ various conventional methods, such as tablet molding, ball rolling molding, or strip extrusion molding.

[0080] This application does not have any particular requirements for the shape of the carrier. It can be spherical, strip-shaped, hollow strip-shaped, spherical, block-shaped, etc. The strip-shaped carrier can be clover-shaped, four-leaf clover-shaped, or other multi-leaf clover-shaped and their variants.

[0081] According to this application, in some embodiments, the first metal precursor is a compound soluble in the impregnation solution containing the first metal, including but not limited to at least one of an inorganic acid of the first metal, an inorganic salt of the first metal, an oxide of the first metal, and an organometallic compound; the inorganic salt may be at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; the organic substituent in the first organometallic compound may be at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups. For example, when the first metal is molybdenum, the first metal precursor may be at least one selected from molybdic acid, secondary molybdic acid, molybdate, secondary molybdate, and molybdenum oxide; when the first metal is tungsten, the first metal precursor may be at least one selected from tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstate.

[0082] According to this application, in some embodiments, the second metal precursor is a compound containing the second metal that is soluble in the impregnation solution, including but not limited to at least one of the following: an inorganic acid of the second metal, an inorganic salt of the second metal, an oxide of the second metal, and an organometallic compound; the inorganic salt may be at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; the organic substituent in the second organometallic compound may be at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups.

[0083] According to this application, in some embodiments, the impregnation solution may further contain organic additives, the concentration of which may be about 2-300 g / L. The organic additives may be oxygen-containing organic compounds and / or nitrogen-containing organic compounds. Specifically, the oxygen-containing organic compounds may be at least one selected from ethylene glycol, glycerol, polyethylene glycol (molecular weight may be about 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid; the nitrogen-containing organic compounds may be at least one selected from ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, aminoacetic acid, hypozoxytriacetic acid, ethylenediaminetetraacetic acid, and ammonium ethylenediaminetetraacetate.

[0084] In the method for preparing hydrocracking catalysts in this application, there is no particular limitation on the contact impregnation temperature; it can be any temperature achievable by the impregnation solution. There is also no particular limitation on the impregnation time, as long as the catalyst support is loaded with the required amount of the metallic active component precursor. Generally, the higher the impregnation temperature and the greater the concentration of the impregnation solution, 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. Once the required impregnation amount and conditions are determined, those skilled in the art can easily select a suitable impregnation time based on the teachings of this application.

[0085] This application does not specify any particular requirements for the impregnation method. The impregnation can be saturated or supersaturated. There are no particular restrictions on the impregnation environment; it can be carried out under sealed conditions or in an open environment according to conventional methods in the art. Lost water solvent may or may not be replenished during the impregnation process. Various gases, such as air, nitrogen, and water vapor, may be introduced during the impregnation process, or no new components may be introduced.

[0086] In some embodiments, the method for preparing hydrocracking catalyst of this application may further include the steps of drying and calcining the impregnated material. The drying and calcining are conventional steps in catalyst preparation, and this application does not impose any particular limitations. For example, the drying conditions may be: a temperature of approximately 80-350°C, preferably approximately 100-300°C, and a time of approximately 0.5-24 h, preferably approximately 1-12 h. The calcining conditions may be: a temperature of approximately 350-600°C, preferably approximately 400-550°C; and a time of approximately 0.2-12 h, preferably approximately 1-10 h.

[0087] The hydrocracking catalyst provided in this application can be used as a catalyst for various acid catalysis reactions such as catalytic cracking, hydroisomerization, alkylation, and hydrocracking. It is particularly suitable for hydrocracking hydrocarbon feedstocks to produce hydrocarbon fractions with lower boiling points and lower molecular weights.

[0088] Therefore, in a sixth aspect, this application provides the use of the hydrocracking catalyst according to this application in the hydrocracking reaction of hydrocarbon feedstock, including contacting the hydrocarbon feedstock with the hydrocracking catalyst.

[0089] According to this application, the hydrocarbon feedstock can be various heavy mineral oils or synthetic oils, or their mixed distillate oils, such as straight run gas oil, vacuum gas oil, demetallized oils, atmospheric residue, deasphalted vacuum residue, coker distillates, catalytic cracking distillates, shale oil, tar sand oil, coal liquefaction oil, etc.

[0090] In particular, the catalyst provided in this application is applicable to the hydrocracking of heavy and low-grade distillate oils to produce middle distillate oils with a distillation range of about 149-371°C, and especially about 180-370°C.

[0091] When the hydrocracking catalyst provided in this application is applied to the hydrocracking reaction of hydrocarbon feedstock, it is preferable to further include pre-sulfurizing the hydrocracking catalyst with sulfur, hydrogen sulfide or sulfur-containing feedstock in the presence of hydrogen at a temperature of about 140-370°C before using the hydrocracking catalyst. This pre-sulfurization can be carried out outside the reactor or in situ in the reactor to convert the catalyst into a sulfide form.

[0092] The catalyst provided in this application can be used under conventional hydrocracking process conditions when applied to distillate oil hydrocracking. For example, the hydrocracking reaction conditions can be: a reaction temperature of about 200-650°C, preferably about 300-510°C; a reaction pressure of about 3-24 MPa, preferably about 4-15 MPa; and a liquid hourly space velocity of about 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

[0093] The hydrocracking reaction can be carried out in any apparatus that allows the hydrocarbon feedstock to contact and react with the catalyst under hydrogenation conditions, such as a fixed-bed reactor, a moving-bed reactor, a fluidized-bed reactor, or a slurry-bed reactor.

[0094] In a preferred embodiment, this application provides the following technical solution:

[0095] A1. A phosphorus-containing high-silicon molecular sieve, based on oxides and on a dry basis, wherein the molecular sieve contains about 90-99.8% by weight of silicon, about 0.1-9.0% by weight of aluminum, and about 0.01-2.5% by weight of phosphorus.

[0096] The XRD pattern of the molecular sieve has at least three diffraction peaks, with the first strong peak located at a diffraction angle of approximately 5.9-6.9°, the second strong peak at approximately 10.0-11.0°, and the third strong peak at approximately 15.6-16.7°.

[0097] Preferably, the molecular sieve has a pore volume of about 0.20-0.50 mL / g and a specific surface area of ​​about 260-600 m². 2 / g.

[0098] A2. According to the phosphorus-containing high-silica molecular sieve described in Project A1, in the XRD pattern of the molecular sieve, the diffraction angle of the first strong peak is about 6.1-6.8°, the diffraction angle of the second strong peak is about 10.2-10.7°, and the diffraction angle of the third strong peak is about 15.8-16.5°.

[0099] A3. The phosphorus-containing high-silica molecular sieve according to any one of the foregoing items, wherein in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5 The value is approximately 3.0-11.0, I² / I. 23.5-24.5 The value is approximately 2.9-7.0, I3 / I 23.5-24.5 The value is approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0100] A4. The phosphorus-containing high-silica molecular sieve according to any one of the preceding items, wherein the XRD pattern of the molecular sieve has at least five diffraction peaks, wherein the diffraction angle of the fourth strongest peak is located at about 20.4-21.6° and the diffraction angle of the fifth strongest peak is located at about 11.8-12.8°.

[0101] A5. According to the phosphorus-containing high-silica molecular sieve described in Project A4, in the XRD pattern of the molecular sieve, the diffraction angle of the fourth strongest peak is located at approximately 20.8-21.4°, and the diffraction angle of the fifth strongest peak is located at approximately 12.1-12.6°; and / or,

[0102] I4 / I 23.5-24.5 It is approximately 1.0-4.0, I5 / I 23.5-24.5 The value is approximately 1.0-2.0, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5. represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0103] A6. A method for preparing phosphorus-containing high-silica molecular sieves, comprising the following steps:

[0104] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-8.0MPa, and in the presence of water vapor for about 0.5-10 hours to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-15% by weight, a sodium content of about 0.5-4.5% by weight, a silicon content of about 70-85% by weight, and an aluminum content of about 16.0-21.0% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0105] b) The hydrothermally treated molecular sieve material obtained in step a) is slurried with water to obtain a first slurry. The first slurry is heated to approximately 40-95°C, preferably approximately 50-85°C. The temperature is then maintained, and a first acid solution is added to the first slurry. The amount of the first acid solution added is such that the pH of the resulting acidified first slurry is approximately 2.5-4. The reaction is then carried out at a constant temperature for approximately 0.5-20 hours, and the first solid product is collected.

[0106] c) Add water to the first solid product obtained in step b) and slurry to obtain a second slurry. Heat the second slurry to about 40-95°C, preferably about 50-85°C, and then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acidified second slurry is about 1.0-2.0. Then, react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0107] A7. According to the method described in Project A6, in step a), the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, the cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, and the specific surface area is about 250-750 m². 2 / g, with a pore volume of approximately 0.2-0.95mL / g.

[0108] A8. The method according to item A6 or A7, wherein in step b), the weight ratio of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is about 14:1 to about 5:1.

[0109] A9. The method according to any one of items A6 to A8, wherein in step c), the weight ratio of water in the second slurry to the dry weight ratio of the phosphorus-containing molecular sieve raw material is about 0.5:1 to about 20:1.

[0110] A10. The method according to any one of items A6 to A9, wherein in step c), the second acid solution is added in the manner of: based on 1L of the second slurry, using H... + The second acid solution is added to the second slurry at a rate of about 0.05-15 mol / h, preferably about 0.05-10 mol / h, and more preferably about 2-8 mol / h.

[0111] A11. The method according to any one of items A6 to A10, wherein in step b), the acid concentration of the first acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 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, preferably selected from sulfuric acid and nitric acid; and / or,

[0112] In step c), the acid concentration of the second acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 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, preferably selected from sulfuric acid and nitric acid.

[0113] A12. The method according to any one of items A6 to A11 further includes the step of: collecting the second solid product, then washing it with water and drying it to obtain the phosphorus-containing silicon-aluminum molecular sieve; preferably, the drying conditions are: temperature about 50-350°C, preferably about 70-200°C; time about 1-24h, preferably about 2-6h.

[0114] A13. A phosphorus-containing high-silica molecular sieve prepared by any one of the methods in items A6 to A12.

[0115] A14. Application of phosphorus-containing high-silicon molecular sieves according to any one of items A1-A5 and A13 in the hydrocracking reaction of hydrocarbon feedstocks.

[0116] A15. According to the application described in item A14, the hydrocarbon feedstock is straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coking distillate, catalytic cracking distillate, shale oil, bituminous sands, or coal liquefaction oil, or a combination of two or more of these; and / or,

[0117] The conditions for the hydrocracking reaction are as follows: reaction temperature approximately 200-650℃, preferably approximately 300-510℃; reaction pressure approximately 3-24 MPa, preferably approximately 4-15 MPa; and liquid hourly space velocity approximately 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1The hydrogen-to-oil volume ratio is approximately 100-5000.

[0118] A16. A hydrocracking catalyst, based on the dry weight of the catalyst, comprising about 45-90% by weight of a support, about 1-40% by weight of a first metal component based on metal oxides, and about 1-15% by weight of a second metal component based on metal oxides, on a dry weight basis.

[0119] The carrier comprises a phosphorus-containing high-silica molecular sieve and a heat-resistant inorganic oxide, wherein the weight ratio of the phosphorus-containing high-silica molecular sieve to the heat-resistant inorganic oxide is approximately 0.03:1 to approximately 20:1.

[0120] Wherein, the first metal component comprises a Group VIB metal; the second metal component comprises a Group VIII metal; and

[0121] Based on oxides and the dry weight of the molecular sieve, the phosphorus-containing high-silica molecular sieve comprises approximately 90-99.8 wt% silicon, approximately 0.1-9.0 wt% aluminum, and approximately 0.01-2.5 wt% phosphorus. The XRD pattern of the phosphorus-containing high-silica molecular sieve exhibits at least three diffraction peaks, with the first strong peak at a diffraction angle of approximately 5.9-6.9°, the second strong peak at approximately 10.0-11.0°, and the third strong peak at approximately 15.6-16.7°. Preferably, the pore volume of the phosphorus-containing high-silica molecular sieve is approximately 0.20-0.50 mL / g, and the specific surface area is approximately 260-600 m². 2 / g.

[0122] A17. According to the hydrocracking catalyst described in Project A16, in the XRD pattern of the phosphorus-containing high-silica molecular sieve, the diffraction angle of the first strong peak is about 6.1-6.8°, the diffraction angle of the second strong peak is about 10.2-10.7°, and the diffraction angle of the third strong peak is about 15.8-16.5°.

[0123] A18. The hydrocracking catalyst according to item A16 or A17, wherein in the XRD pattern of the phosphorus-containing high-silica molecular sieve, I1 / I 23.5-24.5 The value is approximately 3.0-11.0, I² / I. 23.5-24.5 The value is approximately 2.9-7.0, I3 / I 23.5-24.5 The value is approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0124] A19. The hydrocracking catalyst according to any one of items A16 to A18, wherein the XRD pattern of the phosphorus-containing high-silica molecular sieve has at least five diffraction peaks, wherein the diffraction angle of the fourth strongest peak is located at about 20.4-21.6° and the diffraction angle of the fifth strongest peak is located at about 11.8-12.8°.

[0125] A20. According to the hydrocracking catalyst described in Project A19, in the XRD pattern of the phosphorus-containing high-silica molecular sieve, the diffraction angle of the fourth strongest peak is located at approximately 20.8-21.4°, and the diffraction angle of the fifth strongest peak is located at approximately 12.1-12.6°; and / or,

[0126] I4 / I 23.5-24.5 It is approximately 1.0-4.0, I5 / I 23.5-24.5 The value is approximately 1.0-2.0, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0127] A21. The hydrocracking catalyst according to any one of items A16 to A20, wherein the phosphorus-containing high-silica molecular sieve is prepared by a method comprising the following steps:

[0128] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-8.0MPa, and in the presence of water vapor for about 0.5-10 hours to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-15% by weight, a sodium content of about 0.5-4.5% by weight, a silicon content of about 70-85% by weight, and an aluminum content of about 16.0-21.0% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0129] b) The hydrothermally treated molecular sieve material obtained in step a) is slurried with water to obtain a first slurry. The first slurry is heated to approximately 40-95°C, preferably approximately 50-85°C. The temperature is then maintained, and a first acid solution is added to the first slurry. The amount of the first acid solution added is such that the pH of the resulting acidified first slurry is approximately 2.5-4. The reaction is then carried out at a constant temperature for approximately 0.5-20 hours, and the first solid product is collected.

[0130] c) Add water to the first solid product obtained in step b) and slurry to obtain a second slurry. Heat the second slurry to about 40-95°C, preferably about 50-85°C, and then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acidified second slurry is about 1.0-2.0. Then, react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0131] A22. According to the hydrocracking catalyst described in Project A21, in step a), the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, the cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, and the specific surface area is about 250-750 m². 2 / g, with a pore volume of approximately 0.2-0.95mL / g.

[0132] A23. The hydrocracking catalyst according to item A21 or A22, wherein in step b), the weight ratio of water in the first slurry to the dry weight ratio of the phosphorus-containing molecular sieve feedstock is about 14:1 to about 5:1.

[0133] A24. The hydrocracking catalyst according to any one of items A21 to A23, wherein in step c), the weight ratio of water in the second slurry to the dry weight ratio of the phosphorus-containing molecular sieve feedstock is about 0.5:1 to about 20:1.

[0134] A25. The hydrocracking catalyst according to any one of items A21 to A24, wherein in step c), the second acid solution is added in the manner of: based on 1L of the second slurry, using H... + The second acid solution is added to the second slurry at a rate of about 0.05-15 mol / h, preferably about 0.05-10 mol / h, and more preferably about 2-8 mol / h.

[0135] A26. The hydrocracking catalyst according to any one of items A21 to A25, wherein in step b), the acid concentration of the first acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 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, preferably selected from sulfuric acid and nitric acid; and / or,

[0136] In step c), the acid concentration of the second acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 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, preferably selected from sulfuric acid and nitric acid.

[0137] A27. The hydrocracking catalyst according to any one of items A21 to A26, wherein the preparation step of the phosphorus-containing high-silicon molecular sieve further includes: collecting the second solid product, then washing it with water and drying it to obtain the phosphorus-containing high-silicon molecular sieve; preferably, the drying conditions are: a temperature of about 50-350°C, preferably about 70-200°C; and a time of about 1-24 hours, preferably about 2-6 hours.

[0138] A28. A hydrocracking catalyst according to any one of items A21 to A27, wherein the heat-resistant inorganic oxide is alumina, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, thorium oxide, beryllium oxide, boron oxide, or cadmium oxide, or a combination of two or more thereof; and / or,

[0139] 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 more of them.

[0140] A29. A method for preparing a hydrocracking catalyst as described in any one of items A16 to A28, the method comprising: impregnating a support with an impregnation solution containing a first metal precursor and a second metal precursor, wherein the support comprises the phosphorus-containing high-silica molecular sieve and a heat-resistant inorganic oxide.

[0141] A30. The method described in Project A29 further includes the step of mixing the phosphorus-containing high-silica molecular sieve with a heat-resistant inorganic oxide, and then molding, drying, and calcining to obtain the carrier.

[0142] A31. The method according to item A29 or A30, wherein the first metal precursor is an inorganic acid of a first metal, an inorganic salt of a first metal, or an organometallic compound; the inorganic salt is at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; the organic substituent in the first organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups; and / or,

[0143] The second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organometallic compound of the second metal; the inorganic salt is at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; the organic substituent in the second organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups.

[0144] A32. The method according to any one of items A29 to A31 further includes the steps of drying and calcining the material obtained after impregnation;

[0145] Preferably, the drying conditions are: a temperature of about 80-350°C, more preferably about 100-300°C, and a time of about 0.5-24 hours, more preferably about 1-12 hours; and / or,

[0146] Preferably, the calcination conditions are: a temperature of about 350-600℃, more preferably about 400-550℃, and a time of about 0.2-12h, more preferably about 1-10h.

[0147] A33, Application of any one of the hydrocracking catalysts in the hydrocracking reaction of hydrocarbon feedstocks.

[0148] A34. In accordance with the application described in Project A33, the hydrocarbon feedstock is straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coking distillate, catalytic cracking distillate, shale oil, bituminous sands, or coal liquefaction oil, or a combination of two or more of these; and / or,

[0149] The conditions for the hydrocracking reaction are as follows: reaction temperature approximately 200-650℃, preferably approximately 300-510℃; reaction pressure approximately 3-24 MPa, preferably approximately 4-15 MPa; and liquid hourly space velocity approximately 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

[0150] B1. A phosphorus-containing high-silica molecular sieve, characterized in that the pore volume of the molecular sieve is about 0.20-0.50 mL / g, and the specific surface area is about 260-600 m². 2 / g, calculated as oxides and based on the dry weight of the molecular sieve, the molecular sieve has a silicon content of about 90-99.8% by weight, an aluminum content of about 0.1-9.0% by weight, and a phosphorus content of about 0.01-2.5% by weight;

[0151] In the XRD pattern of the molecular sieve, the diffraction angle of the first strong peak is about 5.9-6.9°, the diffraction angle of the second strong peak is about 10.0-11.0°, and the diffraction angle of the third strong peak is about 15.6-16.7°.

[0152] B2. According to the molecular sieve described in item B1, in the XRD pattern of the molecular sieve, the diffraction angle of the first strong peak is about 6.1-6.8°, the diffraction angle of the second strong peak is about 10.2-10.7°, and the diffraction angle of the third strong peak is about 15.8-16.5°.

[0153] B3. The molecular sieve described in item B1 or B2, wherein in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5 The value is approximately 3.0-11.0, I² / I. 23.5-24.5 The value is approximately 2.9-7.0, I3 / I 23.5-24.5 The value is approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0154] B4. The molecular sieve according to item B1 or B2, wherein in the XRD pattern of the molecular sieve, the diffraction angle position of the fourth strongest peak is about 20.4-21.6° and the diffraction angle position of the fifth strongest peak is about 11.8-12.8°.

[0155] B5. The molecular sieve described in item B4, wherein in the XRD pattern of the molecular sieve, the diffraction angle of the fourth strongest peak is located at approximately 20.8-21.4°, and the diffraction angle of the fifth strongest peak is located at approximately 12.1-12.6°; and / or,

[0156] I4 / I 23.5-24.5 It is approximately 1.0-4.0, I5 / I 23.5-24.5 The value is approximately 1.0-2.0, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0157] B6. A method for preparing phosphorus-containing high-silica molecular sieves as described in any one of items B1 to B5, comprising the following steps:

[0158] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-2MPa, and in the presence of water vapor for about 0.5-10h to obtain the hydrothermally treated molecular sieve material; the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight and the sodium content is about 0.5-4.5% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0159] b) Add water to the hydrothermally treated molecular sieve material obtained in step a) to make a slurry, heat the first slurry to about 40-95°C, then maintain the temperature and add a first acid solution to the first slurry. The amount of the first acid solution added is such that the pH value of the first slurry after acid addition is about 2.5-4. Then react at a constant temperature for about 0.5-20 hours and collect the first solid product.

[0160] c) Add water to the first solid product obtained in step b) and slurry to obtain a second slurry. Heat the second slurry to about 40-95°C, then maintain the temperature and continuously add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the second slurry after acidification is about 1.0-2.0. Then react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0161] B7. According to the method described in B6 of the project, in step a), the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, and the cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, and the specific surface area is about 250-750 m². 2 / g, with a pore volume of approximately 0.2-0.95mL / g.

[0162] B8. According to the method described in Project B6, in step b), the weight ratio of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is about 14:1 to about 5:1.

[0163] B9. According to the method described in Project B6, 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 about 0.5:1 to about 20:1.

[0164] B10. According to the method described in B6 of the project, in step c), the second acid solution is added in the following manner: based on 1L of the second slurry, H... + The second acid solution is added to the second slurry at a rate of approximately 0.05-10 mol / h.

[0165] B11. According to the method described in item B6, wherein in step b), the acid concentration of the first acid solution is about 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,

[0166] In step c), the acid concentration of the second acid solution is about 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.

[0167] B12. The method according to item B6, wherein the method further includes: collecting the second solid product, then washing and drying it with water to obtain a phosphorus-containing silicon-aluminum molecular sieve; and / or, the drying conditions are: a temperature of about 50-350°C, preferably about 70-200°C; and a time of about 1-24 hours, preferably about 2-6 hours.

[0168] B13. The application of any one of the phosphorus-containing high-silica molecular sieves in the hydrocracking reaction of hydrocarbon feedstocks.

[0169] B14. According to the application described in item B13, the hydrocarbon feedstock is straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coking distillate, catalytic cracking distillate, shale oil, bituminous sands, or coal liquefaction oil, or a combination of two or three of these; and / or,

[0170] The conditions for the hydrocracking reaction are as follows: reaction temperature of approximately 200-650℃, preferably approximately 300-510℃; reaction pressure of approximately 3-24 MPa, preferably approximately 4-15 MPa; and liquid hourly space velocity of approximately 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

[0171] C1. A hydrocracking catalyst, characterized in that, based on the dry weight of the catalyst, the catalyst comprises 45-90% by weight of a support, 1-40% by weight of a first metal component based on metal oxides, and 1-15% by weight of a second metal component based on metal oxides.

[0172] The carrier comprises a phosphorus-containing high-silica molecular sieve and a heat-resistant inorganic oxide, wherein the weight ratio of the phosphorus-containing high-silica molecular sieve to the heat-resistant inorganic oxide is approximately 0.03:1 to approximately 20:1; the first metal component is a metal component selected from Group VIB metals; the second metal component is a metal component selected from Group VIII metals.

[0173] The phosphorus-containing high-silica molecular sieve has a pore volume of approximately 0.20-0.50 mL / g and a specific surface area of ​​approximately 260-600 m². 2 / g, calculated as oxides and based on the dry weight of the molecular sieve, the phosphorus-containing high-silicon molecular sieve has a silicon content of about 90-99.8% by weight, an aluminum content of about 0.1-9.0% by weight, and a phosphorus content of about 0.01-2.5% by weight; in the XRD pattern of the phosphorus-containing high-silicon molecular sieve, the diffraction angle of the first strong peak is about 5.9-6.9°, the diffraction angle of the second strong peak is about 10.0-11.0°, and the diffraction angle of the third strong peak is about 15.6-16.7°.

[0174] C2. According to the catalyst described in Project C1, in the XRD pattern of the phosphorus-containing high-silica molecular sieve, the diffraction angle of the first strong peak is about 6.1-6.8°, the diffraction angle of the second strong peak is about 10.2-10.7°, and the diffraction angle of the third strong peak is about 15.8-16.5°.

[0175] C3. The catalyst described in project C1 or C2, wherein in the XRD pattern of the phosphorus-containing high-silica molecular sieve, I1 / I 23.5-24.5 The value is approximately 3.0-11.0, I² / I.23.5-24.5 The value is approximately 2.9-7.0, I3 / I 23.5-24.5 The value is approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0176] C4. According to the catalyst described in item C1 or C2, in the XRD pattern of the phosphorus-containing high-silica molecular sieve, the diffraction angle of the fourth strongest peak is located at approximately 20.4-21.6°, and the diffraction angle of the fifth strongest peak is located at approximately 11.8-12.8°.

[0177] C5. According to the catalyst described in item C4, in the XRD pattern of the phosphorus-containing high-silica molecular sieve, the diffraction angle of the fourth strongest peak is located at approximately 20.8-21.4°, and the diffraction angle of the fifth strongest peak is located at approximately 12.1-12.6°; and / or,

[0178] I4 / I 23.5-24.5 It is approximately 1.0-4.0, I5 / I 23.5-24.5 The value is approximately 1.0-2.0, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5 . represents the peak height of the peak located at a diffraction angle of approximately 23.5-24.5°.

[0179] C6. The catalyst according to item C1 or 2, wherein the phosphorus-containing high-silica molecular sieve is prepared by a method comprising the following steps:

[0180] a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700℃, a pressure of about 0.1-2MPa, and in the presence of water vapor for about 0.5-10h to obtain the hydrothermally treated molecular sieve material; the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight and the sodium content is about 0.5-4.5% by weight, based on oxides and the dry weight of the phosphorus-containing molecular sieve raw material.

[0181] b) Add water to the hydrothermally treated molecular sieve material obtained in step a) to make a slurry, heat the first slurry to about 40-95°C, then maintain the temperature and add a first acid solution to the first slurry. The amount of the first acid solution added is such that the pH value of the first slurry after acid addition is about 2.5-4. Then react at a constant temperature for about 0.5-20 hours and collect the first solid product.

[0182] c) Add water to the first solid product obtained in step b) and slurry to obtain a second slurry. Heat the second slurry to about 40-95°C, then maintain the temperature and continuously add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the second slurry after acidification is about 1.0-2.0. Then react at a constant temperature for about 0.5-20 hours and collect the second solid product.

[0183] C7. According to the catalyst described in C6 of the project, in step a), the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, the cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, and the specific surface area is about 250-750 m². 2 / g, with a pore volume of approximately 0.2-0.95mL / g.

[0184] C8. The catalyst according to item C6, wherein in step b), the weight ratio of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is about 14:1 to about 5:1.

[0185] C9. The catalyst according to item C6, wherein in step c), the weight ratio of water in the second slurry to the dry weight of the phosphorus-containing molecular sieve raw material is about 0.5:1 to about 20:1.

[0186] C10. According to the catalyst described in project C6, in step c), the second acid solution is added as follows: based on 1L of the second slurry, H... + The second acid solution is added to the second slurry at a rate of approximately 0.05-10 mol / h.

[0187] C11. The catalyst according to item C6, wherein in step b), the acid concentration of the first acid solution is about 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,

[0188] In step c), the acid concentration of the second acid solution is about 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.

[0189] C12. According to the catalyst described in item C6, the preparation step of the phosphorus-containing high-silicon molecular sieve further includes: collecting the second solid product, then washing it with water and drying it to obtain the phosphorus-containing high-silicon molecular sieve; and / or, the drying conditions are: a temperature of about 50-350°C, preferably about 70-200°C; and a time of about 1-24 hours, preferably about 2-6 hours.

[0190] C13. The catalyst according to item C1, wherein the heat-resistant inorganic oxide is alumina, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, thorium oxide, beryllium oxide, boron oxide, or cadmium oxide, or a combination of two or three of them; and / or,

[0191] 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 of them.

[0192] C14. A method for preparing a hydrocracking catalyst as described in any one of items C1 to C13, comprising: impregnating a support by contacting an impregnation solution containing a first metal precursor and a second metal precursor.

[0193] C15. The method described in project C14, wherein the method further includes: mixing phosphorus-containing high-silica molecular sieve and heat-resistant inorganic oxide, then molding, drying and calcining to obtain the carrier.

[0194] C16. According to the method described in item C14, wherein the first metal precursor is an inorganic acid of the first metal, an inorganic salt of the first metal, or an organometallic compound of the first metal; the inorganic salt is a nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate, or chloride; the organic substituent in the first organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups; and / or,

[0195] The second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organometallic compound of the second metal; the inorganic salt is a nitrate, carbonate, basic carbonate, hypophosphite, phosphate, sulfate, or chloride; the organic substituent in the second organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups.

[0196] C17. The method according to item C14, wherein the method further includes the steps of drying and calcining the impregnated material; and / or,

[0197] The drying conditions are: a temperature of approximately 80-350°C and a time of approximately 0.5-24 hours; and / or,

[0198] The roasting conditions are: a temperature of approximately 350-600℃ and a time of approximately 0.2-12 hours.

[0199] C18. The application of a hydrocracking catalyst as described in any one of items C1-13 in the hydrocracking reaction of hydrocarbon feedstocks.

[0200] C19. According to the application described in item C18, the hydrocarbon feedstock is straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coking distillate, catalytic cracking distillate, shale oil, bituminous sands, or coal liquefaction oil, or a combination of two or three of these; and / or,

[0201] The conditions for the hydrocracking reaction are as follows: reaction temperature of approximately 200-650℃, preferably approximately 300-510℃; reaction pressure of approximately 3-24 MPa, preferably approximately 4-15 MPa; and liquid hourly space velocity of approximately 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

[0202] Example

[0203] The present application will be further described below through embodiments, but this does not limit the content of the present application.

[0204] Instruments and methods

[0205] In the following examples and comparative examples, the pore volume and specific surface area of ​​the molecular sieve were determined using an ASAP 2400 automatic adsorption analyzer from Micromertics Instruments, Inc., USA, by the static low-temperature adsorption capacity method (according to the method of national standard GB / T5816-1995). The specific method was as follows: the molecular sieve to be tested was degassed under vacuum at 250℃ and 1.33 Pa for 4 hours, and then contacted with nitrogen gas as the adsorbate at -196℃ until static adsorption reached adsorption equilibrium; the amount of nitrogen adsorbed by the adsorbent was calculated from the difference between the amount of nitrogen gas introduced and the amount of nitrogen remaining in the gas phase after adsorption; then the pore size distribution was calculated using the BJH formula, and the specific surface area and pore volume were calculated using the BET formula.

[0206] The crystal structure of the molecular sieve was determined using a Siemens D5005 X-ray diffractometer, according to the industry standard SH / T0339-92. The experimental conditions were: Cu target, kα radiation, solid-state detector, tube voltage 40 kV, tube current 40 mA, step scan, step size 0.02°, pre-set time 2 s, and scan range 5°–70°. The diffraction angle position refers to the 2θ angle value of the highest peak value.

[0207] The silicon, aluminum, phosphorus, and sodium contents of the molecular sieve were determined using a Rigaku Electric Industries, Ltd. 3271E X-ray fluorescence spectrometer. The determination method was as follows: powder sample was pressed into a pellet, rhodium target was used, laser voltage was 50 kV, laser current was 50 mA, scintillation counter and proportional counter were used to detect the intensity of each element's spectral line, and external standard method was used for quantitative and semi-quantitative analysis of the element content.

[0208] Molecular sieve preparation examples

[0209] Preparation Examples 1-2 are used to illustrate the phosphorus-containing high-silica molecular sieve and its preparation method according to this application.

[0210] Preparation Example 1

[0211] The phosphorus-containing molecular sieve used was USY molecular sieve (produced by Sinopec Catalyst Changling Branch, with a cell constant of 2.456 nm and a specific surface area of ​​672 m²). 2 500g of molecular sieve material (with a pore volume of 0.357mL / g, Na2O content of 1.44 wt%, P2O5 content of 1.37 wt%, SiO2 content of 76.7 wt%, and Al2O3 content of 20.5 wt%) was placed in a hydrothermal reactor, and 100% steam was introduced. The material was then hydrothermally treated at 560℃ and 0.8MPa for 3 hours. The hydrothermally treated molecular sieve material was then removed.

[0212] Take 50g (dry basis) of the above-mentioned hydrothermally treated molecular sieve material, add 500mL of deionized water, stir and slurry to obtain the first slurry. Heat it to 80℃, add 2.0mol / L sulfuric acid solution, and stop adding acid when the pH value of the first slurry after acid addition is 2.8. Then, keep the reaction at a constant temperature for 4h, filter, and obtain 40g of the first solid product.

[0213] The first solid product was added to 400 mL of deionized water and stirred to obtain a second slurry. This slurry was then heated to 80°C. Using 1 L of the second slurry as a reference, H... + A 2 mol / L sulfuric acid solution was added to the second slurry at a rate of 5 mol / h. The addition of acid was stopped when the pH of the second slurry after acid addition was measured to be 1.4. The reaction was then carried out at a constant temperature for 3 hours, filtered, and the second solid product was collected.

[0214] The obtained solid product was dried at 180℃ for 3 h to obtain phosphorus-containing high-silica molecular sieve Y-1, the XRD pattern of which is shown in Figure 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the peak heights are listed in Table 2, and other properties are listed in Table 3.

[0215] Preparation Example 2

[0216] Phosphorus-containing high-silica molecular sieves were prepared according to the method in Example 1, except that the second acid solution was added at a rate of 15 mol / h. Phosphorus-containing high-silica molecular sieve Y-2 was obtained, and its XRD pattern is shown in Figure 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the peak heights in Table 2, and other properties in Table 3.

[0217] Comparative Examples 1-3 are prepared to illustrate molecular sieves not included in this application and their preparation methods.

[0218] Preparation of Comparative Example 1

[0219] PSRY molecular sieve, designated as molecular sieve DY-1, was prepared according to Example 1 of Chinese Patent ZL98117286.5, and its XRD pattern is shown in Figure 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the peak heights are listed in Table 2, and other properties are listed in Table 3.

[0220] Preparation of Comparative Example 2

[0221] Phosphorus-free HY molecular sieve (produced by Sinopec Catalyst Changling Branch, trade name HY, with a cell constant of 2.465 nm and a specific surface area of ​​580 m²) was used. 2 500g of a molecular sieve material (with a pore volume of 0.33mL / g, Na2O content of 0.3 wt%, SiO2 content of 77.7 wt%, and Al2O3 content of 22 wt%) was placed in a hydrothermal reactor, and 100% steam was introduced. The material was then hydrothermally treated at 500℃ and 2.0MPa for 1 hour, after which the hydrothermally treated molecular sieve material was removed.

[0222] Take 80g (dry basis) of the above-mentioned hydrothermally treated molecular sieve material, add 500mL of deionized water, stir and slurry to obtain the first slurry. Heat it to 80℃, add 1.0mol / L sulfuric acid solution, and stop adding acid when the pH of the first slurry after acid addition is 3.0. Then, keep the reaction at a constant temperature for about 4 hours, filter, and obtain 65g of the first solid product.

[0223] The first solid product was added to 600 mL of deionized water and stirred to obtain a second slurry. This slurry was then heated to 80°C. Using 1 L of the second slurry as a reference, H... + A 1.0 mol / L phosphoric acid solution was added to the second slurry at a rate of 2 mol / h. Acid addition was stopped when the pH of the second slurry reached 1.4. The reaction was then carried out at a constant temperature for approximately 3 hours. After filtration, the second solid product was collected. The obtained solid product was dried at 180℃ for 3 hours to obtain phosphorus-containing silica-alumina molecular sieve DY-2, the XRD pattern of which is shown in Figure 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the peak heights in Table 2, and other properties in Table 3.

[0224] Preparation of Comparative Example 3

[0225] Take 500g of phosphorus-containing molecular sieve (same as in Example 1) and place it in a hydrothermal reactor. Pass 100% steam through it and perform hydrothermal treatment at 560℃ and 0.8MPa for 3 hours. Then take out the hydrothermally treated molecular sieve material.

[0226] Take 60g (dry basis) of the above-mentioned hydrothermally treated molecular sieve material, add 500mL of deionized water, stir and slurry to obtain the first slurry. Heat the slurry to 90℃, add 2.0mol / L sulfuric acid solution, and stop adding acid when the pH of the first slurry after acid addition is 2.5. Then, maintain the temperature for about 4 hours, filter, and obtain 60g of the first solid product. Dry the obtained solid product at 180℃ for 3 hours to obtain phosphorus-containing silica-alumina molecular sieve DY-3, whose XRD pattern is shown in Figure 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the peak heights are listed in Table 2, and other properties are listed in Table 3.

[0227] Table 1. XRD diffraction peak positions of the molecular sieves obtained in Preparation Examples 1-2 and Comparative Examples 1-3

[0228]

[0229] Table 2. Peak heights of XRD diffraction peaks for the molecular sieves obtained in Preparation Examples 1-2 and Comparative Examples 1-3.

[0230]

[0231] Table 3 Other properties of the molecular sieves obtained in Preparation Examples 1-2 and Comparative Examples 1-3

[0232]

[0233] Catalyst Examples

[0234] Examples 1-6 illustrate the hydrocracking catalyst and its preparation method according to this application. Comparative Examples 1-3 illustrate hydrocracking catalysts and their preparation methods not included in this application.

[0235] Example 1

[0236] 80g of molecular sieve Y-1 (dry basis) was mixed with 28.8g of pseudoboehmite (Sinopec Catalyst Changling Branch, trade name PB90, 70% by weight on dry basis, wherein the dry basis condition is that the sample is calcined at 600℃ for 3h and the resulting sample is the same as the initial sample by weight). The mixture was extruded into a trilobal strip with an outer circle diameter of 1.6 mm, dried at 120℃ for 3h, and calcined at 600℃ for 3h to obtain the support CS-1.

[0237] After cooling to room temperature, 100g of CS-1 support was impregnated with 70mL of aqueous solution containing 34.65g of ammonium metatungstate (Sichuan Zigong Hard Alloy Factory, tungsten oxide content of 82 wt%) and 24.37g of nickel nitrate (Beijing Xinguang Chemical Reagent Factory, nickel oxide content of 27.85 wt%), dried at 120℃ for 3h, and calcined at 480℃ for 4h to obtain the hydrocracking catalyst, the composition of which is shown in Table 4.

[0238] Example 2

[0239] The catalyst was prepared according to the method of Example 1, except that molecular sieve Y-2 was used instead of molecular sieve Y-1. The composition of the resulting catalyst is shown in Table 4.

[0240] Example 3

[0241] 95g of molecular sieve Y-1 (dry basis) was mixed with 7.2g of pseudoboehmite and extruded into a trilobal strip with an outer circle diameter of 1.6 mm. The strip was dried at 120℃ for 3 h and calcined at 600℃ for 3 h to obtain the carrier CS-3.

[0242] After cooling to room temperature, 100g of CS-3 support was impregnated with 45mL of aqueous solution containing 13.86g of ammonium metatungstate and 8.16g of nickel nitrate, dried at 120℃ for 3h, and calcined at 480℃ for 4h to obtain the hydrocracking catalyst, the composition of which is shown in Table 4.

[0243] Example 4

[0244] 5g of molecular sieve Y-1 (dry basis) was mixed with 135.7g of pseudoboehmite and extruded into a trilobal strip with an outer circle diameter of 1.6 mm. The strip was dried at 120℃ for 3 h and calcined at 600℃ for 3 h to obtain the carrier CS-4.

[0245] After cooling to room temperature, 100g of CS-4 support was impregnated with a 70mL aqueous solution containing 74g of ammonium metatungstate and 43g of nickel nitrate, dried at 120℃ for 3h, and calcined at 480℃ for 4h to obtain the hydrocracking catalyst, the composition of which is shown in Table 4.

[0246] Example 5

[0247] 50g of molecular sieve Y-1 (dry basis) was mixed with 10g of titanium dioxide (Beijing Chemical Reagent Factory, purity 99%) and 57.1g of boehmite (dry basis), and extruded into a trilobal strip with an outer circle diameter of 1.6 mm. The mixture was dried at 120℃ for 3 h and calcined at 600℃ for 3 h to obtain the carrier CS-5.

[0248] After cooling to room temperature, 100g of CS-5 support was impregnated with an 80mL aqueous solution containing 69g of ammonium metatungstate and 17g of nickel nitrate, dried at 120℃ for 3h, and calcined at 480℃ for 4h to obtain the hydrocracking catalyst, the composition of which is shown in Table 4.

[0249] Example 6

[0250] 30g of molecular sieve Y-1 (dry basis) was mixed with 160g of silica sol (Beijing Feilongma Economic and Trade Co., Ltd., trade name JN-25, silica content 25%, silica particle diameter 9-11nm) and 42.9g of pseudoboehmite (Sinopec Catalyst Changling Branch, trade name PB90, 70% by weight on dry basis), and extruded into trilobal strips with an outer circle diameter of 1.6mm. The mixture was dried at 120℃ for 3h and calcined at 600℃ for 3h to obtain the support CS-6.

[0251] After cooling to room temperature, 100g of CS-6 support was impregnated with a 95mL aqueous solution containing 29g of molybdenum trioxide (Luoyang Jinduicheng Molybdenum Industry, purity 99.6%), 67g of cobalt nitrate (Beijing Xinguang Chemical Reagent Factory, cobalt oxide content 27.85% by weight) and 11.8g of phosphoric acid (Beijing Chemical Reagent Factory, purity 85%). The solution was dried at 120℃ for 3h and calcined at 480℃ for 4h to obtain the hydrocracking catalyst, the composition of which is shown in Table 4.

[0252] Comparative Examples 1-3

[0253] The catalyst was prepared according to the method of Example 1, except that molecular sieve Y-1 was replaced with molecular sieves DY-1, DY-2, and DY-3, respectively. The composition of the resulting catalyst is shown in Table 4.

[0254] Table 4. Properties of the catalysts obtained in the examples and comparative examples.

[0255]

[0256] Test Implementation Examples

[0257] This test example is used to test the catalytic activity of the catalysts of Examples 1-3 and Comparative Examples 1-3 for hydrocracking reactions.

[0258] The hydrocracking activity of a catalyst was evaluated in a small-scale fixed-bed hydrocracking unit using n-octane containing 5.61% tetrahydronaphthalene and 0.29% pyridine as feedstock. The catalyst loading was 0.2 mL, the reaction temperature was 320 °C, the reaction pressure was 4.0 MPa, the hydrogen-to-oil volume ratio was 3600, and the liquid hourly space velocity was 30 h⁻¹. -1 After the reaction feed stabilized for 4 hours, the activity of the catalyst was represented by the percentage of tetrahydronaphthalene converted in the product composition. The evaluation results are shown in Table 5.

[0259] Table 5. Test results of the catalysts in Examples 1-3 and Comparative Examples 1-3

[0260] Catalyst Conversion Rate (%) Example 1 78.0 Example 2 71.2 Example 3 76.3 Comparative Example 1 54.3 Comparative Example 2 63.2 Comparative Example 3 58.3

[0261] As can be seen from the results in Table 5, under comparable conditions, compared with catalysts containing phosphorus-containing silica-alumina molecular sieves not included in this application, catalysts containing phosphorus-containing high-silica molecular sieves provided in this application exhibit hydrocracking catalytic activity improved by at least 7% in the presence of high-nitrogen substances (such as pyridine).

[0262] The preferred embodiments of this application have been described in detail above with reference to the accompanying drawings. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0263] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.

[0264] Furthermore, various different implementations of this application can be combined in any way, as long as they do not violate the spirit of this application, they should also be regarded as the content disclosed in this application.

Claims

1. A phosphorus-containing high-silica molecular sieve, based on oxides and on a dry basis, wherein the molecular sieve comprises about 86.5-99.8% by weight, preferably about 90-99.8% by weight, of silicon, about 0.1-13.5% by weight, preferably about 0.1-9.0% by weight, of aluminum, and about 0.01-6% by weight, preferably about 0.01-2.5% by weight, of phosphorus. The XRD pattern of the molecular sieve has at least three diffraction peaks, wherein the diffraction angle of the first strong peak is located at approximately 5.9-6.9°, preferably at approximately 6.1-6.8°; the diffraction angle of the second strong peak is located at approximately 10.0-11.0°, preferably at approximately 10.2-10.7°; and the diffraction angle of the third strong peak is located at approximately 15.6-16.7°, preferably at approximately 15.8-16.5°. Preferably, the molecular sieve has a pore volume of about 0.20-0.50 mL / g, more preferably about 0.30-0.45 mL / g, and a specific surface area of ​​about 250-670 m². 2 / g, preferably about 260-600m 2 / g.

2. The molecular sieve according to claim 1, wherein in the XRD pattern of the molecular sieve, I1 / I 23.5-24.5° The value is approximately 3.0-11.0, I² / I. 23.5-24.5° It is approximately 2.9-7.0, and I3 / I 23.5-24.5° The value is approximately 1.0-4.0, where I1 is the peak height of the first strong peak, I2 is the peak height of the second strong peak, and I3 is the peak height of the third strong peak. 23.5-24.5° This represents the peak height of the peak located at a diffraction angle of approximately 23.5–24.5°.

3. The molecular sieve according to any one of the preceding claims, wherein the XRD pattern of the molecular sieve has at least five diffraction peaks, wherein the diffraction angle of the fourth strongest peak is located at about 20.4-21.6°, preferably at about 20.8-21.4°; and the diffraction angle of the fifth strongest peak is located at about 11.8-12.8°, preferably at about 12.1-12.6°. Preferably, in the XRD pattern of the molecular sieve, I4 / I 23.5-24.5° It is approximately 1.0-4.0, and I5 / I 23.5-24.5° It is approximately 1.0-2.0, where I4 is the peak height of the fourth strongest peak, I5 is the peak height of the fifth strongest peak, and I... 23.5-24.5° This represents the peak height of the peak located at a diffraction angle of approximately 23.5–24.5°.

4. A method for preparing phosphorus-containing high-silica molecular sieves, comprising the following steps: a) The phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700°C, preferably about 400-650°C, a pressure of about 0.1-8.0 MPa, preferably about 0.5-5 MPa, and in the presence of water vapor for about 0.5-10 hours, preferably about 1-7 hours, to obtain the hydrothermally treated molecular sieve material; the phosphorus-containing molecular sieve raw material has a phosphorus content of about 0.1-15 wt%, preferably about 0.1-6 wt%, sodium content of about 0.5-4.5 wt%, preferably about 0.5-3.0 wt%, silicon content of about 70-85 wt%, preferably about 70-80 wt%, and aluminum content of about 16.0-21.0 wt%, preferably about 18.0-21.0 wt%; b) The hydrothermally treated molecular sieve material obtained in step a) is mixed with water to prepare a first slurry. The first slurry is heated to approximately 40-95°C, preferably approximately 50-85°C. The temperature is then maintained, and a first acid solution is added to the first slurry. The amount of the first acid solution added is such that the pH of the resulting acid-added first slurry is approximately 2.3-4.0, preferably approximately 2.5-4.

0. The mixture is then reacted at a constant temperature for approximately 0.5-20 hours, preferably approximately 1-10 hours, and the first solid product is collected. c) Add water to the first solid product obtained in step b) to prepare a second slurry, heat the second slurry to about 40-95°C, preferably about 50-85°C, then maintain the temperature and add a second acid solution to the second slurry. The amount of the second acid solution added is such that the pH value of the resulting acidified second slurry is about 0.8-2.0, preferably about 1.0-2.0, and then react at a constant temperature for about 0.5-20 h, preferably about 1-10 h, and collect the second solid product.

5. The method according to claim 4, wherein in step a), the phosphorus-containing molecular sieve raw material is a phosphorus-containing Y-type molecular sieve, the phosphorus-containing Y-type molecular sieve having a cell constant of approximately 2.425-2.47 nm and a specific surface area of ​​approximately 250-750 m². 2 / g, with a pore volume of approximately 0.2-0.95mL / g.

6. The method according to claim 4 or 5, wherein in step b), the weight ratio of water in the first slurry to the dry weight of the phosphorus-containing molecular sieve raw material is about 14:1 to about 5:1; and / or 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 approximately 0.5:1 to approximately 20:

1.

7. The method according to any one of claims 4-6, wherein in step c), the second acid solution is added in the manner of: based on 1L of the second slurry, using H... + The second acid solution is added to the second slurry at a rate of about 0.05-15 mol / h, preferably about 0.05-10 mol / h, and more preferably about 2-8 mol / h.

8. The method according to any one of claims 4-7, wherein in step b), the acid concentration of the first acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 mol / L, and the acid in the first acid solution is selected from at least one of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid, preferably selected from sulfuric acid and nitric acid; and / or In step c), the acid concentration of the second acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 mol / L, and the acid in the second acid solution is selected from at least one of phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid, preferably selected from sulfuric acid and nitric acid.

9. The method according to any one of claims 4-8, further comprising: The steps include collecting the second solid product, washing it with water, and drying it to obtain the phosphorus-containing high-silicon molecular sieve; preferably, the drying conditions are: temperature of about 50-350℃, more preferably about 70-200℃; time of about 1-24h, more preferably about 2-6h.

10. A hydrocracking catalyst, based on the dry weight of the catalyst, comprising about 45-90% by weight of a support, about 1-40% by weight of a first metal component based on metal oxides, and about 1-15% by weight of a second metal component based on metal oxides; The carrier comprises a phosphorus-containing high-silica molecular sieve and a heat-resistant inorganic oxide, wherein the weight ratio of the phosphorus-containing high-silica molecular sieve to the heat-resistant inorganic oxide is about 0.03:1 to about 20:1; in, The first metal component contains a Group VIB metal, the second metal component contains a Group VIII metal, and the phosphorus-containing high-silicon molecular sieve is the phosphorus-containing high-silicon molecular sieve according to any one of claims 1-3 or the phosphorus-containing high-silicon molecular sieve prepared by the method according to any one of claims 4-9.

11. The hydrocracking catalyst according to claim 10, wherein the heat-resistant inorganic oxide is selected from alumina, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, thorium oxide, beryllium oxide, boron oxide, cadmium oxide, and any combination thereof, preferably selected from silicon oxide and alumina; The first metal component is selected from molybdenum, tungsten, and any combination thereof; and / or The second metal component is selected from iron, nickel, cobalt, and any combination thereof.

12. A method for preparing the hydrocracking catalyst according to any one of claims 10-11, comprising the following steps: i) A carrier is prepared by mixing the phosphorus-containing high-silica molecular sieve according to any one of claims 1-3 or the phosphorus-containing high-silica molecular sieve prepared by any one of claims 4-9 with a heat-resistant inorganic oxide; and ii) Impregnate the carrier by contacting the impregnation solution containing the first metal precursor and the second metal precursor. Preferably, the first metal precursor is an inorganic acid of a first metal, an inorganic salt of a first metal, an oxide of a first metal, or a first organometallic compound; the inorganic salt is at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; the organic substituent in the first organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups; and / or Preferably, the second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, an oxide of the second metal, or an organometallic compound of the second metal; the inorganic salt is at least one selected from nitrates, carbonates, basic carbonates, hypophosphites, phosphates, sulfates, and chlorides; and the organic substituent in the second organometallic compound is at least one selected from hydroxyl, carboxyl, amino, ketone, ether, and alkyl groups.

13. The method according to claim 12, further comprising the steps of drying and calcining the material obtained after impregnation; Preferably, the drying conditions are: a temperature of about 80-350°C, more preferably about 100-300°C, and a time of about 0.5-24 hours, more preferably about 1-12 hours; and / or Preferably, the calcination conditions are: a temperature of about 350-600℃, more preferably about 400-550℃, and a time of about 0.2-12h, more preferably about 1-10h.

14. The use of the hydrocracking catalyst according to any one of claims 10-11 or the hydrocracking catalyst prepared by the method according to any one of claims 12-13 in the hydrocracking reaction of hydrocarbon feedstock, comprising contacting the hydrocarbon feedstock with the hydrocracking catalyst.

15. The application according to claim 14, wherein the hydrocarbon feedstock is selected from straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coking distillate, catalytic cracking distillate, shale oil, bituminous sands, coal liquefaction oil, and any combination thereof; and / or, The conditions for the hydrocracking reaction are as follows: reaction temperature approximately 200-650℃, preferably approximately 300-510℃; reaction pressure approximately 3-24 MPa, preferably approximately 4-15 MPa; and liquid hourly space velocity approximately 0.1-50 h⁻¹. -1 Preferably, it takes about 0.2-30 hours. -1 The hydrogen-to-oil volume ratio is approximately 100-5000.

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