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    • 专利摘要:
    The present invention discloses a molecular sieve of the Na-Y type and a process for the preparation of the Na-Y type molecular sieve, an HY type molecular sieve and a process for the preparation of the HY type molecular sieve, a hydrocracking catalyst, and a hydrocracking process. The average grain diameter of the Na-Y molecular sieve is 2 to 5 μm, and the sum of the pore volumes of 1 to 10 nm in diameter represents 70 to 90% of the total pore volume of the Na-type molecular sieve. -Y. The H-Y molecular sieve obtained from the coarse grain Na-Y molecular sieve can be used as an acid component in the hydrocracking catalyst. When the hydrocracking catalyst containing the HY-type molecular sieve is applied in the hydrocracking reaction of heavy oils which contain macromolecules, it can provide a better cracking activity and a better product selection capability in the reaction reaction. hydrocracking.
    公开号:FR3029189A1
    申请号:FR1561443
    申请日:2015-11-27
    公开日:2016-06-03
    发明作者:Chang Liu；Fenglai Wang；Minghua Guan；Yanze Du；Wei Huang；Hong Zhao
    申请人:China Petroleum and Chemical Corp；Sinopec Fushun Research Institute of Petroleum and Petrochemicals ；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a molecular sieve of the Na-Y type and to a hydrocracking process. method for preparing the Na-Y molecular sieve, a molecular sieve of the HY type obtained from the molecular sieve and a method for preparing the HY-type molecular sieve, a hydrocracking catalyst containing the HY-type molecular sieve, and a hydrocracking process using the hydrocracking catalyst. STATE OF THE INVENTION Currently, in the field of heavy oil cracking, molecular sieves that can be used as cracking active components include molecular sieve type Y, molecular sieve type (3, and ZSM-type molecular sieves, etc., in which the Y-type molecular sieve is most widely used Existing processes for producing Y-type molecular sieve products in industrial production are essentially based on the process of use a crystallization directing agent (CDA: crystallization agent) disclosed by the company GRACE (US company) in US Patents 3,639,099 and US 4,166,099, and the ordinary products of molecular sieve type Y produced with such The processes have crystalline grains usually about 1 μm in grain size, with about 300 to 400 crystalline cells in each dimension. conventionally synthesized ordinary size Y-type molecular sieve, the percentage of pore distribution of diameter less than 1 nm is 15 to 20%, the percentage of pore diameter distribution in the range of 1 to 10 nm is 45 to 50%, and the percent distribution of pore diameter greater than 10 nm is 30 to 40%. For a macromolecular cracking reaction, the ideal range of pore diameter suitable for raw material reaction and product diffusion is 1 to 10 nm. Although the Y-type molecular sieve can be suitably modified to achieve an ideal pore diameter distribution range by subsequent modification, the final pore diameter distribution in the subsequently modified molecular sieve depends directly on the distribution. original pore diameter in the molecular sieve; furthermore, the pore expansion has impacts on the structure of the molecular sieve backbone, and therefore has impacts on the activity and stability of the molecular sieve. In the prior art, the direct synthesis process involves a process in which a Y-type molecular sieve (usually a Na-Y molecular sieve) to be prepared is synthesized directly in a single operation without further processing. Currently, a CDA method is used in a conventional manner. With this method, the silica-alumina chemical ratio (SiO 2 / Al 2 O 3) in the synthesized Y-type molecular sieve is 3.5 to 5.5. To obtain a Y-type molecular sieve with a higher silica-to-alumina chemical ratio, expensive and highly toxic organic materials such as crown ethers must be added. In addition, in the process of preparing a Y-type molecular sieve, the lower the silica-alumina ratio, the easier the preparation; on the other hand, the higher the silica-alumina ratio, the harder the conditions and the more difficult the preparation. There are many influencing factors in the preparation of a molecular sieve with a high silica-to-alumina ratio, such as the composition of the reaction mixture, the preparation process, the source of the reagents, the preparation of the directing agent , the acidity / alkalinity of the gel, and the conditions of crystallization, etc.
    [0002] In CN103449468A, a process for synthesizing a Na-Y molecular sieve is disclosed, comprising - mixing sodium silicate, sodium metaaluminate, and deionized water, and aging from 15 to 70 ° C for 0.5 to 48.0 hours to obtain a crystallization directing agent; mixing the crystallization directing agent, sodium silicate, an acidic aluminum salt, and a sodium aluminate solution in a homogeneous state to prepare a silica-alumina gel; crystallization of the silica-alumina gel from 80 to 140 ° C for 0.1 to 80.0 h; addition of peroxide in the crystalline silica-alumina gel in a molar ratio of peroxide to Al 2 O 3 in the equilibrium gel of 0.05 to 20, followed by further crystallization for 5 to 20 h. With this process, no organic or inorganic matrix agent is added, no further processing or modification is required, and a Y-type molecular sieve with a high silica-to-alumina ratio can be prepared directly over a short period of time, and the crystallinity of the resulting molecular sieve is equal to or greater than 80%, the silica-alumina ratio is not less than 5.8, and the average grain diameter is in the range of 200 to 300 nm. Although this method can be used to synthesize a Y-type molecular sieve with a high silica-to-alumina ratio, the preparation process is complex, the grain size of the resulting molecular sieve is too small and a specific amount of peroxide must be added in the gel. Therefore, the conditions of synthesis of the molecular sieve are demanding.
    [0003] In US 3,671,191 and US 3,639,099, a CDA process is used to synthesize a Y-type molecular sieve, in which a directing agent is prepared first; then a silica-alumina gel is prepared; then, the aged mastering agent is added, and the crystallization is carried out at high temperature. In the process described above, an inorganic acid and an aluminum salt are used to decrease the alkalinity of the reaction system, and thus improve the silica-alumina ratio of the resulting molecular sieve. However, only an ordinary type Y molecular sieve can be prepared with this method, and a directing agent must first be synthesized in the preparation process. In addition, the preparation process encompasses many steps and involves a high cost.
    [0004] In CN101481120A, a process for preparing a Y-type molecular sieve through a rapid crystallization process is disclosed. In this process, first a silica-alumina gel is prepared from a source of silica, a source of alumina, and an alkaline source; then, a W / O emulsion system is prepared from the silica-alumina gel, oil, surfactant, and co-surfactant; then, the W / O emulsion system is transferred to a reactor for rapid crystallization. The process utilizes an expensive surfactant to prepare the Y-type molecular sieve, and the preparation process is complex; therefore, the cost of preparation is severely increased. In CN1209358A, a secondary pore rich Y zeolite is disclosed. Specifically, a process for preparing a zeolite is disclosed, wherein the Na-Y zeolite is used as an initial powder, an ammonium exchange is first performed to release Na +; then hydrothermal treatment and acid extraction are performed twice, in which the second round of hydrothermal treatment and the second round of acid extraction are carried out after the first round of hydrothermal treatment and the first round of acid extraction. In zeolite Y obtained, the pore volume with a diameter greater than 2 nm represents 40 to 66% of the total pore volume. In the hydrocracking process, the conversion of macromolecular aromatics in the raw materials is adversely affected, and the distribution and quality of the prepared catalyst product must be further improved. Considering the aspect of the application of molecular sieve products with a cracking function in industrial catalytic processes, the performance of molecular sieve products mainly depends on two aspects: selective absorptivity and reactivity. The molecules of the reagents can diffuse into the molecular sieve pore channels and have specific catalyzed reactions only if the molecular size of the reagent is smaller than the pore size of the molecular sieve and the molecules can overcome the surface energy barrier of the crystals in the molecular sieve; here, the diffusivity of the molecules absorbed through the pores and cages of the crystals in the molecular sieve plays a decisive role. Therefore, it is desirable to overcome the disadvantages of existing Y-type molecular sieve products in terms of ideal diameter distribution. pores and provide a Y-type molecular sieve with a pore diameter distribution suitable for macromolecular cracking reactions. SUMMARY OF THE INVENTION To overcome the disadvantages of the prior art, the present invention provides a molecular sieve of the type Na-Y, a HY-type molecular sieve and a method for preparing the Na-Y molecular sieve, a HY-type molecular sieve and a method for preparing the HY-type molecular sieve, a hydrocracking catalyst, and a hydrocracking process. In order to achieve the objects described above, the present invention provides a Na-Y molecular sieve, wherein the average grain diameter of the Na-Y molecular sieve is 2 to 5 μm, and the sum pore volumes of 1 to 10 nm in diameter represent 70 to 90% of the total pore volume of the Na-Y molecular sieve. The present invention further provides a method for preparing the Na-Y molecular sieve of the present invention comprising: (1) the sodium silicate mixture, the highly alkaline sodium metaaluminate solution, the aluminum sulphate, and the weakly alkaline sodium metaaluminate solution in a molar ratio of Na 2 O: Al 2 O 3: SiO 2: H 2 O equal to (10 to 15): 1: (10 to 20): (500 to 600), and aging the mixture obtained to obtain a gel; and (2) treating the gel obtained in step (1) by hydrothermal crystallization, and then filtering, washing, and drying the gel after hydrothermal crystallization. The present invention further provides a H-Y molecular sieve, wherein the crystal cell parameter of the H-Y molecular sieve is 2.425 to 2.450 nm; the molar ratio of SiO 2 / Al 2 O 3 in the H-Y molecular sieve is from 10 to 120: 1; the sum of pore volumes of 2 to 7 min in the H-Y molecular sieve is 60 to 95% of the total pore volume, preferably 70 to 90%; the specific surface area of the H-Y molecular sieve is 750 to 980 m 2 / g; and the total amount of acid measured by near infrared spectroscopy in the H-Y molecular sieve is 0.1 to 1.0 mmol / g.
    [0005] The present invention further provides a process for preparing an HY-type molecular sieve, comprising - (A) treating the Na-Y molecular sieve proposed in the present invention by ammonium exchange to prepare a molecular sieve NH4-Na-Y type; (B) treating the NH4-Na-Y molecular sieve obtained in step (A) by hydrothermal treatment; and (C) controlling the material obtained in step (B) to cause it to have a contact reaction with the (NH4) 2SiF6 solution. The present invention further provides a H-Y molecular sieve prepared with the method provided in the present invention. The present invention further provides a hydrocracking catalyst, wherein the carrier in the catalyst contains the H-Y type molecular sieve provided in the present invention. The present invention further provides a hydrocracking process, comprising - (a) hydropretreatment of a crude oil with hydrogen and in the presence of a pretreatment agent; and (b) hydrocracking the pretreated product obtained in step (a) with hydrogen and in the presence of a hydrocracking catalyst; Wherein the hydrocracking catalyst is the hydrocracking catalyst provided in the present invention. The coarse grain Na-Y molecular sieve proposed in the present invention has a crystalline granularity of 2 to 5 μm, a high silica-to-alumina ratio, a more efficient pore diameter distribution, a high thermostability, and high hydrothermal stability. In the process for preparing the molecular sieve, no additive such as a directing agent, a matrix agent or a surfactant is added; the product is synthesized by hydrothermal crystallization in a single operation, selecting appropriate raw materials and optimizing the preparation process; moreover, the efficiency of using the silica source and the alumina source is high, the process is short and the cost is low. In addition, the H-Y molecular sieve obtained from the coarse grain Na-Y molecular sieve can be used as an acid component in the hydrocracking catalyst. Since the coarse grain synthesized molecular sieve in the present invention has large crystal grains, with 1000 to 2000 crystalline cells in each dimension, it is ideal for use in macromolecular cracking. In addition, the molecular sieve has a better range of pore diameter distribution, so that the degree of cracking of the reagents can be effectively controlled and is useful for diffusion of the product through the pores and channels. Therefore, when a molecular sieve containing catalyst is applied in a heavy oil hydrocracking reaction that contains macromolecules, the molecular sieve may provide more active sites such that the macromolecules in the heavy oil are cracked to an appropriate degree; therefore, the molecular sieve catalyst can improve the cracking potential of heavy oils, decrease the coke yield, and provide better cracking activity and product selection capability in the hydrocracking reaction. Other aspects and advantages of the present invention will be described in more detail in the following embodiments. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are provided to facilitate the understanding of the present invention and form part of this document. They are used in conjunction with the following embodiments to explain the present invention, but are not to be construed as limiting of the present invention, in which drawings: Fig. 1 is a SEM photo of LY-1 obtained in Example 1; Figure 2 is a SEM picture of DLY-1 obtained in Comparative Example 1; Fig. 3 is an XRD diagram of LY-1 obtained in Example 1. DETAILED DESCRIPTION Embodiments of the present invention will be detailed in the following. It will be appreciated that the embodiments described herein are provided solely to describe and explain the present invention, but should not be construed as limiting of the present invention. The present invention provides a Na-Y type molecular sieve, wherein the average grain diameter of the Na-Y molecular sieve is 2 to 5 μm, and the sum of the pore volumes of 1 to 10 μm diameter. nm represents 70 to 90% of the total pore volume of the Na-Y type molecular sieve. The present invention provides a coarse-grain Na-Y molecular sieve, which, compared to conventional molecular sieves, has a larger internal surface area, is more suitable for use as pore and channel structures in reactions. macromolecular, provides a chance for secondary cracking and transformation of more macromolecules into the molecular sieve, is more suitable for use in the treatment of petroleum products which contain large molecules or raw materials which contain heavy fractions and has superior performance in terms of improving the likelihood of transformation of macromolecules, etc. In the present invention, preferably, the average grain diameter is from 2 to 4.5 μm, more preferably from 3 to 4.5 μm. In the present invention, preferably, the sum of pore volumes of 1 to 10 nm in diameter represents 70 to 85% of the total pore volume in the Na-Y molecular sieve. On the other hand, in prior art Na-Y molecular sieves, particularly in coarse-grain Na-Y molecular sieves, the sum of pore volumes of 1 to 10 nm in diameter usually represents a percentage. less than 50% of the total pore volume in the Na-Y molecular sieves. In addition, the coarse grain Na-Y molecular sieve proposed in the present invention has a high silicon content, a more concentrated effective distribution of pore diameter, as well as better thermostability and hydrothermal stability. According to the present invention, the molar ratio of LiO 2 / Al 2 O 3 in the Na-Y molecular sieve is 3.5 to 6.5: 1, preferably 4 to 6: 1. According to the present invention, the specific surface area of the Na-Y molecular sieve is 800 to 1000 m 2 / g, the total pore volume of the Na-Y molecular sieve is 0.3 to 0.4 mL / g, and the outer surface area area of the Na-Y molecular sieve is 60 to 100 m 2 / g.
    [0006] According to the present invention, the relative crystallinity of the Na-Y molecular sieve is 110 to 150%, and the crystal cell parameter of the Na-Y molecular sieve is 2.46 to 2.465 nm. The present invention further provides a method for preparing the Na-Y molecular sieve, comprising - (1) the sodium silicate mixture, the highly alkaline sodium metaaluminate solution, the aluminum sulphate solution , and the weakly alkaline sodium metaaluminate solution in a molar ratio of Na 2 O: Al 2 O 3: 5: O: H 2 O equal to (10 to 15): 1: (10 to 20): (500 to 600), and the aging of the mixture obtained to obtain a gel; and (2) treating the gel obtained in step (1) by hydrothermal crystallization, and then filtering, washing, and drying the gel after hydrothermal crystallization. In the method of preparing the Na-Y molecular sieve proposed in the present invention, no additive such as a directing agent, matrix agent, or surfactant is added in step (1); the gel to be used for synthesizing the molecular sieve is directly prepared from the appropriately selected silica source and alumina source materials, and then the coarse grain Na-Y molecular sieve is synthesized by hydrothermal crystallization. in a single operation in step (2). The Na-Y molecular sieve prepared with the process has a crystalline granularity of 2.0 to 5.0 μm, a high silica-to-alumina ratio, and a more concentrated effective distribution of pore diameter; Specifically, the percent distribution of pores with a diameter of 1 nm to 10 nm, which are useful for the transformation of macromolecules, reaches a high level of 70% to 90%, much higher than in molecular sieves. conventional Y-type synthesized using a guiding agent. In the prior art, in the process of preparing a Y-type molecular sieve using a directing agent, the directing agent must first be prepared, and the directing agent must be aged for several years. days. In the crystallization procedure, the directing agent provides a crystal nucleus in the Y-type molecular sieve, then the source of silica and the source of alumina in the gel are deposited and crystallized on the crystalline core, such as so that a conventional type Y molecular sieve is obtained. In such a conventional type Y molecular sieve, the grain diameter is about 1 μm, and the percent distribution of pores with a diameter of 1 nm to 10 nm is 45% to 50%.
    [0007] In the present invention, in step (1), the sodium silicate, the highly alkaline sodium metaaluminate solution, the aluminum sulfate solution, and the weakly alkaline sodium metaaluminate solution are mixed as follows mixing the sodium silicate with the highly alkaline sodium metaaluminate solution while stirring, then mixing the resulting mixture with the aluminum sulphate solution and the weakly alkaline sodium metaaluminate solution. In which, water can be added separately or added together with the aqueous source solution of alumina and / or silica source, the source of silica is sodium silicate, and the source of alumina is sulphate aluminum, the highly alkaline sodium metaaluminate, and the weakly alkaline sodium metaaluminate. According to the present invention, aluminum sulphate, highly alkaline sodium metaaluminate, and weakly alkaline sodium metaaluminate control the amount of alumina supplied; preferably, in step (1), calculated in Al 2 O 3, the weight ratio of aluminum sulphate dosage: highly alkaline sodium metaaluminate: weakly alkaline sodium metaaluminate is 1: (0.5 to 0.7) : (0.6 to 0.8). According to the present invention, preferably, in the solution of highly alkaline sodium metaaluminate, the Na 2 O content is from 260 to 320 g / L, and the Al 2 O 3 content is from 30 to 50 g / L.
    [0008] According to the present invention, in the weakly alkaline sodium metaaluminate solution, the Na 2 O content is 100 to 130 g / L, and the Al 2 O 3 content is 60 to 90 g / L. According to the present invention, in the aluminum sulfate solution, the Al 2 O 3 content is 80 to 100 g / L.
    [0009] According to the present invention, in the sodium silicate, the TiO 2 content is 200 to 300 g / L, and the modulus of the sodium silicate is 2.8 to 3.5.
    [0010] According to the present invention, preferably, in step (1), the mixing temperature is 20 to 40 ° C, preferably 25 to 35 ° C. According to the present invention, in step (2), the gel is heated for hydrothermal crystallization at a temperature of 2 to 4 ° C / min, and then is treated by hydrothermal crystallization. According to the present invention, in step (2), the hydrothermal crystallization is carried out at a temperature of 80 to 120 ° C for 12 to 24 hours. The present invention further provides a H-Y molecular sieve, wherein the crystal cell parameter of the H-Y molecular sieve is 2.425 to 2.450 nm; the molar ratio of 5iO 2 / Al 2 O 3 in the H-Y molecular sieve is from 10 to 120: 1; the sum of pore volumes of 2 to 7 nm diameter in the H-Y molecular sieve is 60 to 95% of the total pore volume, preferably 70 to 90%; the specific surface area of the H-Y molecular sieve is 750 to 980 m 2 / g; and the total amount of acid measured by near infrared spectroscopy in the H-Y molecular sieve is 0.1 to 1.0 mmol / g. According to the present invention, in a preferred embodiment of the present invention, specifically, the average grain diameter of the HY molecular sieve is 2 to 5 μm, preferably 2 to 4.5 μm. more preferably 20 is from 3 to 4.5 am. The relative crystallinity of the H-Y molecular sieve is 110 to 150%. The crystal cell parameter of the H-Y molecular sieve is from 2,436 to 2,450 nm. The molar ratio of 5 102 / Al 2 O 3 in the H-Y molecular sieve is 10 to 50: 1. In the H-Y molecular sieve, the sum of pore volumes of 2 to 6 nm in diameter represents 60 to 90% of the total pore volume, preferably 70 to 85%. The total pore volume of the H-Y molecular sieve is 0.35 to 0.50 cc / g. The specific surface area of the H-Y molecular sieve is 750 to 950 m 2 / g. In the H-Y molecular sieve, the amount of non-backbone aluminum is 0.1 to 1% of the total amount of aluminum, preferably 0.1 to 0.5%. The total amount of acid measured by near infrared spectroscopy (NIS) in the H-Y molecular sieve is 0.5 to 1.0 mmol / g. The Na 2 O content in the H-Y molecular sieve is 0.15% by weight or less. According to the present invention, in another preferred embodiment of the present invention, specifically, the average grain diameter of the HY-type molecular sieve is 2 to 5 μm, preferably 2 to 4.5 μm. ! am, more preferably is 3 to 4.5! am. The relative crystallinity of the H-Y molecular sieve is 110 to 150%. The crystal cell parameter of the H-Y molecular sieve is 2.425 to 2.435 min, preferably 2.427 to 2.344 min. The molar ratio of 5iO 2 / Al 2 O 3 in the H-Y molecular sieve is 60 to 120: 1. In the H-Y molecular sieve, the sum of the pore volumes of 3 to 7 nm diameter in the H-Y molecular sieve is 70 to 95% of the total pore volume, preferably 75 to 90%. The total pore volume of the H-Y molecular sieve is 0.35 to 0.50 cm3 / g. The specific surface area of the H-Y molecular sieve is 800 to 980 m2 / g. In the H-Y molecular sieve, the amount of non-backbone aluminum is 0.1 to 1.0% of the total amount of aluminum, preferably 0.1 to 0.5%. The total amount of acid measured by NIS in the H-Y molecular sieve is 0.1 to 0.5 mmol / g. The present invention further provides a process for preparing a HY-type molecular sieve, comprising - (A) treating the Na-Y molecular sieve proposed in the present invention by ammonium exchange. to prepare an NH4-Na-Y molecular sieve; (B) treatment of the NH4-Na-Y molecular sieve obtained in step (A) by hydrothermal treatment, under the following conditions: gauge pressure of 0.05 to 0.25 MPa, temperature of 400 to 550 ° C, and treatment time of 0.5 to 5 hours; and (C) controlling the material obtained in step (B) to cause it to have a contact reaction with the (NH4) 2SiF6 solution.
    [0011] According to the present invention, the ammonium exchange can be repeated several times, since the Na 2 O content in the NH 4 -Na-Y molecular sieve after the ammonium exchange is acceptable. Preferably, the Na 2 O content in the NH 4 -Na-Y molecular sieve obtained in step (A) is 2.5 to 5% by weight.
    [0012] In the present invention, the ammonium salt may be one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate and ammonium oxalate, and the concentration of the aqueous ammonium salt solution can be from 0.3 to 6 mol / L. In a preferred embodiment of the present invention, in step (B), the hydrothermal treatment conditions include: gauge pressure: 0.05 to 0.25 MPa, preferably 0.1 to 0.2 MPa; temperature: 400 to 550 ° C, preferably 450 to 550 ° C; duration: 0.5 to 5 hours, preferably 1 to 3 hours. In step (C), the material obtained in step (B) is mixed with the solution (NH4) 2SiF6 in a weight ratio of liquid: solid equal to 3: 1 to 8: 1 from 70 to 90 ° C, then the mixture obtained is maintained at 80 to 120 ° C for 0.5 to 5 hours for the reaction, in which relative to 100 pbw of NH4-NaY type molecular sieve, the (NH4) 2SiF6 assay is 10 to 35 pbw; more preferably, every hour, relative to 100 pbw of NH4-Na-Y molecular sieve, the assay of (NH4) 2SiF6 is from 3 to 30 pbw.
    [0013] According to the preferred embodiment, the present invention further provides a H-Y molecular sieve prepared with the method provided in the present invention. Specifically, the average grain diameter of the H-Y molecular sieve is 2 to 5 μm, preferably 2 to 4.5 μm, more preferably 3 to 4.5 μm. The relative crystallinity of the H-Y molecular sieve is 110-150%, and the crystal cell parameter of the H-Y molecular sieve is 2,436-2,450 nm. The molar ratio of 5iO 2 / Al 2 O 3 in the H-Y molecular sieve is 10 to 50: 1. In the H-Y molecular sieve, the sum of pore volumes of 2 to 6 nm in diameter represents 60 to 90% of the total pore volume, preferably 70 to 85%. The total pore volume of the H-Y molecular sieve is 0.35 to 0.50 cm3 / g, and the specific surface area of the H-Y molecular sieve is 750 to 950 m2 / g. In the H-Y molecular sieve, the amount of non-backbone aluminum is 0.1 to 1% of the total amount of aluminum, preferably 0.1 to 0.5%. The total amount of acid measured by NIS in the H-Y molecular sieve is 0.5 to 1.0 mmol / g. The Na 2 O content in the H-Y molecular sieve is 0.15% by weight or less. In another preferred embodiment of the present invention, in step (B), hydrothermal treatment conditions include: gauge pressure: 0.28 to 0.5 MPa, preferably 0.3 to 0.5 MPa ; temperature: 450 to 700 ° C, preferably 600 to 700 ° C; duration: 0.5 to 5 hours, preferably 1 to 3 hours. In step (C), the material obtained in step (B) is mixed with the solution (NH4) 2SiF6 in a weight ratio of liquid: solid of 8: 1 to 15: 1 of 95 to 130 ° C, then the mixture obtained is maintained at 80 to 120 ° C for 0.5 to 5 hours for the reaction, in which relative to 100 pbw of molecular sieve of NH4Na-Y type, the (NH4) 2SiF6 assay is 35 to 80 pbw; more preferably, every hour, relative to 100 pbw of NH4-Na-Y molecular sieve, the assay of (NH4) 2SiF6 is from 3 to 30 pbw.
    [0014] According to the preferred embodiment above, the present invention further provides a H-Y molecular sieve prepared with the method provided in the present invention. Specifically, the average grain diameter of the H-Y molecular sieve is 2 to 5 μm, preferably 2 to 4.5 μm, more preferably 3 to 4.5 μm. The relative crystallinity of the H-Y molecular sieve is 110 to 150%, and the crystal cell parameter of the H-Y molecular sieve is 2.425 to 2.435 min, preferably 2,427 to 2,434 min. The molar ratio of 5 102 / Al 2 O 3 in the H-Y molecular sieve is 60 to 120: 1. In the H-Y molecular sieve, the sum of pore volumes of 3 to 7 nm in diameter represents 70 to 95% of the total pore volume, preferably 75 to 90%. The total pore volume of the H-Y molecular sieve is 0.35 to 0.50 cm3 / g, and the specific surface area of the H-Y molecular sieve is 800 to 980 m2 / g. In the H-Y molecular sieve, the amount of non-backbone aluminum is 0.1 to 1.0% of the total amount of aluminum, preferably 0.1 to 0.5%. The total amount of acid measured by NIS in the H-Y molecular sieve is 0.1 to 0.5 mmol / g. The Na 2 O content in the H-Y molecular sieve is 0.15% by weight or less. The present invention further provides a hydrocracking catalyst, wherein the carrier in the catalyst contains the H-Y type molecular sieve provided in the present invention.
    [0015] According to the present invention, preferably, the content of the H-Y type molecular sieve in the support is from 15 to 90% by weight. The support may further contain silica-alumina and / or amorphous alumina. According to the present invention, preferably, the specific surface area of the catalyst is 200 to 400 m 2 / g, and the pore volume of the catalyst is 0.2 to 0.5 ml / g. The catalyst can further comprise active hydrogenation components. According to the present invention, preferably, the hydrogenation active components are a metal element of the VIB family and a metal element of the VIII family; preferably, the metal element of the VIB family is Mo and / or W, and the metal element of the VIII family is Co and / or Ni. According to the present invention, preferably, on the basis of the total weight of the catalyst and calculated in the metal oxide, the metal element content of the VIB family is from 10 to 40% by weight, and the metal element content of the Family VIII is from 3 to 15% by weight; the support content is 45 to 87% by weight. The present invention further provides a hydrocracking process, comprising - (a) hydropretreatment of a crude oil in the presence of hydrogen and a pretreatment agent; and (b) hydrocracking the pretreated product obtained in step (a), in the presence of hydrogen and a hydrocracking catalyst, wherein the hydrocracking catalyst is the hydrocracking catalyst proposed in present invention. According to the present invention, preferably, the hydro-pretreatment conditions in step (a) include: a reaction pressure of 6 to 20 MPa, a reaction temperature of 350 to 420 ° C, a volumetric space velocity of crude oil input of 0.1 to 211-1, and a volume ratio of hydrogen to crude oil of 500: 1 to 2000: 1. According to the present invention, preferably, the hydrocracking conditions in step (b) include: a reaction pressure of 6 to 20 MPa, a reaction temperature of 350 to 420 ° C, an input volumetric space velocity pretreatment product from 0.1 to 211-1, and a volume ratio of hydrogen gas on pretreatment of 500: 1 to 2000: 1. The present invention is described in more detail in the following with the aid of some embodiments. In the following examples and comparative examples, the specific surface area, the pore volume, the outer surface area, and the pore distribution are measured with a cryogenic nitrogen adsorption analyzer ASAP2420 from Micromeritics, US Pat. using the cryogenic nitrogen physical adsorption method defined in GB / T 19587-2004; the relative crystallinity and the crystal cell parameter are measured with a Rigaku X-ray diffractometer Dmax-2500 using an X-ray diffraction method; the silica-alumina molar ratio is measured with a Rigaku ZSX100e XRF analyzer, using a chemical analysis method; the grain size of the molecular sieve is measured with a JEM-7500L SEM of 15 at JEOL. Example 1 (1) Preparation of the gel: add 165 mL of sodium silicate (the SiO 2 content is 235 g / L, the modulus is 2.9) in 63 mL of a solution of highly alkaline sodium metaaluminate ( the Na 2 O content is 280 g / L, the Al 2 O 3 content is 35 g / L) slowly at 25 ° C with stirring; once the mixture has been mixed until a homogeneous state is obtained, add 42.5 mL of an aluminum sulfate solution (A1203 content is 85 g / L) and 35.6 mL of a weakly alkaline sodium metaaluminate solution (the Na 2 O content is 110 g / L, and the Al 2 O 3 content is 68 g / L) sequentially, and stirring for 0.5 h at temperature; then, maintain the synthetic liquid obtained at the temperature for 1 hour for aging; thus, a gel is obtained; (2) Crystallization: Heat the gel in the synthesis reactor at a heating rate of 2.5 ° C / min to 100 ° C with stirring, then stir for 16 h at the temperature for crystallization; then cool rapidly with cold water, and remove the synthesized molecular sieve from the synthesis reactor, filter, wash and dry the molecular sieve; thus, a LY-1 product of a coarse grain Na-Y molecular sieve is obtained. The properties of the product are shown in Table 1. Observe LY-1 on a SEM and perform XRD analysis. The SEM picture is shown in Figure 1. It can be seen that the grain size of the molecular sieve obtained in the present invention is 3.5 μm, which is very large, and the crystal grains. The XRD diagram is shown in FIG. 3. It can be seen that the coarse grain type Y molecular sieve obtained in the present invention has obvious characteristic peaks, indicating that the molecular sieve prepared with the method disclosed in the present invention has Integral crystalline morphology and high relative crystallinity. Example 2 (1) Preparation of the gel: add 170 mL of sodium silicate (the SiO 2 content is 235 g / L, the modulus is 2.9) in 56 mL of a solution of highly alkaline sodium metaaluminate (the Na 2 O content is 275 g / L, the Al 2 O 3 content is 40 g / L) slowly at 30 ° C with stirring; once the mixture has been mixed to a homogeneous state, add 45.6 mL of an aluminum sulfate solution (A1203 content is 90 g / L) and 39.8 mL of a weakly alkaline sodium metaaluminate solution (the Na 2 O content is 120 g / L, and the Al 2 O 3 content is 77 g / L) sequentially, and stir for 0.5 h at a constant stirring rate at the temperature; then, maintain the synthetic liquid obtained at the temperature for 1 hour for aging; thus, a gel is obtained; (2) Crystallization: Heat the gel in the synthesis reactor at a heating rate of 3 ° C / min to 120 ° C with stirring, then stir for 20 h at the temperature for crystallization; then cool rapidly with cold water, and remove the synthesized molecular sieve from the synthesis reactor, filter, wash and dry the molecular sieve; thus, a LY-2 product of a coarse grain Na-Y type molecular sieve is obtained. The properties of the product are shown in Table 1.
    [0016] Observe LY-2 on a SEM and perform XRD analysis. The results obtained are similar to those presented in Figure 1 and Figure 3, and are not presented here. Example 3 (1) Preparation of the gel: add 156 mL of sodium silicate (the SiO 2 content is 260 g / L, the modulus is 3.0) in 48 mL of a solution of highly alkaline sodium metaaluminate ( the Na 2 O content is 300 g / L, the Al 2 O 3 content is 45 g / L) slowly at 35 ° C with stirring; once the mixture has been mixed until a homogeneous state is obtained, add 39.6 mL of aluminum sulfate solution (A1203 content is 90 g / L) and 28.5 mL of a weakly alkaline sodium metaaluminate solution (the Na 2 O content is 120 g / L, and the Al 2 O 3 content is 82 g / L) sequentially, and stirring for 1 h at a constant stirring rate at room temperature; ; then, maintain the synthetic liquid obtained at the temperature for 2 hours for aging; thus, a gel is obtained; (2) Crystallization: Heat the gel in the synthesis reactor at a heating rate of 3 ° C / min to 110 ° C with stirring, then stir for 24 h at the temperature for crystallization; then cool rapidly with cold water, and remove the synthesized molecular sieve from the synthesis reactor, filter, wash and dry the molecular sieve; thus, a LY-3 product of a coarse grain Na-Y molecular sieve is obtained. The properties of the product are shown in Table 1. Observe LY-3 on a SEM and perform XRD analysis. The results obtained are similar to those shown in Figure 1 and Figure 3, and are not presented here. Example 4 (1) Preparation of the gel: add 156 mL of sodium silicate (the SiO 2 content is 280 g / L, the modulus is 3.0) in 52.5 mL of a solution of highly sodium metaaluminate alkaline (the Na 2 O content is 280 g / L, the Al 2 O 3 content is 35 g / L) slowly at 35 ° C with stirring; once the mixture has been mixed to a homogeneous state, add 47.9 mL of an aluminum sulfate solution (A1203 content is 85 g / L) and 42.3 mL of a weakly alkaline sodium metaaluminate solution (the Na 2 O content is 120 g / L, and the Al 2 O 3 content is 70 g / L) sequentially, and stirring for 1 h at a constant stirring rate at room temperature; ; then, maintain the synthetic liquid obtained at the temperature for 2 hours for aging; thus, a gel is obtained; (2) Crystallization: Heat the gel in the synthesis reactor at a heating rate of 3 ° C / min to 120 ° C with stirring, then stir for 24 h at the temperature for crystallization; then cool rapidly with cold water, and remove the synthesized molecular sieve from the synthesis reactor, filter, wash and dry the molecular sieve; thus, a LY-4 product of a coarse grain Na-Y molecular sieve is obtained. The properties of the product are shown in Table 1. Observe LY-4 on a SEM and perform XRD analysis. The results obtained are similar to those shown in Figure 1 and Figure 3, and are not shown here. Comparative Example 1 Prepare a molecular sieve with the CDA process disclosed in USP 3,639,099. The preparation process is as follows: Preparation of a directing agent: Dissolve 26 g of aluminum hydroxide in 153 g of sodium hydroxide and 279 mL of water to form a raw material A; add 525 g of sodium silicate (the content of SiO 2 is 150 g / l, and the modulus is 3.3) in the raw material A, rapidly stir the gel and then maintain for 24 h at room temperature for aging; Add 601 g of an aluminum sulphate solution (the content of the aluminum sulphate is calculated in Al 2 O 3, = 16.9% by weight) in 2223 g of sodium silicate at 37.8 ° C., then add 392 g of the guiding agent in the solution and stir until a homogeneous state is obtained; then, add 191 g of a sodium aluminate solution (containing 126 g of aluminum hydroxide and 96.5 g of sodium hydroxide), stir the solution rapidly, and then treat the solution by hydrothermal crystallization during 10 h at 98.8 ° C; thus, a DLY-1 of Na-Y molecular sieve is obtained; the physical and chemical properties of DLY-1 are shown in Table 1. Observe DLY-1 on SEM and perform XRD analysis. The SEM picture is shown in Figure 2. It can be seen that the molecular sieve prepared with the method described in Comparative Example 1 has a grain size of 1.0 μm, which indicates that the type Y molecular sieve prepared with the method described in Comparative Example 1 is a conventional molecular sieve. Comparative Example 2 Prepare a molecular sieve with the method disclosed in CN101481120A. Mix and shake 0.699 g of siliceous sol (40% by weight), 0.156 g of sodium hydroxide, 0.212 g of sodium aluminate, and 2.94 ml of deionized water at room temperature until a homogeneous state to obtain a white gel; then, add 2.4 g of OP10, 1.6 g of normal butyl alcohol, and 1.8 ml of cyclohexane, stir until a homogeneous state, and treat by hydrothermal crystallization for 24 h at 100 °. C; thus, a DLY-2 product is obtained; the properties of the product are shown in Table 1. Comparative Example 3 Preparation of a guiding agent: Dissolve 153 g of solid sodium hydroxide in 279 ml of deionized water, cool the solution to room temperature, add 22.5 g of sodium metaaluminate to prepare a solution of highly alkaline sodium metaaluminate (the Na 2 O content is 140 g / L, and the Al 2 O 3 content is 25 g / L). Then, add the highly alkaline sodium metaaluminate solution in 525 g of sodium silicate (the SiO 2 content is 230 g / L, and the modulus is 2.9), and maintain the mixture for 24 h at room temperature for aging once the mixture has been mixed until a homogeneous state is achieved. Add 720 g of deionized water, 222.5 g of a weakly alkaline sodium metaaluminate solution (the Na 2 O content is 80 g / L, and the A1203 content is 45 g / L) and 242 g of sequentially, the mixture is blended until a homogeneous state is obtained, and then charged to a stainless steel reactor; maintain for 24 h at 100 ° C for crystallization, then filter, wash and dry; thus, a DLY-3 product is obtained; the properties of the product are shown in Table 1. Comparative Example 4 Prepare a Na-Y molecular sieve with the method disclosed in CN104773741A. 1) Charge 200 g of sodium silicate (the Na 2 O content is 6.91% by weight, and the SiO 2 content is 19.87% by weight) in a beaker, and place the beaker in a water bath at 34 ° C; add 145 g of highly alkaline sodium metaaluminate (the Na 2 O content is 21.02% by weight, and the Al 2 O 3 content is 3.10% by weight) in the beaker rapidly while stirring, then shake for 1 hour. h in the sealed state; then, treating the mixture by aging for 16 hours; thus, a directing agent is obtained, and the molar feed ratio of material is 16 Na 2 O: Al 2 O 3: 15 SiO 2: 325H 2 O; 2) Load 450 g of sodium silicate into a beaker and place the beaker in a 50 ° C water bath; then, add 100.02 g of a guiding agent, 149.30 g of highly alkaline sodium metaaluminate, and 170 g of water sequentially with stirring; continue stirring for 5 h, then add 281.74 g of aluminum sulphate (the content of Al 2 O 3 is 7.09 wt%) slowly, and mix and stir for 1 h; thus, a gel mixture is obtained, and the molar feed ratio of material is 2.5 Na 2 O: Al 2 O 3: 6.6 SiO 2: 207H 2 O; 3) Charge the gel mixture in a reactor, and hold for 40 h at 100 ° C for crystallization; then filter, wash and dry; thus a DLY-4 molecular sieve Na-Y type is obtained; the properties of the product are shown in Table 1. EXAMPLE 5 First, perform ammonium exchange for LY-1 of coarse-grain Na-Y molecular sieve. Prepare 10 L of 0.5 mol / L ammonium nitrate solution. Weigh 2,000 g of fine-grained Na-Y molecular sieve, dissolve in 10 L of the ammonium nitrate solution prepared above, and stir for 1 h at a stirring speed of 300 rpm. at 90 ° C; then filter the molecular sieve, and take samples to analyze the Na2O content; repeat the above operations until the Na 2 O content in the molecular sieve reaches 3% by weight; thus, a dried sample of LYN-1 is obtained. Weigh 200 g of molecular sieve LYN-1 and load it into a tubular hydrothermal treatment furnace, heat to 530 ° C by programmed heating, and treat for 1 hour at a pressure of 0.15 MPa; after the hydrothermal treatment, dissolve the molecular sieve in 1 L of deionized water, and warm rapidly to 80 ° C while stirring at a stirring speed of 300 rpm. Add the (NH4) 2SiF6 solution to the slurry of the molecular sieve at a constant rate of addition for 2 hours until 28.6.6 g (NH4) 2SiF6 is added; then stir for 2 hours at a constant stirring rate and at a constant temperature, then filter and dry; thus a product LYNS1 molecular sieve type H-Y is obtained. The properties of the product are shown in Table 2. Example 6 First, perform ammonium exchange for LY-2 of coarse-grain Na-Y molecular sieve. Prepare 10 L of 0.5 mol / L ammonium nitrate solution. Weigh 2000 g fine-grained Na-Y molecular sieve, dissolve it in 10 L of the ammonium nitrate solution prepared above, and shake for 1 h at a stirring speed of 300 rpm. min at 90 ° C; then filter the molecular sieve, and take samples to analyze the Na2O content; repeat the above operations until the Na 2 O content in the molecular sieve reaches 2.5% by weight; thus, a dried sample of LYN-2 is obtained. Weigh 200 g of molecular sieve LYN-2 and load it into a tubular hydrothermal treatment furnace, heat up to 500 ° C with programmed heating, and treat for 2 h at a pressure of 0.2 MPa; after the hydrothermal treatment, dissolve the molecular sieve in 1 L of deionized water, and warm rapidly to 75 ° C while stirring at a stirring speed of 300 rpm. Add the (NH4) 2SiF6 solution in the slurry of the molecular sieve at a constant rate of addition for 2 hours, until 24.6.6 g (NH4) 2SiF6 is added; then stir for 2 hours at a constant stirring rate and at a constant temperature, then filter and dry; thus, a LYNS-2 product of H-Y molecular sieve is obtained. The properties of the product are shown in Table 2.
    [0017] Example 7 First, perform ammonium exchange for LY-3 of coarse-grain Na-Y molecular sieve. Prepare 10 L of 0.5 mol / L ammonium nitrate solution. Weigh 2000 g fine-grained Na-Y molecular sieve, dissolve it in 10 L of the ammonium nitrate solution prepared above, and shake for 1 h at a stirring speed of 300 rpm at 90 ° C; then filter the molecular sieve, and take samples to analyze the Na2O content; repeat the above operations until the Na 2 O content in the molecular sieve reaches 2.5% by weight; thus, a dried sample of LYN-3 is obtained.
    [0018] Weigh 200 g of molecular sieve LYN-3 and load it into a tubular hydrothermal treatment furnace, heat up to 590 ° C with programmed heating, and treat for 2 h at a pressure of 0.3 MPa; after the hydrothermal treatment, dissolve the molecular sieve in 1 L of deionized water, and warm rapidly to 100 ° C while stirring at a stirring speed of 300 rpm Add the solution (NH4) 2SiF6 in the slurry molecular sieve at a constant rate of addition for 2 hours, until 38.6.6 g (NH4) 2SiF6 is added; then stir for 2 hours at a constant stirring rate and at constant temperature, filter and dry; thus, a LYNS-3 product of H-Y molecular sieve is obtained. The properties of the product are shown in Table 2. Example 8 First, perform ammonium exchange for LY-4 of coarse-grain Na-Y molecular sieve. Prepare 10 L of 0.5 mol / L ammonium nitrate solution. Weigh 2000 g fine-grained Na-Y molecular sieve, dissolve it in 10 L of the ammonium nitrate solution prepared above, and shake for 1 h at a stirring speed of 300 rpm at 90 ° C; then filter the molecular sieve, and take samples to analyze the Na2O content; repeat the above operations until the Na 2 O content in the molecular sieve reaches 2.5% by weight; thus, a dried sample of LYN-4 is obtained.
    [0019] Weigh 200 g of molecular sieve LYN-4 and load it into a tubular hydrothermal treatment furnace, heat up to 650 ° C with programmed heating, and treat for 1 hour at a pressure of 0.4 MPa; after the hydrothermal treatment, dissolve the molecular sieve in 1 L of deionized water, and warm rapidly to 120 ° C while stirring at a stirring speed of 300 rpm. Add the (NH4) 2SiF6 solution in the slurry of the molecular sieve at a constant rate of addition for 2 hours, until 67.6 g (NH4) 2SiF6 is added; then stir for 2 hours at a constant stirring rate and at a constant temperature, then filter and dry; thus, a LYNS-4 product of H-Y molecular sieve is obtained. The properties of the product are shown in Table 2. EXAMPLE 9 Load 111.1 g of molecular sieve LYNS-1 (90% by weight on a dry basis), 100 g of macropore alumina (1.0 mL pore volume) g / g, specific surface area of 400 m 2 / g, and 70% by weight on a dry basis), 100 g of binder (micropore alumina, with a pore volume of 0.40 to 0.56 ml / g, 30% by weight on a dry basis, and a molar ratio of nitric acid to micropore alumina equal to 0.4) in a mill for mixed grinding, add water and grind to a pasty state and spinning in strips; drying the strips spun for 4 h at 110 ° C and then calcining for 4 h at 550 ° C; thus, FHS-1 support is obtained.
    [0020] Impregnate the substrate with an impregnating liquid containing wolfram and nickel for 2 hours; then dry for 4 hours at 120 ° C, and heat up to 500 ° C with programmed heating and then calcine for 4 h; thus, a CATI catalyst is obtained. The carrier and catalyst compositions are shown in Table 3.
    [0021] Examples 10 to 12 Use the method described in Example 9, but replace "LYNS-1" with "LYNS-2", "LYNS-3", and "LYNS-4" respectively; thus, FHS-2, FHS-3 and FHS-4 supports and CAT-2, CAT-3 and CAT-4 catalysts are obtained, respectively. The compositions are shown in Table 3.
    [0022] Comparative Examples 5-8 Use the method described in Example 5, but replace "LY-1" with "DLY1", "DLY-2", "DLY-3" and "DLY-4" respectively; thus, molecular sieves of H-Y type DLYNS-1, DLYNS-2, DLYNS-3 and DLYNS-4 are obtained, respectively. The properties of the product are shown in Table 2. Use the method described in Example 9, but replace "LYNS-1" with "DLYNS-1", "DLYNS-2", "DLYNS-3" and "DLYNS- 4 "respectively; thus, DFHS-1, DFHS-2, DFHS-3 and DFHS-4 supports and DCAT-1, DCAT-2, DCAT-3 and DCAT-4 catalysts are obtained, respectively. The compositions of the supports and catalysts are shown in Table 3. EXAMPLE 13 Treat HLCO Low Quality Inlet Material and High-Dry VGO with CAT-1. The properties of the crude oils are listed in Table 4, and the comparative evaluation results of the hydrocracking catalysts are listed in Table 5 and Table 6. Examples 14-16 Use the method described in Example 13, but replace "CAT-1" with "CAT-2", "CAT-3" and "CAT-4" respectively. Comparative evaluation results of the hydrocracking catalysts are listed in Table 5 and Table 6. Comparative Examples 9-12 Using the method described in Example 13, but replacing "CAT-1" with "DCAT-1 "," DCAT-2 "," DCAT-3 "and" DCAT-4 "respectively. The comparative evaluation of the hydrocracking catalyst results are listed in Table 5 and Table 6.
    [0023] Table 1 Example No. LY-1 LY-2 LY-3 LY-4 Specific Surface Area, m2 / g 897 906 956 918 Pore Volume, cm3 / g 0.35 0.34 0.37 0.33 External surface area, m2 / g 80 75 82 79 Crystalline cell constant, nm 2,465 2,462 2,463 2,465 Relative crystallinity, in% 118 126 128 116 Average grain size,! Am 3.0 3.5 2.5 4, SiO 2 / Al 2 O 3 molar ratio 5.68 5.84 5.32 5.10 Sum of pore volumes with a diameter of 1 nm to 10 nm on total pore volume, in% 78 83 87 82 Relative crystallinity after calcination *, in% Relative Crystallinity after Hydrothermal Treatment *,% 108 112 115 104 Comparative Example No. DLY-1 DLY-2 DLY-3 DLY-4 Specific Surface Area, m 2 / g 840 820 738 719 Volume pore, cm3 / g 0.32 0.32 0.30 0.31 External surface area, m2 / g 150 132 121 110 Crystalline cell constant, nm 2,468 2,468 2,472 2,743 Relative crystallinity,% 96 146.7 92 102 Size average grain,! am 0.95 1.80 1.10 3.0 Ratio molar 5122 / A1203 4.21 4.35 5.10 5.17 Sum of pore volumes with a diameter of 1 nm to 10 nm on total pore volume, in% 51 56 43 29 Relative crystallinity after calcination *,% 69 81 44 79 Relative crystallinity after hydrothermal treatment *,% 70 70 76 58 Note: * The calcination conditions are: calcining for 3 hours at 600 ° C in air - * The hydrothermal treatment conditions are: treat for 1 hour at 650 ° C in steam. Table 2 Example # LYNS-1 LYNS-2 LYNS-3 LYNS-4 Specific Area Area, m2 / g 920 899 965 947 Pore Volume, cm3 / g 0.44 0.45 0.46 0.47 Crystalline cell constant, nm 2,440 2,442 2,433 2,428 Relative crystallinity, in% 133 130 136 143 Average grain size,! Am 3.0 3.0 3.0 3.0 Molar ratio 5i02 / A1203 33.5 28.4 69 , 8 105.6 Sum of pore volumes with a diameter of 3 nm to 7 nm on a total pore volume, in% 78 75 83 91 Percentage of the amount of non-skeletal aluminum on total aluminum content, in% 0, 3 0.1 0.2 0.1 Total amount of acid measured by NIS, mmol / g 0.67 0.75 0.42 0.28 Na 2 O,% by weight 0.12 0.10 0.10 0, 09 Comparative Example No. DYNS-1 DYNS-2 DYNS-3 DYNS-4 Specific Area Area, m2 / g 611 650 569 585 Pore Volume, cm3 / g 0.36 0.35 0.37 0.36 Crystalline cell constant, nm 2,443 2,439 2,429 2,431 Relative crystallinity,% 91 81 79 81 Average grain size,! Am 0.95 0.95 0.95 0.95 SiO 2 / Al 2 O 3 molar ratio 9.8 15.3 16 , 23 23.5 Sum of pore volumes with a diameter of 3 nm to 7 nm on a total pore volume, in% 29 32 36 33 Percentage of the amount of non-skeletal aluminum on total aluminum content, in% 1, 8 1.5 1.8 2.1 Total amount of acid measured by NIS, mmol / g 1.02 0.87 0.29 0.38 Na2 O,% by weight 0.16 0.18 0.116 0, Table 3 Examples Support FHS-1 FHS-2 FHS-3 FHS-4 Modified Y-type molecular sieve,% by weight 25.0 25.0 25.0 25.0 Macropore alumina,% by weight 40.0 40, 0 40.0 40.0 Binder,% wt. 35 35 Catalyst CAT-1 CAT-2 CAT-3 CAT-4 WO 3, wt% 22.50 22.51 22.48 22.49 NiO,% wt. weight 6.02 5.97 6.03 6.02 Comparative Examples Carrier DFHS-1 DFHS-2 DFHS-3 DFHS-4 Modified Y-type molecular sieve,% by weight 25.0 25.0 25.0 25.0 Macropore Alumina, wt.% 40.0 40.0 40.0 40.0 Binder, wt.% 35 Catalyst DCAT-1 DCAT-2 DCAT-3 DCAT-4 WO 3, wt% 22.48 22, 49 22.51 22.36 NiO, wt.% 6.01 6.02 5.99 5.87 Table 4 Raw Oil HLCO VGO Density ( at 20 ° C), g / cm3 0.9440 0.9096 Distillation range, E IBP / 10% 136/227 305/361 30% / 50% 252/275 394/417 70% / 90% 303/343 443 / 481 95% / EBP 357/371 509/533 Pour point, E-24 33 Cetane number 15 Cetane number (ASTMD 4737-96a) 23.8 S, wt% 0.81 1.98 N, 12.46 BMCI value 45.0 Table 5 Crude oil HLCO HLCO HLCO HLCO Catalyst CAT-1 DCAT-1 DCAT-2 914 1228 C, wt.% 89.70 85.28 H, wt% 9.40 12.46 DCAT-3 Total reaction pressure, MPa 14.7 14.7 14.7 14.7 Total LHSV, wire 1.2 1.2 1.2 1.2 Ratio of hydrogen to oil 1200: 1200: 1 1200: 1 1200: 1 Reaction temperature, E 385 390 401 393 Product distribution and main properties of the product Fraction <65 E Yield,% by weight 5.97 6.55 7.65 6.89 Octane number (RON ) 85.5 85.4 82.11 84.61 Fraction in the range of 65 ° C to 165 ° C Yield,% by weight 50.35 44.70 46.69 45.11 Aromatic potential,% by weight 75.5 72 , 1 68.5 70.3 Fraction> 165L11 Yield,% by weight 35.09 37.78 35 , 50 36.08 Cetane number (ASTMD 4737-96a) 41.8 38.3 37.5 39.1 Table 6 VGO crude oil VGO VGO VGO Catalyst in the example CAT-1 CAT-2 CAT-3 CAT- 4 LHSV, 1-11 1.0 1.0 1.0 1.0 Ratio of hydrogen to oil 1200: 1200: 1200: 1200: 1 Total reaction pressure, MPa 14.7 14.7 14.7 14.7 Reaction temperature, E 390 392 391 393 Yield yield and properties Naphtha heavy Yield,% 8.8 9.2 9.9 9.6 Aromatic potential,% by weight 62.7 61.5 62 , 9 61.9 Carboreactor Yield,% 23.1 23.8 23.8 24.3 Smoke point, mm 23 24 25 25 Aromatic, v% 10.0 9.8 8.7 8.6 Diesel fuel Efficiency ,% 35.5 34.6 34.1 34.0 Cetane number 62.0 63.0 65.0 65.0 Raw paraffins Yield,% 28.9 28.1 28.0 28.5 BMCI value 9.0 8.5 7.3 7.3 Chemical hydrogen consumption,% by weight 2.18 2.19 2.20 2.20 Liquid yield,% 98.4 98.3 98.3 98.2 Catalyst in Comparative Example DCAT-1 DCAT-2 DCAT-3 DCAT-4 LHSV, 1-11 1.0 1.0 1.0 1.0 Ratio of hydro gene / oil 1200: 1200: 1200: 1200: 1 Total reaction pressure, MPa 14.7 14.7 14.7 14.7 Reaction temperature, E 396 400 398 407 Yield yield and properties Naphtha heavy Yield, in% 9.9 10.6 10.5 11.2 Aromatic potential,% by weight 61.6 59.8 59.9 57.6 Carboreactor Yield,% 22.6 23.2 24.0 25.6 Point Smoke, mm 22 23 21 22 Aromatic, v% 12.5 11.8 15.6 14.7 Diesel fuel Yield,% 33.2 31.5 32.3 33.2 Cetane number 60.1 61, 2 59.6 57.3 Crude paraffins Yield,% 28.0 26.0 25.6 26.8 BMCI value 10.8 10.3 11.3 11.0 Chemical hydrogen consumption,% by weight 2, 24 2.32 2.30 2.36 Liquid yield, in% 97.6 97.1 96.8 96.8 From the examples, comparative examples, and data in Tables 5 to 6 it can be seen that: the performance of catalysts prepared from the coarse grain Na-Y molecular sieve proposed in the present invention in hydrocracking reactions are higher than those of catalysts prepared from comparative molecular sieves.
    权利要求:
    Claims (2)
    [0001]
    CLAIMS 1 ° / Na-Y type molecular sieve, wherein the mean grain diameter of the Na-Y type molecular sieve is 2 to 5 μm, and the sum of the pore volumes of diameter from 1 nm to 10 nm represents 70 to 90% of the total pore volume of the Na-Y molecular sieve.
    [0002]
    2. Na-Y type molecular sieve according to claim 1, wherein the average grain diameter is 2 to 4.5 μm, preferably 3 to 4.5 μm. 3. The Na-Y molecular sieve according to claim 1 or 2, wherein the sum of pore volumes of 1 to 10 nm in diameter represents 70 to 85% of the total pore volume of the Na-type molecular sieve. Y. 4. The Na-Y molecular sieve according to any one of claims 1 to 3, wherein the specific surface area of the Na-Y molecular sieve is 800 to 1000 m2 / g, the total pore volume. Na-Y molecular sieve is 0.3 to 0.4 mL / g, and the outer surface area of the Na-Y molecular sieve is 60 to 100 m 2 / g. 5. Na-Y type molecular sieve according to any one of claims 1 to 4, wherein the relative crystallinity of the Na-Y molecular sieve is 110 to 150%, and the crystal cell parameter of the Na-Y molecular sieve. Na-Y type is from 2.46 to 2.465 nm. 6. The Na-Y molecular sieve according to any of claims 1 to 5, wherein the molar ratio of SiO 2 / Al 2 O 3 in the Na-Y molecular sieve is 3.5 to 6.5: 1, preferably 4 to 6: 1. 3070 / A method for preparing a Na-Y molecular sieve as defined in any one of claims 1 to 6, comprising: (1) the sodium silicate mixture, the highly alkaline sodium metaaluminate solution , aluminum sulphate solution, and the weakly alkaline sodium metaaluminate solution in a molar ratio of Na 2 O: Al 2 O 3: SiO 2: 1120 equal to (10 to 15): 1: (10 to 20): (500 600), and the aging of the mixture obtained to obtain a gel; and (2) treating the gel obtained in step (1) by hydrothermal crystallization, and then drying, washing, and drying the gel after hydrothermal crystallization. The process according to claim 7, wherein in step (1), calculated in Al 2 O 3, the weight ratio of aluminum sulphate: highly alkaline sodium metaaluminate: sodium metaaluminate weakly alkaline is 1: ( 0.5 to 0.7): (0.6 to 0.8). 9 ° / A method according to claim 7 or 8, wherein in the solution of highly alkaline sodium metaaluminate, the Na20 content is 260 to 320 g / L, and the Al203 content is 30 to 50 g / L; in the weakly alkaline sodium metaaluminate solution, the Na 2 O content is 100 to 130 g / L, and the Al 2 O 3 content is 60 to 90 g / L; in the aluminum sulphate solution, the A1203 content is 80 to 100 g / L; in the sodium silicate, the SiO 2 content is 200 to 300 g / L, and the sodium silicate modulus is 2.8 to 3.5. 10 ° / A method according to any one of claims 7 to 9, wherein in step (1), the mixing temperature is 20 to 40 ° C, preferably is 25 to 35 ° C. A process according to any one of claims 7 to 10, wherein in step (1), sodium silicate, highly alkaline sodium metaaluminate solution, aluminum sulfate solution, and aluminum halide solution. The weakly alkaline sodium is mixed as follows: mixing the sodium silicate with the highly alkaline sodium metaaluminate solution while stirring, and then mixing the resulting mixture with the aluminum sulfate solution and the sodium metaaluminate solution weakly. alkaline. 12 ° / A method according to any one of claims 7 to 11, wherein in step (2), the gel is heated to the temperature for hydrothermal crystallization 2 to 4 ° C / min, and then is treated by hydrothermal crystallization. 13. Process according to any one of claims 7 to 12, wherein in step (2), the hydrothermal crystallization is carried out at a temperature of 80 to 120 ° C for 12 to 24 hours. 14 ° / Process for preparing a HY-type molecular sieve from a Na-Y molecular sieve as defined in any one of claims 1 to 6, comprising: (A) sieve treatment Na-Y type molecular molecule according to any one of claims 1 to 6 by ammonium exchange to prepare an NH 4 -Na-Y molecular sieve; (B) treating the N114-Na-Y molecular sieve obtained in step (A) by hydrothermal treatment; and (C) controlling the material obtained in step (B) to cause it to have a contact reaction with the (NH4) 2SiF6 solution. 15. The process according to claim 14, wherein in the NH4-Na-Y molecular sieve obtained in step (A), the Na 2 O content is 2.5 to 5% by weight. 16. The process according to claim 14, wherein in step (B) the hydrothermal treatment conditions comprise: gauge pressure: 0.05 to 0.25 MPa, preferably 0.1 to 0.2 MPa; temperature: 400 to 550 ° C, preferably 450 to 550 ° C; duration: 0.5 to 5 hours, preferably 1 to 3 hours. 17 ° / A method according to claim 16, wherein in step (C), the material obtained in step (B) is mixed with the solution (NH4) 2SiF6 in a weight ratio of liquid: solid equal to 3: 1 to 8: 1 from 70 to 90 ° C, then the resulting mixture is maintained at 80 to 120 ° C for 0.5 to 5 hours for the reaction, in which relative to 100 pbw of Na-Y molecular sieve the dosage of (NH4) 2SiF6 is from 10 to 35 pbw. 18. The process as claimed in claim 14, wherein in step (B), the hydrothermal treatment conditions comprise: gauge pressure: 0.28 to 0.5 MPa, preferably 0.3 to 0.5 MPa; temperature: 450 to 700 ° C, preferably 600 to 700 ° C; duration: 0.5 to 5 hours, preferably 1 to 3 hours. 19 ° / A method according to claim 18, wherein in step (C), the material obtained in step (B) is mixed with the solution (NH4) 2SiF6 in a weight ratio of liquid: solid equal to 8: 1 to 15: 1 of 95 to 130 ° C, then the resulting mixture is maintained at 80 to 120 ° C for 0.5 to 5 hours for the reaction, in which relative to 100 pbw of NH4-Na type molecular sieve -Y, the assay of (NH4) 2SiF6 is 35 to 80 pbw. 20 ° / H-Y molecular sieve prepared with the process of any one of claims 14 to 17, wherein the crystal cell parameter of the H-Y molecular sieve is from 2,436 to 2,450 nm; the molar ratio of SiO 2 / Al 2 O 3 in the H-Y molecular sieve is from 10 to 50: 1; the sum of pore volumes of 2 to 6 nm diameter in the H-Y molecular sieve is 60 to 90% of the total pore volume, preferably 70 to 85%; the specific surface area of the H-Y type molecular sieve is 750 to 950 m 2 / g; and the total amount of acid measured by near-infrared spectroscopy (NIS) in the H-Y molecular sieve is 0.5 to 1.0 mmol / g. 210 / HY-type molecular sieves prepared with the process of any one of claims 14, 15, 18, and 19, wherein the crystal cell parameter of the HY-type molecular sieve is 2.425 to 2.455 nm, preferably 2,427 to 2,434 nm; the molar ratio of SiO 2 / Al 2 O 3 in the H-Y molecular sieve is 60 to 120: 1; the sum of pore volumes of 3 to 7 nm diameter in the H-Y molecular sieve is 70 to 95% of the total pore volume, preferably 75 to 90%; the specific surface area of the H-Y molecular sieve is 800 to 980 m 2 / g; and the total amount of acid measured by near infrared spectroscopy in the H-Y molecular sieve is 0.1 to 0.5 mmol / g. 22 ° / hydrocracking catalyst, wherein the carrier in the catalyst contains the HY-type molecular sieve according to any one of claims 20 to 21. 23 ° / hydrocracking process, comprising: (a) hydro-pretreatment a crude oil in the presence of hydrogen gas and a pretreatment agent; and (b) hydrocracking the pretreated product obtained in step (a) in the presence of hydrogen gas and a hydrocracking catalyst; wherein the hydrocracking catalyst is the hydrocracking catalyst of claim 22.
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    GB2546614A|2017-07-26|
    US10525452B2|2020-01-07|
    GB2535584A|2016-08-24|
    US10265687B2|2019-04-23|
    US20160151771A1|2016-06-02|
    GB2535584B|2017-02-08|
    KR20160065761A|2016-06-09|
    GB2546614B|2019-02-13|
    CA2913269C|2018-10-09|
    CA2913269A1|2016-06-01|
    US20190168193A1|2019-06-06|
    KR101792229B1|2017-11-20|
    GB201621466D0|2017-02-01|
    FR3029189B1|2021-12-10|
    GB201520976D0|2016-01-13|
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    优先权:
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    CN201410711208.4A|CN105712368B|2014-12-01|2014-12-01|A kind of Y type molecular sieve and preparation method thereof|
    CN201410711228.1A|CN105621449B|2014-12-01|2014-12-01|A kind of NaY types molecular sieve and preparation method thereof|
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