WO2020082880A1 - 含磷高硅分子筛及其制备方法和应用 - Google Patents

含磷高硅分子筛及其制备方法和应用 Download PDF

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Publication number
WO2020082880A1
WO2020082880A1 PCT/CN2019/102008 CN2019102008W WO2020082880A1 WO 2020082880 A1 WO2020082880 A1 WO 2020082880A1 CN 2019102008 W CN2019102008 W CN 2019102008W WO 2020082880 A1 WO2020082880 A1 WO 2020082880A1
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Prior art keywords
molecular sieve
acid
phosphorus
weight
slurry
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PCT/CN2019/102008
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English (en)
French (fr)
Inventor
毛以朝
李明丰
龙湘云
张润强
赵阳
赵广乐
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority claimed from CN201811259943.0A external-priority patent/CN111097482B/zh
Priority claimed from CN201811261400.2A external-priority patent/CN111097491B/zh
Application filed by Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to US17/287,903 priority Critical patent/US12172903B2/en
Priority to KR1020217015911A priority patent/KR102709889B1/ko
Publication of WO2020082880A1 publication Critical patent/WO2020082880A1/zh
Anticipated expiration legal-status Critical
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
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    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof

Definitions

  • the present application relates to the technical field of molecular sieve and hydrocracking, in particular to a phosphorus-containing high-silicon molecular sieve, a hydrocracking catalyst containing it, and their preparation methods and applications.
  • Industrial hydrocracking feeds include heavy and inferior fractions such as VGO, containing large amounts of polycyclic aromatic hydrocarbons and naphthenes, and a large number of nitrogen-containing compounds.
  • the mass percentage of nitrogen in conventional hydrocracking feed is generally between 0.1-0.2%.
  • secondary oil refining processes such as coking and solvent deasphalting often generate large amounts of nitrogen-containing compounds.
  • the nitrogen content of the resulting materials often exceeds 0.3%, and some even reaches 0.6%. This makes the nitrogen content of conventional refined catalysts after treatment. The content is difficult to remove to a level of 10-100 ppm that conventional molecular sieve type hydrocracking catalysts can withstand.
  • weakly acidic amorphous silicon aluminum or silicon-containing alumina is used as the main acid component of the high nitrogen content hydrocracking catalyst.
  • a salt solution of silicon oxide and aluminum oxide is usually used to synthesize weakly acidic silicon aluminum at a low pH value, and there is also a method of grafting alumina on a silicon oxide precursor or grafting oxidation on an alumina precursor Silicon, and through further reaction to form silicon aluminum tetrahedron, thereby generating acidity in the sample.
  • Chinese patent ZL97121663.0 discloses a hydrocracking catalyst particularly suitable for producing middle distillate oil, containing amorphous silica-alumina component, small pore alumina binder, at least one group VIB element and at least A Group VIII element, the content of amorphous silica-alumina is 30-60% by weight, the total content of hydrogenated metal oxide is 20-35% by weight, and the balance is a small pore alumina binder, its characteristics
  • the specific surface of the catalyst is 150-300 m 2 / g, the pore volume is 0.25-0.50 mg / g, the pore distribution of 4-15 nm is 60-90%, and the infrared acidity is 0.30-0.50 mmol / g.
  • the purpose of the present application is to provide a phosphorus-containing high-silicon molecular sieve, a hydrocracking catalyst containing it, and their preparation method and application.
  • the molecular sieve used in the preparation of hydrocracking catalyst exhibits an improved performance in the presence of nitrogen-containing substances Hydrocracking activity.
  • the present application provides a phosphorus-containing high-silicon molecular sieve, calculated as oxides and based on the dry basis weight of the molecular sieve, the molecular sieve contains about 86.5-99.8% by weight of silicon 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, wherein 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 third strong peak The diffraction angle position is about 15.6-16.7 °,
  • the pore volume of the molecular sieve is about 0.20-0.50 mL / g, and the specific surface area is about 250-670 m 2 / g.
  • the present application provides a method for preparing a phosphorus-containing high-silicon molecular sieve.
  • the method includes the following steps:
  • the phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700 ° C, a pressure of about 0.1-8.0 MPa and the presence of water vapor for about 0.5-10 hours to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus-containing molecular sieve raw material is based on the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight, the sodium content is about 0.5-4.5% by weight, the silicon content is about 70-85% by weight, the aluminum content About 16.0-21.0% by weight;
  • step b) Add the hydrothermally-treated molecular sieve material obtained in step a) to make a first slurry, heat the first slurry to about 40-95 ° C, then maintain the temperature and add the first acid to the first slurry Solution, 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, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the first solid product is collected;
  • step b) Adding the first solid product obtained in step b) to a second slurry by adding water, heating the second slurry to about 40-95 ° C, then maintaining the temperature and adding 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, and then the reaction is carried out at a constant temperature for about 0.5-20 hours, and the second solid product is collected.
  • the present application provides the use of the phosphorus-containing high-silicon molecular sieve according to the present application in the hydrocracking reaction of hydrocarbon feedstock, including contacting the hydrocarbon feedstock with a hydrocracking catalyst including the phosphorus-containing high-silicon molecular sieve .
  • the present application provides a hydrocracking catalyst, based on the dry basis weight of the catalyst, the catalyst includes a support of about 45-90% by weight based on the dry basis weight, and about 1 based on the metal oxide -40% by weight of the first metal component, and about 1-15% by weight of the second metal component in terms of metal oxides;
  • the carrier includes a phosphorus-containing high-silicon molecular sieve and a heat-resistant inorganic oxide, and the weight ratio of the phosphorus-containing high-silicon molecular sieve and the heat-resistant inorganic oxide is about 0.03: 1 to about 20: 1;
  • the first metal component includes a group VIB metal
  • the second metal component includes a group VIII metal
  • the phosphorus-containing high-silicon molecular sieve is a phosphorus-containing high-silicon molecular sieve according to the present application.
  • the present application provides a method for preparing a hydrocracking catalyst, including the following steps:
  • the impregnation solution containing the first metal precursor and the second metal precursor is brought into contact with the carrier for impregnation.
  • the present application provides the use of the hydrocracking catalyst according to the present application in the hydrocracking reaction of hydrocarbon feedstock, including contacting the hydrocarbon feedstock with the hydrocracking catalyst.
  • This application uses phosphorus-containing molecular sieve raw materials for hydrothermal treatment and two-step pickling treatment under specific conditions to prepare a phosphorus-containing high-silicon molecular sieve with novel structural features.
  • the phosphorus-containing high-silicon molecular sieve of the present application shows an improved hydrocracking activity in the presence of nitrogen-containing substances when used in the preparation of hydrocracking catalysts.
  • the hydrocracking catalyst prepared by using the phosphorus-containing high silicon molecular sieve also has improved hydrocracking activity.
  • FIG. 1 shows the XRD spectrum of the molecular sieve prepared in Preparation Example 1-2 and Preparation Comparative Example 1-3.
  • any specific numerical value disclosed herein is not limited to the precise value of the numerical value, but should be understood to also cover values close to the precise value, such as within ⁇ 5% of the precise value All possible values.
  • between the endpoints of the range, between the endpoints and the specific point values in the range, and between the specific point values can be arbitrarily combined to obtain one or more new Numerical ranges, these new numerical ranges should also be considered as specifically disclosed herein.
  • 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.
  • any matters or matters not mentioned are directly applicable to those known in the art without any change.
  • any of the embodiments described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are considered as part of the original disclosure or original record of this application, and should not be It is regarded as new content that has not been disclosed or anticipated in this article, unless those skilled in the art consider that the combination is obviously unreasonable.
  • the present application provides a phosphorus-containing high-silicon molecular sieve, calculated as oxides and based on the dry basis weight of the molecular sieve, the molecular sieve contains about 86.5-99.8% by weight, preferably about 90-99.8% by weight % Silicon, about 0.1-13.5% by weight, preferably about 0.1-9.0% by weight aluminum, and about 0.01-6% by weight, preferably about 0.01-2.5% by weight phosphorus.
  • the molecular sieve may also contain a small amount of sodium, based on the oxide and based on the dry basis weight of the molecular sieve, the sodium content of the molecular sieve may be about 0.01-1.0% by weight, such as about 0.01 -0.6% by weight.
  • the phosphorus-containing high-silicon molecular sieve contains about 90-99.8% by weight of silicon, about 0.1-9.0% by weight of aluminum and about 0.01 in terms of oxides and based on the dry weight of the molecular sieve. -2.5% by weight of phosphorus.
  • the molecular sieve may also contain about 0.01-1.0% by weight, such as about 0.01-0.6% by weight of sodium, based on the oxide and based on the dry weight of the molecular sieve.
  • the phosphorus-containing high-silicon molecular sieve contains about 95.0-99.0% by weight silicon, about 0.5-5.0% by weight aluminum and about 0.1 in terms of oxides and based on the dry basis weight of the molecular sieve -1.0% by weight of phosphorus.
  • the molecular sieve may also contain about 0.01-0.6% by weight of sodium based on the oxide and based on the dry weight of the molecular sieve.
  • the pore volume of the molecular sieve may 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 ratio of the molecular sieve
  • the surface area may be about 250-670 m 2 / g, preferably about 260-600 m 2 / g, for example about 400-600 m 2 / g.
  • the molecular sieve has a pore volume of about 0.20-0.50 mL / g and a specific surface area of about 260-600 m 2 / g.
  • the molecular sieve has different structural characteristics from conventional silicon aluminum materials. Specifically, the molecular sieve has at least three diffraction peaks in the XRD spectrum, wherein the diffraction angle position of the first strong peak is about 5.9-6.9 °, preferably about 6.1-6.8 °; the diffraction angle position of the second strong peak At about 10.0-11.0 °, preferably at about 10.2-10.7 °; and the diffraction angle position of the third strongest peak is at about 15.6-16.7 °, preferably at about 15.8-16.5 °, where the diffraction angle position refers to diffraction in the XRD spectrum The peak value of the peak value of 2 ⁇ .
  • the ordinal numbers "first”, “second”, and “third” in the expression of the first, second, and third strong peaks, etc. represent the relative intensity of the diffraction peaks determined by the peak height Weak order, where the first strong peak represents the diffraction peak with the highest peak height in the XRD spectrum, the second strong peak represents the diffraction peak with the second highest peak height in the XRD spectrum, and the third strong peak represents the highest peak height in the XRD spectrum Three high diffraction peaks, and so on.
  • the D value can usually be calculated from the wavelength and the diffraction angle, and according to the strongest three diffraction peaks (ie The characteristics of the first strong peak, the second strong peak and the third strong peak in this application are used for preliminary identification of the phase.
  • the concept of the above three strong peaks can also be referred to the document "Research Methods of Heterogeneous Catalysts", edited by Yin Yuangen, Beijing: Chemical Industry Press, 1988, pages 140-170.
  • the XRD spectrum of the molecular sieve is I 1 / I 23.5-24.5 . It may be about 3.0-11.0, for example about 4.0-10.5 or about 4.6-10.1; I 2 / I 23.5-24.5 . It may be about 2.5-8.0, for example about 2.9-7.0 or about 3.0-6.4; I 3 / I 23.5-24.5 . It can be about 1.0-4.5, such as about 1.5-4.0 or about 2.1-3.8; where I 1 is the peak height of the first strong peak, I 2 is the peak height of the second strong peak, and I 3 is the The height of the third strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the molecular sieve XRD spectrum I 1 / I 23.5-24.5 . It can be about 3.0-11.0, I 2 / I 23.5-24.5 . It can be about 2.9-7.0, I 3 / I 23.5-24.5 . It can be about 1.0-4.0, where I 1 is the peak height of the first strong peak, I 2 is the peak height of the second strong peak, I 3 is the peak height of the third strong peak, I 23.5- 24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the molecular sieve XRD spectrum I 1 / I 23.5-24.5 . It can be about 4.0-10.5, I 2 / I 23.5-24.5 . It can be about 2.9-7.0, I 3 / I 23.5-24.5 . It can be about 1.5-4.0, where I 1 is the peak height of the first strong peak, I 2 is the peak height of the second strong peak, I 3 is the peak height of the third strong peak, I 23.5- 24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the molecular sieve has at least five diffraction peaks in the XRD spectrum, wherein the diffraction angle position of the fourth strongest peak may be about 20.4-21.6 °, preferably about 20.8-21.4 °, The diffraction angle position of the fifth strongest peak may be about 11.8-12.8 °, preferably about 12.1-12.6 °.
  • I 4 / I 23.5-24.5 It can be about 1.0-4.0, for example about 1.1-3.0 or about 1.2-2.3, I 5 / I 23.5-24.5 . It may be about 1.0-2.0, such as about 1.0-1.6 or about 1.0-1.2, where I 4 is the peak height of the fourth strongest peak and I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the concepts of the fourth strongest peak and the fifth strongest peak can be understood based on the introduction of the above three strongest peaks, which will not be repeated here.
  • I 4 / I 23.5-24.5 It can be about 1.1-3.0, I 5 / I 23.5-24.5 . It may be about 1.0-1.6, where I 4 is the peak height of the fourth strongest peak, I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the phosphorus-containing high-silicon molecular sieve of the present application When used to prepare a hydrocracking catalyst, it shows improved hydrocracking activity in the presence of a nitrogen-containing substance.
  • the present application provides a method for preparing a phosphorus-containing high-silicon molecular sieve.
  • the method includes the following steps:
  • the phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700 ° C, a pressure of about 0.1-8.0 MPa and the presence of water vapor for about 0.5-10 hours to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus-containing molecular sieve raw material is based on the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight, the sodium content is about 0.5-4.5% by weight, the silicon content is about 70-85% by weight, the aluminum content About 16.0-21.0% by weight;
  • step b) Add the hydrothermally-treated molecular sieve material obtained in step a) to make a first slurry, heat the first slurry to about 40-95 ° C, then maintain the temperature and add the first acid to the first slurry Solution, 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, preferably about 2.5-4.0, and then the reaction is carried out at a constant temperature for about 0.5-20h, and the first solid product is collected; as well as
  • step b) Adding the first solid product obtained in step b) to a second slurry by adding water, heating the second slurry to about 40-95 ° C, then maintaining the temperature and adding 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, preferably about 1.0-2.0, and then the reaction is carried out at a constant temperature for about 0.5-20 hours, and the second solid product is collected.
  • the method for preparing a phosphorus-containing high-silicon molecular sieve includes the following steps:
  • the raw material of the phosphorus-containing molecular sieve is hydrothermally treated at a temperature of about 400-650 ° C, for example about 560 ° C, at a pressure of about 0.5-5MPa, for example about 0.8MPa and in the presence of water vapor for about 1-7h, for example about 3h, Hydrothermally-treated molecular sieve material; based on oxides and based on the dry basis weight of the phosphorus-containing molecular sieve material, the phosphorus content of the phosphorus-containing molecular sieve material is about 0.1-6% by weight, such as about 1.37% by weight, and the sodium content is About 0.5-3.0% by weight, for example about 1.44% by weight, the silicon content is about 70-80% by weight, for example about 67.7% by weight, and the aluminum content is about 18.0-21.0% by weight, for example about 20.5% by weight;
  • step b) Add the hydrothermally-treated molecular sieve material obtained in step a) to make a first slurry, heat the first slurry to about 50-85 ° C, for example about 80 ° C, then maintain the temperature and apply to the first slurry A first acid solution is added to the solution, and the amount of the first acid solution added is such that the resulting acid-added first slurry has a pH value of about 2.5-3.5, such as about 2.8, and then a constant temperature reaction is performed for about 1-10 hours, such as about 4 hours. To collect the first solid product; and
  • step b) Adding the first solid product obtained in step b) to a second slurry by adding water, heating the second slurry to about 50-85 ° C, for example about 80 ° C, then maintaining the temperature and adding to the second slurry A second acid solution, the amount of the second acid solution added is such that the resulting acid-added second slurry has a pH value of preferably about 1.0-1.8, such as about 1.4, and then a constant temperature reaction is performed for about 1-10 hours, such as about 3 hours, The second solid product was collected.
  • the phosphorus-containing molecular sieve raw material refers to a phosphorus-containing molecular sieve.
  • This application uses phosphorus-containing molecular sieve raw materials.
  • the phosphorous aluminum species outside the molecular sieve framework can improve the stability of the molecular sieve framework, thereby further improving the performance of the molecular sieve.
  • the phosphorus-containing molecular sieve material may have a faujasite molecular sieve structure, preferably a phosphorus-containing Y-type molecular sieve, the unit cell constant may be about 2.425-2.47nm, for example about 2.456nm, and the specific surface area may be about 250-750m 2 / g, for example, about 672 m 2 / g, and the pore volume may be about 0.2-0.95 mL / g, for example, about 0.357 mL / g.
  • the specific selection of the Y-type molecular sieve can be varied within a wide range, as long as the phosphorus-containing molecular sieve raw material satisfies the above conditions.
  • the Y-type molecular sieve may be selected from NaY, HNaY (hydrogen Y-type molecular sieve), REY (rare-earth Y-type molecular sieve), USY (ultra-stable Y-type molecular sieve), and the like.
  • the cation site of the phosphorus-containing Y-type molecular sieve may be occupied by one or more of sodium ions, ammonium ions, and hydrogen ions; or it may be, before or after the molecular sieve is introduced with phosphorus, through a conventional ion Exchange, so that all or part of the sodium ions, ammonium ions and hydrogen ions are replaced by other ions.
  • the raw material of the phosphorus-containing molecular sieve may be a commercially available product, or may be prepared by any existing technology, for example, the method for preparing USY disclosed in Chinese Patent ZL00123139.1 or the preparation of PUSY disclosed in Chinese Patent ZL200410071122.6 Methods and other preparations will not be repeated in this application.
  • step b) and step c) of beating with water is well known to those skilled in the art.
  • the ratio of the weight of water in the first slurry obtained after beating to the dry basis weight of the phosphorus-containing molecular sieve raw material may be about 14: 1 to about 5: 1, for example About 10: 1; and / or step c), the ratio of the weight of water in the second slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material may be about 0.5: 1 to about 20: 1, for example about 10: 1 .
  • the first slurry in step b), is heated to about 50-85 ° C, for example about 80 ° C, then the temperature is maintained and the first slurry is continuously added to the first slurry
  • the acid solution stops until the pH value of the first slurry after the acid addition reaches the desired size.
  • the amount of the first acid solution added can vary within a wide range. Those skilled in the art can understand that the amount of the first acid solution added is satisfactory as long as the pH value of the first slurry after the acid addition meets the above-mentioned suitable range.
  • the addition rate of the first acid solution is not particularly limited, and can be varied within a relatively wide range.
  • the operation of adding the first acid solution may be performed multiple times (for example, 1-5 times), and each time the acid is added, the reaction may be performed at a constant temperature for a period of time. Continue the next acid addition until the pH of the first slurry after the acid addition reaches the required range.
  • the acid concentration of the first acid solution may 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 may be about 0.01-3.
  • the acid in the first acid solution may be a conventional inorganic acid and / or organic acid, for example, it may be at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid, It is preferably selected from sulfuric acid and nitric acid.
  • the second slurry in step c), is heated to about 50-85 ° C, for example about 80 ° C, then the temperature is maintained and the second slurry is continuously added to the second slurry
  • the acid solution stops until the pH value of the second slurry after the acid addition reaches the required size.
  • the manner of adding the second acid solution may be: based on 1L of the second slurry, based on H + , according to about 0.05-15mol / h, preferably about 0.05-10mol / h, more preferably about 2-8mol / h. Add the second acid solution to the second slurry at a rate of, for example, about 5 mol / h. According to the present application, using a slower acid addition rate in step c) can make the dealumination process more gentle, which is beneficial to improve the performance of the molecular sieve.
  • the operation of adding the second acid solution may be performed multiple times (for example, 1-5 times), and each time the acid is added, the reaction may be performed at a constant temperature for a period of time. Continue the next acid addition until the pH of the second slurry after the acid addition reaches the required range.
  • the acid concentration of the second acid solution may 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 may be about 0.01-3.
  • the acid in the second acid solution may be a conventional inorganic acid and / or organic acid, for example, it may be at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid, It is preferably selected from sulfuric acid and nitric acid.
  • the type and concentration of the second acid solution and the first acid solution may be the same or different, preferably the same acid solution.
  • the method may further include: collecting the second solid product, followed by washing with water and drying to obtain the phosphorus-containing high-silicon molecular sieve.
  • the water washing and drying are conventional steps for preparing molecular sieves, and the present application is not particularly limited.
  • the drying may be performed by oven, mesh belt, converter heating, etc.
  • the drying conditions may be: temperature about 50-350 ° C, preferably about 70-200 ° C, for example about 180 ° C; time about 1-24h, preferably About 2-6h, for example about 3h.
  • phosphorus-containing molecular sieve materials are used for specific hydrothermal treatment and two-step pickling treatment, so that a phosphorus-containing high-silicon molecular sieve with novel structural characteristics can be prepared.
  • the phosphorus-containing high-silicon molecular sieve provided in this application can be used as a variety of acid-catalyzed catalysts in catalytic cracking, hydro-isomerization, alkylation, hydrocracking and other reactions, and is particularly suitable for hydrocracking hydrocarbon feedstocks , To produce hydrocarbon fractions with lower boiling points and lower molecular weights.
  • the present application provides the application of the phosphorus-containing high-silicon molecular sieve according to the present application in the hydrocracking reaction of hydrocarbon feedstocks, including the hydrogenation of hydrocarbon feedstock and the phosphorus-containing high-silicon molecular sieve Cracking catalyst contact.
  • the hydrocarbon raw material may 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 residues, deasphalted vacuum residues, coker distillates, catalytic crackers distillates, cat Rock oil (shale oil), asphalt sand oil (tar sand oil), coal liquefied oil (coal liquid), etc.
  • the catalyst based on the phosphorus-containing high-silicon molecular sieve of the present application is particularly suitable for the hydrocracking of heavy and inferior distillate oils to produce distillation ranges of about 149-371 ° C, especially those with a distillation range of about 180-370 ° C The process of hydrocracking middle distillates.
  • the hydrocracking reaction may be one or more of hydrocracking reactions carried out in conventional equipment such as fixed bed, ebullated bed, slurry bed, and suspended bed.
  • the catalyst based on the phosphorus-containing high-silicon molecular sieve of the present application when used for distillate hydrocracking, it can be used under conventional hydrocracking process conditions.
  • the conditions of the hydrocracking reaction may be: the reaction temperature is about 200-650 ° C, preferably about 300-510 ° C, the reaction pressure is about 3-24MPa, preferably about 4-15MPa, and the liquid hourly space velocity is about 0.1-50h -1 , Preferably about 0.2-30h -1 , hydrogen oil volume ratio is about 100-5000.
  • the present application provides a hydrocracking catalyst, based on the dry basis weight of the catalyst, the catalyst comprising a support of about 45-90% by weight, such as about 60-90% by weight, based on the dry basis weight , About 1-40% by weight of the first metal component, such as about 5-35% by weight of the metal oxide, and about 1-15% by weight, such as about 2-12% by weight of the metal oxide The second metal component.
  • the carrier comprises a phosphorus-containing high-silicon molecular sieve and a heat-resistant inorganic oxide according to the present application, and the weight ratio of the phosphorus-containing high-silicon molecular sieve and 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 contains a Group VIB metal; the second metal component contains a Group VIII metal.
  • the use of the heat-resistant inorganic oxide can improve the strength of the catalyst and improve and adjust the physical and chemical properties of the catalyst, such as the pore structure of the catalyst.
  • the heat-resistant inorganic oxide may be an inorganic oxide commonly used in hydrogenation catalyst supports, such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, thorium oxide, beryllium oxide, oxide Boron and cadmium oxide.
  • the heat-resistant inorganic oxide is alumina
  • the alumina may include gibbsite, such as gibbsite, bayerite and gibbsite (bayeritenordstrandite), And gibbsite such as boehmite (boehmite, diaspor, pseudoboehmite).
  • the first metal is selected from molybdenum components, tungsten components, and any combination thereof; and / or, the second metal component is selected from iron components, nickel groups Components, cobalt components, and any combination of them.
  • the present application provides a method of preparing a hydrocracking catalyst of the present application, the method comprising the following steps:
  • the contact impregnation method of the impregnating liquid and the carrier may adopt any method known to those skilled in the art, for example, the method disclosed in Chinese Patent ZL200810241082.3, which includes the group VIB metal component, the group VIII Group metal components and organic additives are supported on the catalyst carrier.
  • the preparation method of the carrier is well known to those skilled in the art, and the present application is not particularly limited.
  • the method may include: mixing the phosphorus-containing high-silicon molecular sieve according to the present application with a heat-resistant inorganic oxide, and then shaping and drying to obtain the carrier.
  • the molding method may use conventional various methods, such as tablet molding, ball molding, or extrusion molding.
  • the carrier in the present application, may be spherical, strip-shaped, hollow strip-shaped, spherical, block-shaped, etc., and the strip-shaped carrier may be multi-leaf clover-shaped such as clover-shaped, four-leaf clover, and the like Deformation body.
  • the first metal precursor is a compound containing the first metal that is soluble in the impregnating solution, including but not limited to the inorganic acid of the first metal, the first At least one of an inorganic salt of a metal, an oxide of a first metal, and an organic compound of a first metal;
  • the inorganic salt may be selected from the group consisting of nitrate, carbonate, basic carbonate, hypophosphite, and phosphate , At least one of sulfate and chloride;
  • the organic substituent in the first metal organic compound may be at least one selected from the group consisting of hydroxyl group, carboxyl group, amine group, ketone group, ether group and alkyl group.
  • the first metal precursor when the first metal is molybdenum, may be at least one selected from molybdic acid, para-molybdic acid, molybdate, para-molybdate and molybdenum oxide; when the 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. Species.
  • the second metal precursor is a compound containing the second metal that is soluble in the impregnating solution, including but not limited to an inorganic acid of the second metal, a second At least one of an inorganic salt of a metal, an oxide of a second metal, and an organic compound of a second metal;
  • the inorganic salt may be selected from nitrate, carbonate, basic carbonate, hypophosphite, phosphate , At least one of sulfate and chloride;
  • the organic substituent in the second metal organic compound may be at least one selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether and alkyl.
  • the impregnating solution may further contain organic additives, and the concentration of the organic additives may be about 2-300 g / L.
  • the organic additive may be an oxygen-containing organic compound and / or a nitrogen-containing organic compound.
  • the oxygen-containing organic compound may be selected from ethylene glycol, glycerin, polyethylene glycol (the molecular weight may be about 200-1500), diethylene glycol, butylene glycol, acetic acid, maleic acid, At least one of oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid;
  • the nitrogen-containing organic compound may be selected from ethylenediamine, diethylenetriamine At least one of amine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and ethylenediaminetetraacetic acid ammonium.
  • the temperature of the contact impregnation is not particularly limited, and may be various temperatures that can be achieved by the impregnation solution used.
  • the time of impregnation is also not particularly limited, as long as the catalyst carrier can be loaded with the required amount of the metal active component precursor.
  • the impregnation may be saturated impregnation or supersaturated impregnation.
  • the environment for the impregnation is not particularly limited. According to the conventional methods in the art, it may be carried out under sealed conditions or in an open environment, and the water solvent lost during the impregnation process may or may not be replenished.
  • gases such as air, nitrogen, water vapor, etc. can be introduced during the impregnation process, or no new components can be introduced.
  • the method for preparing a hydrocracking catalyst of the present application may further include the steps of drying and calcining the material obtained after the impregnation.
  • the drying and roasting are conventional steps for preparing the catalyst. limits.
  • the drying conditions may be: a temperature of about 80-350 ° C, preferably about 100-300 ° C, and a time of about 0.5-24h, preferably about 1-12h.
  • the firing conditions may be: a temperature of about 350-600 ° C, preferably about 400-550 ° C; a time of about 0.2-12h, preferably about 1-10h.
  • the hydrocracking catalyst provided by this application can be used as various acid-catalyzed catalysts in catalytic cracking, hydro-isomerization, alkylation, hydrocracking and other reactions, and is particularly suitable for hydrocracking hydrocarbon feedstocks. Production of hydrocarbon fractions with lower boiling points and lower molecular weights.
  • the present application provides the use of the hydrocracking catalyst according to the present application in the hydrocracking reaction of hydrocarbon feedstock, including contacting the hydrocarbon feedstock with the hydrocracking catalyst.
  • the hydrocarbon raw material may 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 residues, deasphalted vacuum residues, coker distillates, catalytic crackers distillates, cat Rock oil (shale oil), asphalt sand oil (tar sand oil), coal liquefied oil (coal liquid), etc.
  • the catalyst provided by the present application may be suitable for the hydrocracking of heavy and inferior distillate oils to produce middle distillate oils with a distillation range of about 149-371 ° C, especially about 180-370 ° C Cracking process.
  • the hydrocracking catalyst provided by the present application When the hydrocracking catalyst provided by the present application is applied to the hydrocracking reaction of hydrocarbon feedstock, it preferably further includes the use of the hydrocracking catalyst at a temperature of about 140-370 ° C in the presence of hydrogen before using the hydrocracking catalyst.
  • Sulfur, hydrogen sulfide, or sulfur-containing feedstock presulfurizes the hydrocracking catalyst. This presulfurization can be carried out outside the reactor or in situ within the reactor to convert the catalyst to a sulfide type .
  • the catalyst provided by the present application When the catalyst provided by the present application is used for distillate hydrocracking, it can be used under conventional hydrocracking process conditions.
  • the conditions of the hydrocracking reaction may be: reaction temperature about 200-650 ° C, preferably about 300-510 ° C; reaction pressure about 3-24MPa, preferably about 4-15MPa; liquid hourly space velocity about 0.1-50h -1 , Preferably about 0.2-30h -1 ; Hydrogen oil volume ratio is about 100-5000.
  • the hydrocracking reaction may be carried out in any device sufficient to contact and react the hydrocarbon feedstock with the catalyst under hydrogenation reaction conditions, and the device may be, for example, a fixed bed reactor, a moving bed reactor, Ebullated bed reactor or slurry bed reactor.
  • the present application provides the following technical solutions:
  • a phosphorus-containing high-silicon molecular sieve based on the oxide and based on the dry basis weight of the molecular sieve, 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 phosphorus,
  • the XRD spectrum of the molecular sieve has at least three diffraction peaks, wherein 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 third strong peak The diffraction angle position is about 15.6-16.7 °,
  • the pore volume of the molecular sieve is about 0.20-0.50 mL / g, and the specific surface area is about 260-600 m 2 / g.
  • the phosphorus-containing high-silicon molecular sieve according to any one of the preceding items, wherein the molecular sieve has at least five diffraction peaks in the XRD spectrum, wherein the diffraction angle position of the fourth strongest peak is about 20.4-21.6 °, The diffraction angle position of the fifth strongest peak is about 11.8-12.8 °.
  • I 4 / I 23.5-24.5 It is about 1.0-4.0, I 5 / I 23.5-24.5 . It is about 1.0-2.0, where I 4 is the peak height of the fourth strongest peak, and I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • a method for preparing phosphorus-containing high-silicon molecular sieve including the following steps:
  • the phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700 ° C, a pressure of about 0.1-8.0 MPa and the presence of water vapor for about 0.5-10 hours to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus-containing molecular sieve raw material is based on the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight, the sodium content is about 0.5-4.5% by weight, the silicon content is about 70-85% by weight, the aluminum content About 16.0-21.0% by weight;
  • step b) The hydrothermally treated molecular sieve material obtained in step a) is beaten with water to obtain a first slurry, which is heated to about 40-95 ° C, preferably about 50-85 ° C, and then the temperature is maintained The first acid solution is added to the first slurry, and the amount of the first acid solution is added so that the pH value of the obtained acid-added first slurry is about 2.5-4, and then the constant temperature reaction is about 0.5-20h, and the first solid is collected Products; and
  • step c) Pulp the first solid product obtained in step b) with water to obtain a second slurry, heat the second slurry to about 40-95 ° C, preferably about 50-85 ° C, and then maintain the temperature to the second A second acid solution is added to the slurry, and the amount of the second acid solution is added so that the pH value of the resulting acid-added second slurry is about 1.0-2.0, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the second solid product is collected.
  • step a) the raw material of the phosphorus-containing molecular sieve is a phosphorus-containing Y-type molecular sieve, and the unit cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm,
  • the specific surface area is about 250-750 m 2 / g, and the pore volume is about 0.2-0.95 mL / g.
  • step b) The method according to item A6 or A7, wherein in step b), the ratio of the weight of water in the first slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material is about 14: 1 to about 5: 1.
  • step c) the ratio of the weight of water in the second slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material is about 0.5: 1 to about 20: 1.
  • step c) the method of adding the second acid solution is: taking 1 L of the second slurry as a reference, based on H + , according to 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.
  • the acid concentration of the first acid solution is about 0.01-15.0 mol / L, preferably about 0.1-5.0 mol / L
  • 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,
  • the acid concentration of the second acid solution is about 0.01-15.0mol / L, preferably about 0.1-5.0mol / L, and the acid in the second acid solution is selected from phosphoric acid, sulfuric acid, nitric acid, At least one of hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid is preferably selected from sulfuric acid and nitric acid.
  • A12 The method according to any one of items A6 to A11, further comprising: collecting the second solid product, followed by washing with water and drying to obtain the phosphorous-containing silicoaluminum molecular sieve; preferably, the dried
  • the conditions are: a temperature of about 50-350 ° C, preferably about 70-200 ° C; a time of about 1-24h, preferably about 2-6h.
  • a phosphorus-containing high-silicon molecular sieve prepared by the method described in any one of items A6 to A12.
  • hydrocarbon raw material is straight-run gas oil, vacuum gas oil, demetalized oil, atmospheric residue, deasphalted vacuum residue, coking distillate oil, and catalytic cracking Distillate oil, shale oil, asphalt sand oil or coal liquefied oil, or a combination of two or more of them; and / or,
  • the conditions of the hydrocracking reaction are: the reaction temperature is about 200-650 ° C, preferably about 300-510 ° C; the reaction pressure is about 3-24MPa, preferably about 4-15MPa; the liquid hourly space velocity is about 0.1-50h -1 , preferably about 0.2-30h -1 ; Hydrogen oil volume ratio is about 100-5000.
  • a hydrocracking catalyst based on the dry basis weight of the catalyst, the catalyst includes about 45-90% by weight of the carrier based on the dry basis weight, and about 1-40% by weight of the first metal based on the metal oxide Components, and about 1-15% by weight of the second metal component based on the metal oxide;
  • the carrier includes a phosphorus-containing high-silicon molecular sieve and a heat-resistant inorganic oxide, and the weight ratio of the phosphorus-containing high-silicon molecular sieve and the heat-resistant inorganic oxide is about 0.03: 1 to about 20: 1;
  • the first metal component includes a Group VIB metal
  • the second metal component includes a Group VIII metal
  • the phosphorus-containing high-silicon 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.
  • the XRD spectrum of the phosphorus-containing high-silicon molecular sieve has at least three diffraction peaks, where 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 third The diffraction angle position of the strong peak is about 15.6-16.7 °.
  • the pore volume of the phosphorus-containing high-silicon molecular sieve is about 0.20-0.50 mL / g, and the specific surface area is about 260-600 m 2 / g.
  • A19 The hydrocracking catalyst according to any one of items A16 to A18, wherein the XRD spectrum of the phosphorus-containing high-silicon molecular sieve has at least five diffraction peaks, where the diffraction angle of the fourth strongest peak is at About 20.4-21.6 °, the diffraction angle of the fifth strongest peak is about 11.8-12.8 °.
  • I 4 / I 23.5-24.5 It is about 1.0-4.0, I 5 / I 23.5-24.5 . It is about 1.0-2.0, where I 4 is the peak height of the fourth strongest peak, and I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • hydrocracking catalyst according to any one of items A16 to A20, wherein the phosphorus-containing high-silicon molecular sieve is prepared by a method including the following steps:
  • the phosphorus-containing molecular sieve raw material is subjected to hydrothermal treatment at a temperature of about 350-700 ° C, a pressure of about 0.1-8.0 MPa and the presence of water vapor for about 0.5-10 hours to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus-containing molecular sieve raw material is based on the phosphorus content of the phosphorus-containing molecular sieve raw material is about 0.1-15% by weight, the sodium content is about 0.5-4.5% by weight, the silicon content is about 70-85% by weight, the aluminum content About 16.0-21.0% by weight;
  • step b) The hydrothermally treated molecular sieve material obtained in step a) is beaten with water to obtain a first slurry, which is heated to about 40-95 ° C, preferably about 50-85 ° C, and then the temperature is maintained The first acid solution is added to the first slurry, and the amount of the first acid solution is added so that the pH value of the obtained acid-added first slurry is about 2.5-4, and then the constant temperature reaction is about 0.5-20h, and the first solid is collected Products; and
  • step c) Pulp the first solid product obtained in step b) with water to obtain a second slurry, heat the second slurry to about 40-95 ° C, preferably about 50-85 ° C, and then maintain the temperature to the second A second acid solution is added to the slurry, and the amount of the second acid solution is added so that the pH value of the resulting acid-added second slurry is about 1.0-2.0, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the second solid product is collected.
  • step a) The hydrocracking catalyst according to item A21, wherein in step a), the raw material of the phosphorus-containing molecular sieve is a phosphorus-containing Y-type molecular sieve, and the unit cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425- 2.47nm, a specific surface area of about 250-750m 2 / g, a pore volume of from about 0.2-0.95mL / g.
  • the hydrocracking catalyst according to any one of items A21 to A23, wherein in step c), the ratio of the weight of water in the second slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material is about 0.5: 1 to about 20: 1.
  • step c) The hydrocracking catalyst according to any one of items A21 to A24, wherein in step c), the manner of adding the second acid solution is: taking 1 L of the second slurry as a reference, taking H + In total, 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.
  • the acid concentration of the first acid solution is about 0.01-15.0mol / L, preferably about 0.1-5.0mol / L
  • 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,
  • the acid concentration of the second acid solution is about 0.01-15.0mol / L, preferably about 0.1-5.0mol / L, and the acid in the second acid solution is selected from phosphoric acid, sulfuric acid, nitric acid, At least one of hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid and acetic acid is preferably selected from sulfuric acid and nitric acid.
  • thermofracracking catalyst according to any one of items A21 to A27, wherein the heat-resistant inorganic oxide is alumina, silica, titania, zirconia, magnesia, thorium oxide, beryllium oxide, oxidation Boron or cadmium oxide, or a combination of two or more of them; and / or,
  • the first metal component is a molybdenum component and / or a tungsten component; the second metal component is an iron component, a nickel component or a cobalt component, or a combination of two or more .
  • a method for preparing a hydrocracking catalyst according to any one of items A16 to A28 comprising: a step of contacting an impregnating solution containing a first metal precursor and a second metal precursor with a carrier for impregnation, wherein The carrier includes the phosphorus-containing high-silicon molecular sieve and a heat-resistant inorganic oxide.
  • A30 The method according to item A29, further comprising the steps of mixing the phosphorus-containing high-silicon molecular sieve with a heat-resistant inorganic oxide, and then forming, drying, and baking to obtain the carrier.
  • A31 The method according to item A29 or A30, wherein the first metal precursor is an inorganic acid of the first metal, an inorganic salt of the first metal, or a first metal organic compound; the inorganic salt is selected from nitrates , Carbonate, basic carbonate, hypophosphite, phosphate, sulfate and chloride are at least one; the organic substituent in the first metal organic compound is selected from hydroxyl, carboxyl, amine , At least one of keto, ether and alkyl; and / or,
  • the second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organic compound of the second metal;
  • the inorganic salt is selected from the group consisting of nitrate, carbonate, basic carbonate, and hypophosphorous acid At least one of salt, phosphate, sulfate and chloride;
  • the organic substituent in the second metal organic compound is at least one selected from the group consisting of hydroxyl, carboxyl, amine, ketone, ether and alkyl Species.
  • A32 The method according to any one of items A29 to A31, further comprising the steps of drying and roasting the material obtained after impregnation;
  • the drying conditions are: temperature about 80-350 ° C, preferably about 100-300 ° C, time about 0.5-24h, preferably about 1-12h; and / or,
  • the conditions for the calcination are: a temperature of about 350-600 ° C, preferably about 400-550 ° C, and a time of about 0.2-12h, preferably about 1-10h.
  • hydrocarbon raw material is straight-run gas oil, vacuum gas oil, demetalized oil, atmospheric residue, deasphalted vacuum residue, coking distillate oil, catalytic cracking Distillate oil, shale oil, asphalt sand oil or coal liquefied oil, or a combination of two or more of them; and / or,
  • the conditions of the hydrocracking reaction are: the reaction temperature is about 200-650 ° C, preferably about 300-510 ° C; the reaction pressure is about 3-24MPa, preferably about 4-15MPa; the liquid hourly space velocity is about 0.1-50h -1 , preferably about 0.2-30h -1 ; Hydrogen oil volume ratio is about 100-5000.
  • a phosphorus-containing high-silicon molecular sieve characterized in that the molecular sieve has a pore volume of about 0.20-0.50 mL / g and a specific surface area of about 260-600 m 2 / g. Based on the dry basis weight, the silicon content of the molecular sieve is about 90-99.8% by weight, the aluminum content is about 0.1-9.0% by weight, and the phosphorus content is about 0.01-2.5% by weight;
  • the first strong peak has a diffraction angle position of about 5.9-6.9 °
  • the second strong peak has a diffraction angle position of about 10.0-11.0 °
  • the third strong peak has a diffraction angle position of about 15.6 -16.7 °.
  • I 4 / I 23.5-24.5 It is about 1.0-4.0, I 5 / I 23.5-24.5 . It is about 1.0-2.0, where I 4 is the peak height of the fourth strongest peak, and I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the raw material of phosphorus-containing molecular sieve is hydrothermally treated at a temperature of about 350-700 ° C., a pressure of about 0.1-2 MPa and the presence of water vapor for about 0.5-10 h, to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus molecular sieve raw material is based on 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;
  • step b) The hydrothermally treated molecular sieve material obtained in step a) is beaten with water to obtain a first slurry, the first slurry is heated to about 40-95 ° C, and then the temperature is maintained and the first slurry is added to the first slurry An acid solution, the amount of the first acid solution added is such that the resulting acid-added first slurry has a pH of about 2.5-4, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the first solid product is collected;
  • step c) Pulp the first solid product obtained in step b) with water to obtain a second slurry, heat the second slurry to about 40-95 ° C, then maintain the temperature and continuously add the second acid to the second slurry
  • the amount of the second acid solution added is such that the pH of the resulting acid-added second slurry is about 1.0-2.0, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the second solid product is collected.
  • step a) the raw material of the phosphorus-containing molecular sieve is a phosphorus-containing Y-type molecular sieve, and the unit cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, the ratio The surface area is about 250-750 m 2 / g, and the pore volume is about 0.2-0.95 mL / g.
  • step b) The method according to item B6, wherein in step b), the ratio of the weight of water in the first slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material is about 14: 1 to about 5: 1.
  • step c) the ratio of the weight of water in the second slurry to the dry basis weight of the phosphorus-containing molecular sieve raw material is about 0.5: 1 to about 20: 1.
  • step c) the method of adding the second acid solution is as follows: based on 1 L of the second slurry, based on H + , according to about 0.05-10 mol / h Add the second acid solution to the second slurry at a rate.
  • 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 selected from phosphoric acid, sulfuric acid, At least one of nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid; and / or,
  • the acid concentration of the second acid solution is about 0.01-15.0mol / L, and the acid in the second acid solution is selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, At least one of formic acid and acetic acid.
  • hydrocarbon raw material is straight-run gas oil, vacuum gas oil, demetalized oil, atmospheric residue, deasphalted vacuum residue, coking distillate oil, catalytic cracking Distillate oil, shale oil, asphalt sand oil or coal liquefied oil, or a combination of two or three of them; and / or,
  • the conditions of the hydrocracking reaction are: the reaction temperature is about 200-650 ° C, preferably about 300-510 ° C; the reaction pressure is about 3-24MPa, preferably about 4-15MPa; and the liquid hourly space velocity is about 0.1-50h -1 , preferably about 0.2-30 h -1 ; the volume ratio of hydrogen to oil is about 100-5000.
  • a hydrocracking catalyst characterized in that, based on the dry basis weight of the catalyst, the catalyst includes a carrier of 45-90% by weight based on the weight of the dry basis, and 1-40% by weight based on the metal oxide The first metal component, and 1-15% by weight of the second metal component in terms of metal oxides;
  • the carrier includes a phosphorus-containing high-silicon molecular sieve and a heat-resistant inorganic oxide, and the weight ratio of the phosphorus-containing high-silicon molecular sieve and the heat-resistant inorganic oxide is about 0.03: 1 to about 20: 1;
  • the first metal component Is a metal component selected from Group VIB metal;
  • the second metal component is a metal component selected from Group VIII metal;
  • the phosphorus-containing high-silicon molecular sieve has a pore volume of about 0.20-0.50 mL / g, a specific surface area of about 260-600 m 2 / g, calculated as oxides and based on the dry basis weight of the molecular sieve, the phosphorus-containing high silicon
  • the silicon content of the molecular sieve is about 90-99.8% by weight, the aluminum content is about 0.1-9.0% by weight, and the phosphorus content is about 0.01-2.5% by weight; in the XRD spectrum of the phosphorus-containing high silicon molecular sieve, the first strongest peak The diffraction angle position is about 5.9-6.9 °, the second strongest peak is about 10.0-11.0 °, and the third strongest peak is about 15.6-16.7 °.
  • I 4 / I 23.5-24.5 It is about 1.0-4.0, I 5 / I 23.5-24.5 . It is about 1.0-2.0, where I 4 is the peak height of the fourth strongest peak, and I 5 is the peak height of the fifth strongest peak, I 23.5-24.5 . It is the peak height of the peak whose diffraction angle position is about 23.5-24.5 °.
  • the raw material of phosphorus-containing molecular sieve is hydrothermally treated at a temperature of about 350-700 ° C., a pressure of about 0.1-2 MPa and the presence of water vapor for about 0.5-10 h, to obtain hydrothermally treated molecular sieve material;
  • the dry basis weight of the phosphorus molecular sieve raw material is based on 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;
  • step b) The hydrothermally treated molecular sieve material obtained in step a) is beaten with water to obtain a first slurry, the first slurry is heated to about 40-95 ° C, and then the temperature is maintained and the first slurry is added to the first slurry An acid solution, the amount of the first acid solution added is such that the resulting acid-added first slurry has a pH of about 2.5-4, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the first solid product is collected;
  • step c) Pulp the first solid product obtained in step b) with water to obtain a second slurry, heat the second slurry to about 40-95 ° C, then maintain the temperature and continuously add the second acid to the second slurry
  • the amount of the second acid solution added is such that the pH of the resulting acid-added second slurry is about 1.0-2.0, and then the reaction is carried out at a constant temperature for about 0.5-20 h, and the second solid product is collected.
  • step a) the raw material of the phosphorus-containing molecular sieve is a phosphorus-containing Y-type molecular sieve, and the unit cell constant of the phosphorus-containing Y-type molecular sieve is about 2.425-2.47 nm, and The surface area is about 250-750 m 2 / g, and the pore volume is about 0.2-0.95 mL / g.
  • step c) The catalyst according to item C6, wherein in step c), the method of adding the second acid solution is as follows: based on 1 L of the second slurry, based on H + , based on about 0.05-10 mol / h The second acid solution to the second slurry.
  • 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 selected from phosphoric acid, sulfuric acid, At least one of nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid; and / or,
  • the acid concentration of the second acid solution is about 0.01-15.0mol / L, and the acid in the second acid solution is selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, At least one of formic acid and acetic acid.
  • 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.
  • the first metal precursor is an inorganic acid of the first metal, an inorganic salt of the first metal, or a first metal organic compound
  • the inorganic salt is nitrate, carbonate , Basic carbonate, hypophosphite, phosphate, sulfate or chloride
  • the organic substituent in the first metal organic compound is selected from hydroxyl, carboxyl, amine, ketone, ether, alkyl At least one of; and / or,
  • the second metal precursor is an inorganic acid of the second metal, an inorganic salt of the second metal, or an organic compound of the second metal;
  • the inorganic salt is nitrate, carbonate, basic carbonate, hypophosphite, Phosphate, sulfate or chloride;
  • the organic substituent in the second metal organic compound is at least one selected from the group consisting of hydroxyl group, carboxyl group, amine group, ketone group, ether group and alkyl group.
  • the drying conditions are: the temperature is about 80-350 ° C, and the time is about 0.5-24h; and / or,
  • the conditions of the calcination are: the temperature is about 350-600 ° C., and the time is about 0.2-12 h.
  • hydrocarbon raw material is straight-run gas oil, vacuum gas oil, demetalized oil, atmospheric residue, deasphalted vacuum residue, coking distillate oil, catalytic cracking Distillate oil, shale oil, asphalt sand oil or coal liquefied oil, or a combination of two or three of them; and / or,
  • the conditions of the hydrocracking reaction are: the reaction temperature is about 200-650 ° C, preferably about 300-510 ° C; the reaction pressure is about 3-24MPa, preferably about 4-15MPa; and the liquid hourly space velocity is about 0.1-50h -1 , preferably about 0.2-30 h -1 ; the volume ratio of hydrogen to oil is about 100-5000.
  • the pore volume and specific surface area of the molecular sieve were determined by the ASAP 2400 automatic adsorption instrument of Micromertics Instruments of the United States, by static low-temperature adsorption capacity method (according to the method of GB / T5816-1995), the specific method For: the molecular sieve to be tested is degassed under vacuum at 250 ° C and 1.33Pa for 4h, and it is brought into contact with nitrogen as adsorbate at -196 ° C, the static adsorption reaches the adsorption equilibrium; The difference in the gas phase calculates the amount of nitrogen adsorbed by the adsorbent, and then uses the BJH formula to calculate the pore size distribution, and the BET formula to calculate the specific surface area and pore volume.
  • the crystal structure of the molecular sieve is determined by the D5005 X-ray diffractometer of the German Siemens company, according to the method of the industry standard SH / T0339-92.
  • the experimental conditions were: Cu target, k ⁇ radiation, solid detector, tube voltage 40kV, tube current 40mA, step scan, step width 0.02 °, prefabrication time 2s, scan range 5 ° -70 °.
  • the diffraction angle position refers to the 2 ⁇ angle value of the highest value of the diffraction peak.
  • the silicon content, aluminum content, phosphorus content and sodium content of the molecular sieve were measured by the 3271E X-ray fluorescence spectrometer of Rigaku Electric Industry Co., Ltd.
  • the measurement method was: powder sample compression molding, rhodium target, laser voltage 50kV, laser current 50mA, The scintillation counter and the proportional counter were used to detect the spectral intensity of each element, and the content of the element was quantitatively and semi-quantitatively analyzed by the external standard method.
  • Preparation Example 1-2 is used to illustrate the phosphorus-containing high-silicon molecular sieve according to the present application and its preparation method.
  • Phosphorus-containing molecular sieve (USY molecular sieve produced by Sinopec Catalyst Changling Branch), cell constant 2.456nm, specific surface area 672m 2 / g, pore volume 0.357mL / g, Na 2 O content 1.44% by weight, P 2 O 5 content is 1.37% by weight, SiO 2 content is 76.7% by weight, and Al 2 O 3 content is 20.5% by weight)
  • 500 g is placed in a hydrothermal kettle, 100% water vapor is introduced, and it is conducted at 560 ° C and 0.8 MPa Hydrothermal treatment for 3h, and then take out the hydrothermally treated molecular sieve material.
  • the above first solid product was added to 400 mL of deionized water, stirred and beaten to obtain a second slurry.
  • the temperature was raised to 80 ° C, based on 1L of the second slurry, based on H + , a 2mol / L sulfuric acid solution was added to the second slurry at a rate of 5mol / h, and the pH of the acid-added second slurry was detected When the value is 1.4, the acid addition is stopped, and then the reaction is carried out at a constant temperature for 3 hours, filtered, and the second solid product is collected.
  • the obtained solid product was dried at 180 ° C. for 3 hours to obtain phosphorus-containing high-silicon molecular sieve Y-1, whose XRD spectrum is shown in FIG. 1.
  • the XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the diffraction peak heights are listed in Table 2, and other properties are listed in Table 3.
  • the phosphorus-containing high-silicon molecular sieve was prepared according to the method of Preparation Example 1, except that when the second acid solution was added, it was added at a rate of 15 mol / h.
  • the phosphorus-containing high-silicon molecular sieve Y-2 is prepared, and its XRD spectrum is shown in FIG. 1.
  • the XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the diffraction peak heights are listed in Table 2, and other properties are listed in Table 3.
  • the PSRY molecular sieve was prepared by referring to Example 1 of Chinese Patent ZL98117286.5, and referred to as molecular sieve DY-1. Its XRD spectrum is shown in FIG. 1. The XRD diffraction peak positions of the obtained molecular sieve are listed in Table 1, the diffraction peak heights are listed in Table 2, and other properties are listed in Table 3.
  • HY molecular sieve without phosphorus produced by Sinopec Catalyst Changling Branch, trade name HY, unit cell constant 2.465nm, specific surface area 580m 2 / g, pore volume 0.33mL / g, Na 2 O content 0.3 weight %, SiO 2 content is 77.7% by weight, Al 2 O 3 content is 22% by weight
  • 500g is placed in a hydrothermal kettle, 100% steam is introduced, hydrothermal treatment is performed at 500 ° C and 2.0MPa for 1h, and then the The hydrothermally treated molecular sieve material is taken out.
  • Examples 1-6 are used to illustrate the hydrocracking catalyst according to the present application and the preparation method thereof. Comparative examples 1-3 are used to illustrate the hydrocracking catalysts other than the present application and their preparation methods.
  • Dry basis 80g molecular sieve Y-1 and 28.8g pseudo-boehmite (Sinopec Catalyst Changling Branch, trade name PB90, dry basis 70% by weight, where dry basis conditions are obtained after calcining the sample at 600 ° C for 3h
  • the weight ratio of the sample to the initial sample, the same below is mixed, extruded into a trilobal strip with a circumscribed circle diameter of 1.6 mm, dried at 120 ° C for 3h, and calcined at 600 ° C for 3h to obtain the carrier CS-1.
  • 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 resulting catalyst composition is shown in Table 4.
  • the dry basis 95g molecular sieve Y-1 was mixed with 7.2g pseudo-boehmite, extruded into a trilobal strip with a circumscribed circle diameter of 1.6 mm, dried at 120 °C for 3h, and calcined at 600 °C for 3h to obtain the carrier CS- 3.
  • CS-4 carrier After cooling to room temperature, 100g of CS-4 carrier was impregnated with a 70mL aqueous solution containing 74g of ammonium metatungstate and 43g of nickel nitrate, dried at 120 ° C for 3h, and calcined at 480 ° C for 4h to obtain a hydrocracking catalyst, whose composition is shown in Table 4.
  • the catalyst was prepared according to the method of Example 1, with the difference that molecular sieve Y-1 was replaced with molecular sieve DY-1, DY-2 and DY-3, respectively.
  • the resulting catalyst composition is shown in Table 4.
  • This test example was used to test the catalytic activity of the catalysts of Examples 1-3 and Comparative Examples 1-3 for hydrocracking reactions.
  • the hydrocracking activity of the catalyst was evaluated on a small fixed-bed hydrocracking device.
  • the catalyst loading was 0.2 ml
  • the reaction temperature was 320 ° C
  • the reaction pressure It is 4.0MPa
  • the volume ratio of hydrogen to oil is 3600
  • the liquid hourly space velocity is 30h -1
  • the activity of the catalyst is represented by the percentage of tetralin converted in the product composition.
  • the evaluation results are shown in Table 5.
  • the catalyst containing the phosphorus-containing high-silicon molecular sieve provided in the present application has a higher nitrogen content (such as pyridine )
  • the catalytic activity of hydrocracking in the presence is increased by at least 7%.

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Abstract

一种含磷高硅分子筛及其制备方法和应用，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛包含约86.5-99.8重量％的硅，约0.1-13.5重量％的铝和约0.01-6重量％的磷，所述分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°。所述含磷高硅分子筛用于制备加氢裂化催化剂时表现出提高的在含氮物质存在下的加氢裂化活性。

Description

含磷高硅分子筛及其制备方法和应用
相关申请的交叉引用
本申请要求申请人于2018年10月26日向中国专利局提交的申请号为201811259943.0、名称为“含磷高硅分子筛及其制备方法和应用”的专利申请的优先权，以及申请人于2018年10月26日向中国专利局提交的申请号为201811261400.2、名称为“含高硅分子筛的加氢裂化催化剂及其制备方法和应用”的专利申请的优先权，上述专利申请的内容经此引用全文并入本文。
技术领域
本申请涉及分子筛和加氢裂化的技术领域，具体涉及一种含磷高硅分子筛、包含它的加氢裂化催化剂，以及它们的制备方法和应用。
背景技术
工业加氢裂化进料包括VGO等重质劣质馏分，含有大量的多环芳烃和环烷烃，以及大量含氮化合物。常规加氢裂化进料的氮质量百分数一般在0.1-0.2％之间。然而，炼油二次加工过程如焦化、溶剂脱沥青等常常生成大量的含氮化合物，所得物料的氮含量常常超过0.3％，有些甚至到达0.6％，这使得在采用常规精制催化剂处理后，其氮含量难以脱除到常规分子筛型加氢裂化催化剂所能承受的10-100ppm的水平。通常，采用弱酸性的无定型硅铝或者含硅的氧化铝来作为高氮含量加氢裂化催化剂的主要酸性组分。
现有技术通常采用硅氧化物和铝氧化物的盐溶液在低pH值下进行弱酸性硅铝的合成，也有采用在氧化硅前体上接枝氧化铝或者在氧化铝前体上接枝氧化硅，并通过进一步反应形成硅铝四面体，从而在样品中产生酸性。
中国专利ZL97121663.0公开了一种特别适用于生产中间馏分油的加氢裂化催化剂，含有无定形氧化硅-氧化铝组分、小孔氧化铝粘合剂，至少一种第VIB族元素和至少一种第VIII族元素，无定形氧化硅-氧化铝的含量为30-60重量％，加氢金属氧化物总含量为20-35重量％，余量为小孔氧化铝粘合剂，其特征在于所述催化剂的比表面为150-300m 2/g， 孔容为0.25-0.50mg/g，4-15nm孔的分布在60-90％，红外酸度为0.30-0.50mmol/g。
这些方法尽管可以产生具有一定酸性的材料，但在合成过程中，为了保持基体结构的稳定，所得产物中存在大量的非骨架六配位铝，使得材料仅短程有序，很难做到长程有序。
发明内容
本申请的目的是提供一种含磷高硅分子筛、包含它的加氢裂化催化剂，以及它们的制备方法和应用，该分子筛用于制备加氢裂化催化剂时表现出提高的在含氮物质存在下的加氢裂化活性。
为了实现上述目的，一方面，本申请提供了一种含磷高硅分子筛，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛包含约86.5-99.8重量％的硅，约0.1-13.5重量％的铝和约0.01-6重量％的磷，
所述分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°，
优选地，所述分子筛的孔容为约0.20-0.50mL/g，比表面积为约250-670m 2/g。
另一方面，本申请提供了一种制备含磷高硅分子筛的方法，该方法包括以下步骤：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-8.0MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％，硅含量为约70-85重量％，铝含量为约16.0-21.0重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水制成第一浆液，将该第一浆液加热至约40-95℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.3-4.0，然后恒温反应约0.5-20h，收集第一固体产物；
c)将步骤b)得到的所述第一固体产物加水制成第二浆液，将该第二浆液加热至约40-95℃，然后保持温度并向该第二浆液中加入第二 酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约0.8-2.0，然后恒温反应约0.5-20h，收集第二固体产物。
再一方面，本申请提供了根据本申请的含磷高硅分子筛在烃类原料的加氢裂化反应中的应用，包括使烃类原料与包括所述含磷高硅分子筛的加氢裂化催化剂接触。
再一方面，本申请提供了一种加氢裂化催化剂，以催化剂的干基重量为基准，该催化剂包括以干基重量计为约45-90重量％的载体，以金属氧化物计为约1-40重量％的第一金属组分，和以金属氧化物计为约1-15重量％的第二金属组分；
所述载体包括含磷高硅分子筛和耐热无机氧化物，所述含磷高硅分子筛和耐热无机氧化物的重量比为约0.03∶1至约20∶1；
其中，所述第一金属组分包含第VIB族金属，所述第二金属组分包含第VIII族金属，且所述含磷高硅分子筛为根据本申请的含磷高硅分子筛。
再一方面，本申请提供了一种制备加氢裂化催化剂的方法，包括如下步骤：
将根据本申请的含磷高硅分子筛与耐热无机氧化物混合制成载体；以及
使含有第一金属前驱物和第二金属前驱物的浸渍液与所述载体接触进行浸渍。
再一方面，本申请提供了根据本申请的加氢裂化催化剂在烃类原料的加氢裂化反应中的应用，包括使烃类原料与所述加氢裂化催化剂接触。
本申请采用含磷分子筛原料在特定条件下进行水热处理和两步酸洗处理，制得了具有新型结构特征的含磷高硅分子筛。本申请的含磷高硅分子筛用于制备加氢裂化催化剂时表现出提高的在含氮物质存在下的加氢裂化活性。相应地，采用该含磷高硅分子筛制备的加氢裂化催化剂也具有改善的加氢裂化活性。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1所示为制备实施例1-2和制备对比例1-3制备的分子筛的XRD谱图。
具体实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
在本申请中，物质的干基重量是指该物质在600℃焙烧3小时得到的固体产物重量。本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本申请原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
在第一方面，本申请提供了一种含磷高硅分子筛，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛包含约86.5-99.8重量％、优选约90-99.8重量％的硅，约0.1-13.5重量％、优选约0.1-9.0重量％的铝和约0.01-6重量％、优选约0.01-2.5重量％的磷。此外，任选地， 所述分子筛还可以含有少量的钠，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛的钠含量可以为约0.01-1.0重量％，例如约0.01-0.6重量％。
在一优选实施方式中，以氧化物计并以所述分子筛的干基重量为基准，所述含磷高硅分子筛包含约90-99.8重量％的硅，约0.1-9.0重量％的铝和约0.01-2.5重量％的磷。任选地，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛还可以含有约0.01-1.0重量％、例如约0.01-0.6重量％的钠。
在进一步优选的实施方式中，以氧化物计并以所述分子筛的干基重量为基准，所述含磷高硅分子筛包含约95.0-99.0重量％的硅，约0.5-5.0重量％铝和约0.1-1.0重量％的磷。任选地，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛还可以含有约0.01-0.6重量％的钠。
在一优选实施方式中，所述分子筛的孔容可以为约0.20-0.50mL/g，优选约0.30-0.45mL/g，例如约0.33-0.42mL/g；和/或，所述分子筛的比表面积可以为约250-670m 2/g、优选约260-600m 2/g、例如约400-600m 2/g。
在进一步优选的实施方式中，所述分子筛的孔容为约0.20-0.50mL/g，比表面积为约260-600m 2/g。
根据本申请，所述分子筛具有与常规硅铝材料不同的结构特征。具体地，所述分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，优选在约6.1-6.8°；第二强峰的衍射角位置在约10.0-11.0°，优选在约10.2-10.7°；且第三强峰的衍射角位置在约15.6-16.7°，优选在约15.8-16.5°，其中衍射角位置是指XRD谱图中衍射峰出峰最高值的2θ角数值。
在本申请中，表述第一、第二和第三强峰等中的序数词“第一”、“第二”和“第三”等代表了按峰高确定的所述衍射峰的相对强弱次序，其中第一强峰代表XRD谱图中峰高最高的衍射峰，第二强峰代表XRD谱图中峰高第二高的衍射峰，第三强峰代表XRD谱图中峰高第三高的衍射峰，以此类推。
本领域技术人员熟知的是，在采用X射线衍射(XRD)进行物质结构解析时，通常可以通过波长和衍射角计算出D值(晶面间距)，并 根据最强的三个衍射峰(即本申请中的第一强峰、第二强峰和第三强峰)特征进行物相初步鉴定。上述三强峰的概念还可以参考文献《多相催化剂的研究方法》，尹元根主编，北京：化学工业出版社，1988，第140-170页。
在一优选实施方式中，所述分子筛的XRD谱图中，I 1/I 23.5-24.5。可以为约3.0-11.0，例如约4.0-10.5或约4.6-10.1；I 2/I 23.5-24.5。可以为约2.5-8.0，例如约2.9-7.0或约3.0-6.4；I 3/I 23.5-24.5。可以为约1.0-4.5、例如约1.5-4.0或约2.1-3.8；其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
在进一步优选的实施方式中，所述分子筛的XRD谱图中，I 1/I 23.5-24.5。可以为约3.0-11.0，I 2/I 23.5-24.5。可以为约2.9-7.0，I 3/I 23.5-24.5。可以为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
在某些更进一步优选的实施方式中，所述分子筛的XRD谱图中，I 1/I 23.5-24.5。可以为约4.0-10.5，I 2/I 23.5-24.5。可以为约2.9-7.0，I 3/I 23.5-24.5。可以为约1.5-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
在某些进一步优选的实施方式中，所述分子筛的XRD谱图中具有至少五个衍射峰，其中第四强峰的衍射角位置可以在约20.4-21.6°，优选在约20.8-21.4°，第五强峰的衍射角位置可以在约11.8-12.8°，优选在约12.1-12.6°。
在更进一步优选的实施方式中，I 4/I 23.5-24.5。可以为约1.0-4.0，例如约1.1-3.0或约1.2-2.3，I 5/I 23.5-24.5。可以为约1.0-2.0、例如约1.0-1.6或约1.0-1.2，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。所述第四强峰、第五强峰的概念可以依据对上述三强峰的介绍进行理解，此处不再赘述。
在某些更进一步优选的实施方式中，I 4/I 23.5-24.5。可以为约1.1-3.0，I 5/I 23.5-24.5。可以为约1.0-1.6，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
本申请的含磷高硅分子筛用于制备加氢裂化催化剂时表现出了提高的在含氮物质存在下的加氢裂化活性。
在第二方面，本申请提供了制备含磷高硅分子筛的方法，该方法包括以下步骤：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-8.0MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％，硅含量为约70-85重量％，铝含量为约16.0-21.0重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水制成第一浆液，将该第一浆液加热至约40-95℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.3-4.0、优选约2.5-4.0，然后恒温反应约0.5-20h，收集第一固体产物；以及
c)将步骤b)得到的所述第一固体产物加水制成第二浆液，将该第二浆液加热至约40-95℃，然后保持温度并向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约0.8-2.0、优选约1.0-2.0，然后恒温反应约0.5-20h，收集第二固体产物。
在一优选实施方式中，所述制备含磷高硅分子筛的方法包括以下步骤：
a)使含磷分子筛原料在约400-650℃，例如约560℃的温度，约0.5-5MPa、例如约0.8MPa的压力和水蒸汽存在下进行水热处理约1-7h、例如约3h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-6重量％、例如约1.37重量％，钠含量为约0.5-3.0重量％、例如约1.44重量％，硅含量为约70-80重量％、例如约76.7重量％，铝含量为约18.0-21.0重量％、例如约20.5重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水制成第一浆液，将该第一浆液加热至约50-85℃、例如约80℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.5-3.5、例如约2.8，然后恒温反应约 1-10h、例如约4h，收集第一固体产物；以及
c)将步骤b)得到的所述第一固体产物加水制成第二浆液，将该第二浆液加热至约50-85℃、例如约80℃，然后保持温度并向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为优选约1.0-1.8、例如约1.4，然后恒温反应约1-10h、例如约3h，收集第二固体产物。
根据本申请，在某些实施方式中，步骤a)中，所述含磷分子筛原料指含磷的分子筛。本申请采用含磷分子筛原料，分子筛骨架外的磷铝物种能够提高分子筛的骨架稳定性，从而进一步提高分子筛的性能。所述含磷分子筛原料可具有八面沸石分子筛结构，优选为含磷的Y型分子筛，其晶胞常数可以为约2.425-2.47nm、例如约2.456nm，比表面积可以为约250-750m 2/g、例如约672m 2/g，孔容可以为约0.2-0.95mL/g、例如约0.357mL/g。
进一步地，所述Y型分子筛的具体选择可以在很大范围内变化，只要使得所述含磷分子筛原料满足上述条件即可。例如，所述Y型分子筛可以选自NaY、HNaY(氢Y型分子筛)、REY(稀土Y型分子筛)、USY(超稳Y型分子筛)等。所述含磷的Y型分子筛的阳离子位可以被钠离子、铵离子和氢离子中的一种或多种所占据；或者也可以是，在所述分子筛引入磷之前或之后，通过常规的离子交换，使其中的钠离子、铵离子和氢离子的全部或部分被其它离子所替代。所述含磷分子筛原料可以是市售的商品，也可以采用任意的现有技术制备，例如，可以采用中国专利ZL00123139.1公开的制备USY的方法，或中国专利ZL200410071122.6公开的制备PUSY的方法等制备，本申请不再赘述。
根据本申请，步骤b)和步骤c)中的所述加水打浆的含义为本领域技术人员所熟知。在某些优选实施方式中，步骤b)中，打浆后得到的所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例可以为约14∶1至约5∶1、例如约10∶1；和/或步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例可以为约0.5∶1至约20∶1、例如约10∶1。
根据本申请，在某些优选实施方式中，步骤b)中，所述第一浆液被加热至约50-85℃、例如约80℃，然后保持温度并连续向该第一浆 液中加入第一酸溶液，直到加酸后的第一浆液的pH值达到所需大小时停止。根据含磷分子筛原料性质的不同以及步骤a)的所述水热处理条件的改变，所述第一酸溶液的加入量可以在很大范围内变化。本领域技术人员可以理解的是，所述第一酸溶液的加入量只要使加酸后的第一浆液的pH值满足上述合适的范围，则均是合意的。所述第一酸溶液的加入速度没有特别的限制，可以在较大范围内变化。
根据本申请，在某些优选实施方式中，步骤b)中，所述加入第一酸溶液的操作可以进行多次(例如1-5次)，每次加酸后均可恒温反应一段时间再继续进行下一次的加酸，直到加酸后的第一浆液的pH值达到需要的范围。所述第一酸溶液的酸浓度可以为约0.1-15.0mol/L，优选约0.1-5.0mol/L、例如约2.0mol/L，pH值可以为约0.01-3。所述第一酸溶液中的酸可以为常规的无机酸和/或有机酸，例如可以为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸。
根据本申请，在某些优选实施方式中，步骤c)中，所述第二浆液被加热至约50-85℃、例如约80℃，然后保持温度并连续向该第二浆液中加入第二酸溶液，直到加酸后的第二浆液的pH值达到需要大小时停止。加入所述第二酸溶液的方式可以为：以1L所述第二浆液为基准，以H +计，按照约0.05-15mol/h，优选约0.05-10mol/h，更优选约2-8mol/h、例如约5mol/h的速度将所述第二酸溶液加入到所述第二浆液中。根据本申请，在步骤c)中采用较慢的加酸速度，能够使脱铝过程更为缓和，有利于提高分子筛的性能。
根据本申请，在某些优选实施方式中，步骤c)中，所述加入第二酸溶液的操作可以进行多次(例如1-5次)，每次加酸后均可恒温反应一段时间再继续进行下一次的加酸，直到加酸后的第二浆液的pH值达到需要的范围。所述第二酸溶液的酸浓度可以为约0.1-15.0mol/L，优选约0.1-5.0mol/L、例如约2.0mol/L，pH值可以为约0.01-3。所述第二酸溶液中的酸可以为常规的无机酸和/或有机酸，例如可以为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸。所述第二酸溶液与第一酸溶液的种类和浓度可以相同，也可以不同，优选为相同的酸溶液。
根据本申请，在某些优选实施方式中，所述方法可以进一步包括： 收集所述第二固体产物，然后水洗、干燥，得到所述含磷高硅分子筛。所述水洗和干燥为制备分子筛的常规步骤，本申请没有特别的限制。例如，所述干燥可以采用烘箱、网带、转炉加热等方法进行，干燥的条件可以为：温度约50-350℃，优选约70-200℃、例如约180℃；时间约1-24h，优选约2-6h、例如约3h。
本申请采用含磷分子筛原料进行特定的水热处理和两步酸洗处理，能够制得具有新型结构特征的含磷高硅分子筛。
本申请所提供的含磷高硅分子筛可作为各种酸催化催化剂用于催化裂化、临氢异构化、烷基化、加氢裂化等反应中，特别适用于对烃类原料进行加氢裂化，以生产具有较低沸点和较低分子量的烃类馏分。
因此，在第三方面，本申请提供了根据本申请的含磷高硅分子筛在烃类原料的加氢裂化反应中的应用，包括使烃类原料与包括所述含磷高硅分子筛的加氢裂化催化剂接触。
根据本申请，所述烃类原料可以是各种重质矿物油或合成油，或它们的混合馏分油，如直馏瓦斯油(straight run gas oil)、减压瓦斯油(vacuum gas oil)、脱金属油(demetallized oils)、常压渣油(atmospheric residue)、脱沥青减压渣油(deasphalted vacuum residue)、焦化馏出油(coker distillates)、催化裂化馏出油(cat craker distillates)、页岩油(shale oil)、沥青砂油(tar sand oil)、煤液化油(coal liquid)等。
特别地，基于本申请的含磷高硅分子筛的催化剂特别适用于重质和劣质馏分油的加氢裂化，以生产馏程为约149-371℃，尤其是馏程为约180-370℃的中间馏分油的加氢裂化过程。
根据本申请，所述的加氢裂化反应可以是在固定床、沸腾床、浆态床、悬浮床等常规设备中实施的加氢裂化反应中的一种或者多种。
根据本申请，基于本申请的含磷高硅分子筛的催化剂用于馏分油加氢裂化时，可在常规的加氢裂化工艺条件下使用。例如，所述加氢裂化反应的条件可为：反应温度约200-650℃，优选约300-510℃，反应压力约3-24MPa，优选约4-15MPa，液时空速约0.1-50h -1，优选约0.2-30h -1，氢油体积比约100-5000。
在第四方面，本申请提供了一种加氢裂化催化剂，以催化剂的干基重量为基准，该催化剂包含以干基重量计为约45-90重量％、例如约60-90重量％的载体，以金属氧化物计为约1-40重量％、例如约5-35 重量％的第一金属组分，和以金属氧化物计为约1-15重量％、例如约2-12重量％的第二金属组分。所述载体包含根据本申请的含磷高硅分子筛和耐热无机氧化物，所述含磷高硅分子筛和耐热无机氧化物的重量比为约0.03∶1至约20∶1、例如约0.05∶1至约19∶1；所述第一金属组分包含第VIB族金属；所述第二金属组分包含第VIII族金属。
根据本申请，使用所述耐热无机氧化物能够提高催化剂的强度，并改善和调解催化剂的物化性质，如可以改善催化剂的孔结构。在某些实施方式中，所述耐热无机氧化物可以为加氢催化剂载体中常用的无机氧化物，例如氧化铝、氧化硅、氧化钛、氧化锆、氧化镁、氧化钍、氧化铍、氧化硼和氧化镉等。在本申请的优选实施方式中，所述耐热无机氧化物为氧化铝，所述氧化铝可以包括三水铝石如水矿铝(gibbsite)、三羟铝石诺三水铝石(bayeritenordstrandite)，和一水铝石如一水软铝石(boehmite、diaspor、pseudoboehmite)。
根据本申请，在优选的实施方式中，所述第一金属选自钼组分、钨组分和它们的任意组合；和/或，所述第二金属组分选自铁组分、镍组分、钴组分，和它们的任意组合。
在第五方面，本申请提供了制备本申请的加氢裂化催化剂的方法，该方法包括如下步骤：
i)将根据本申请的含磷高硅分子筛与耐热无机氧化物混合制成载体；以及
ii)使含有第一金属前驱物和第二金属前驱物的浸渍液与所述载体接触进行浸渍。
在本申请中，浸渍液与载体的接触浸渍方式可采用本领域技术人员所公知的任意一种方法，例如中国专利ZL200810241082.3所公开的方法，其包括将第VIB族金属组分、第VIII族金属组分和有机添加剂负载到催化剂载体上。
所述载体的制备方法为本领域技术人员所熟知，本申请没有特别的限制。例如，该方法可以包括：将根据本申请的含磷高硅分子筛与耐热无机氧化物混合，然后成型并干燥，得到所述载体。所述成型的方法可以采用常规的各种方法，如压片成型、滚球成型或挤条成型等。
本申请对所述载体的形状没有特别的要求，可以是球形、条形、中空的条形、球形、块状等，条形载体可以是三叶草形、四叶草形等 多叶草形以及它们的变形体。
根据本申请，在某些实施方式中，所述第一金属前驱物为含有所述第一金属的可溶于所述浸渍液中的化合物，包括但不限于第一金属的无机酸、第一金属的无机盐、第一金属的氧化物和第一金属有机化合物中的至少一种；所述无机盐可以为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中的至少一种；所述第一金属有机化合物中的有机取代基可以为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种。例如，当所述第一金属为钼时，所述第一金属前驱物可以为选自钼酸、仲钼酸、钼酸盐、仲钼酸盐和氧化钼中的至少一种；当所述第一金属为钨时，所述第一金属前驱物可以为选自钨酸、偏钨酸、乙基偏钨酸、钨酸盐、偏钨酸盐和乙基偏钨酸盐中的至少一种。
根据本申请，在某些实施方式中，所述第二金属前驱物为含有所述第二金属的可溶于所述浸渍液中的化合物，包括但不限于第二金属的无机酸、第二金属的无机盐、第二金属的氧化物和第二金属有机化合物中的至少一种；所述无机盐可以为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中的至少一种；所述第二金属有机化合物中的有机取代基可以为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种。
根据本申请，在某些实施方式中，所述浸渍液中还可以含有有机添加剂，所述有机添加剂的浓度可以为约2-300g/L。所述有机添加剂可以为含氧有机化合物和/或含氮有机化合物。具体地，所述含氧有机化合物可以为选自乙二醇、丙三醇、聚乙二醇(分子量可以为约200-1500)、二乙二醇、丁二醇、乙酸、马来酸、草酸、氨基三乙酸、1，2-环己烷二胺四乙酸、柠檬酸、酒石酸和苹果酸中的至少一种；所述含氮有机化合物可以为选自乙二胺、二亚乙基三胺、环己二胺四乙酸、氨基乙酸、次氮基三乙酸、乙二胺四乙酸和乙二胺四乙酸铵中的至少一种。
本申请的制备加氢裂化催化剂的方法中，对所述接触浸渍的温度没有特别限制，可以是所用浸渍液所能达到的各种温度。浸渍的时间也没有特别限制，只要能使催化剂载体负载上所需量的金属活性组分前驱物即可。一般情况下，浸渍温度越高，浸渍液浓度越大，达到同 样浸渍量(即催化剂载体浸渍后与浸渍前的重量差)所需的时间越短；反之亦然。当所需的浸渍量和条件确定后，本领域技术人员根据本申请的教导很容易选择合适的浸渍时间。
本申请对浸渍方法也没有特别的要求，所述浸渍可以是饱和浸渍，也可以是过饱和浸渍。所述浸渍的环境没有特别的限制，按照本领域中的常规方法可以在密封条件下，也可以在开放环境中进行，可以在浸渍过程中补充损失的水溶剂，也可以不补充。在浸渍过程中可以通入各种气体，比如空气、氮气、水蒸汽等，也可以不通入任何新组分。
在某些实施方式中，本申请的制备加氢裂化催化剂的方法中，可以进一步包括将浸渍后得到的物料干燥、焙烧的步骤，所述干燥和焙烧为制备催化剂的常规步骤，本申请没有特别的限制。例如，所述干燥的条件可以为：温度约80-350℃，优选约100-300℃，时间约0.5-24h，优选约1-12h。所述焙烧的条件可以为：温度约350-600℃，优选约400-550℃；时间约0.2-12h，优选约1-10h。
本申请提供的加氢裂化催化剂可作为各种酸催化催化剂用于催化裂化、临氢异构化、烷基化、加氢裂化等反应中，特别适用于对烃类原料进行加氢裂化，以生产具有较低沸点和较低分子量的烃类馏分。
因此，在第六方面，本申请提供了根据本申请的加氢裂化催化剂在烃类原料的加氢裂化反应中的应用，包括使烃类原料与所述加氢裂化催化剂接触。
根据本申请，所述烃类原料可以是各种重质矿物油或合成油，或它们的混合馏分油，如直馏瓦斯油(straight run gas oil)、减压瓦斯油(vacuum gas oil)、脱金属油(demetallized oils)、常压渣油(atmospheric residue)、脱沥青减压渣油(deasphalted vacuum residue)、焦化馏出油(coker distillates)、催化裂化馏出油(cat craker distillates)、页岩油(shale oil)、沥青砂油(tar sand oil)、煤液化油(coal liquid)等。
特别地，本申请提供的催化剂可适用于重质和劣质馏分油的加氢裂化，以生产馏程为约149-371℃，尤其是馏程为约180-370℃的中间馏分油的加氢裂化过程。
本申请提供的加氢裂化催化剂在应用于烃类原料的加氢裂化反应中时，优选进一步包括在使用所述加氢裂化催化剂之前，在氢气存在下，于约140-370℃的温度下用硫、硫化氢或含硫原料对所述加氢裂 化催化剂进行预硫化，这种预硫化可在反应器外进行，也可在反应器内原位硫化，以将所述催化剂转化为硫化物型。
本申请提供的催化剂用于馏分油加氢裂化时，可在常规的加氢裂化工艺条件下使用。例如，所述加氢裂化反应的条件可以为：反应温度约200-650℃，优选约300-510℃；反应压力约3-24MPa，优选约4-15MPa；液时空速约0.1-50h -1，优选约0.2-30h -1；氢油体积比约100-5000。
所述加氢裂化反应可以在任何足以使所述烃类原料在加氢反应条件下与所述催化剂接触并反应的装置中进行，所述装置例如可以为固定床反应器、移动床反应器、沸腾床反应器或者浆态床反应器。
在优选的实施方式中，本申请提供了以下的技术方案：
A1、一种含磷高硅分子筛，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛包含约90-99.8重量％的硅，约0.1-9.0重量％的铝和约0.01-2.5重量％的磷，
所述分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°，
优选地，所述分子筛的孔容为约0.20-0.50mL/g，比表面积为约260-600m 2/g。
A2、根据项目A1所述的含磷高硅分子筛，其中在所述分子筛的XRD谱图中，第一强峰的衍射角位置在约6.1-6.8°，第二强峰的衍射角位置在约10.2-10.7°，第三强峰的衍射角位置在约15.8-16.5°。
A3、根据前述项目中任一项所述的含磷高硅分子筛，其中在所述分子筛的XRD谱图中，I 1/I 23.5-24.5。为约3.0-11.0，I 2/I 23.5-24.5。为约2.9-7.0，I 3/I 23.5-24.5。为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
A4、根据前述项目中任一项所述的含磷高硅分子筛，其中所述分子筛的XRD谱图中具有至少五个衍射峰，其中第四强峰的衍射角位置在约20.4-21.6°，第五强峰的衍射角位置在约11.8-12.8°。
A5、根据项目A4所述的含磷高硅分子筛，其中所述分子筛的XRD谱图中，第四强峰的衍射角位置在约20.8-21.4°，第五强峰的衍射角位 置在约12.1-12.6°；和/或，
I 4/I 23.5-24.5。为约1.0-4.0，I 5/I 23.5-24.5。为约1.0-2.0，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
A6、制备含磷高硅分子筛的方法，包括以下步骤：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-8.0MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％，硅含量为约70-85重量％，铝含量为约16.0-21.0重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水打浆，得到第一浆液，将该第一浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.5-4，然后恒温反应约0.5-20h，收集第一固体产物；以及
c)将步骤b)得到的所述第一固体产物加水打浆，得到第二浆液，将该第二浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约1.0-2.0，然后恒温反应约0.5-20h，收集第二固体产物。
A7、根据项目A6所述的方法，其中在步骤a)中，所述含磷分子筛原料为含磷的Y型分子筛，所述含磷的Y型分子筛的晶胞常数为约2.425-2.47nm，比表面积为约250-750m 2/g，孔容为约0.2-0.95mL/g。
A8、根据项目A6或A7所述的方法，其中在步骤b)中，所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例为约14∶1至约5∶1。
A9、根据项目A6到A8中任一项所述的方法，其中在步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例为约0.5∶1至约20∶1。
A10、根据项目A6到A9中任一项所述的方法，其中在步骤c)中，加入所述第二酸溶液的方式为：以1L所述第二浆液为基准，以H +计，按照约0.05-15mol/h，优选约0.05-10mol/h，更优选约2-8mol/h的速 度将所述第二酸溶液加入到所述第二浆液中。
A11、根据项目A6到A10中任一项所述的方法，其中在步骤b)中，所述第一酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第一酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸；和/或，
步骤c)中，所述第二酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第二酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸。
A12、根据项目A6到A11中任一项所述的方法，进一步包括：收集所述第二固体产物，然后水洗、干燥，得到所述含磷硅铝分子筛的步骤；优选地，所述干燥的条件为：温度约50-350℃，优选约70-200℃；时间约1-24h，优选约2-6h。
A13、通过项目A6到A12中任一项所述的方法制备得到的含磷高硅分子筛。
A14、根据项目A1-A5和A13中任一项所述的含磷高硅分子筛在烃类原料的加氢裂化反应中的应用。
A15、根据项目A14所述的应用，其中所述烃类原料为直馏瓦斯油、减压瓦斯油、脱金属油、常压渣油、脱沥青减压渣油、焦化馏出油、催化裂化馏出油、页岩油、沥青砂油或煤液化油，或者它们中的两种或更多种的组合；和/或，
所述加氢裂化反应的条件为：反应温度约200-650℃，优选约300-510℃；反应压力约3-24MPa，优选约4-15MPa；液时空速约0.1-50h -1，优选约0.2-30h -1；氢油体积比约100-5000。
A16、一种加氢裂化催化剂，以催化剂的干基重量为基准，该催化剂包括以干基重量计约45-90重量％的载体，以金属氧化物计约1-40重量％的第一金属组分，和以金属氧化物计约1-15重量％的第二金属组分；
所述载体包括含磷高硅分子筛和耐热无机氧化物，所述含磷高硅分子筛和耐热无机氧化物的重量比为约0.03∶1至约20∶1；
其中，所述第一金属组分包含第VIB族金属；所述第二金属组分包含第VIII族金属；并且
以氧化物计并以分子筛的干基重量为基准，所述含磷高硅分子筛包含约90-99.8重量％的硅，约0.1-9.0重量％的铝和约0.01-2.5重量％的磷，所述含磷高硅分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°，优选地，所述含磷高硅分子筛的孔容为约0.20-0.50mL/g，比表面积为约260-600m 2/g。
A17、根据项目A16所述的加氢裂化催化剂，其中所述含磷高硅分子筛的XRD谱图中，第一强峰的衍射角位置在约6.1-6.8°，第二强峰的衍射角位置在约10.2-10.7°，第三强峰的衍射角位置在约15.8-16.5°。
A18、根据项目A16或A17所述的加氢裂化催化剂，其中在所述含磷高硅分子筛的XRD谱图中，I 1/I 23.5-24.5。为约3.0-11.0，I 2/I 23.5-24.5。为约2.9-7.0，I 3/I 23.5-24.5。为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
A19、根据项目A16到A18中任一项所述的加氢裂化催化剂，其中在所述含磷高硅分子筛的XRD谱图中具有至少五个衍射峰，其中第四强峰的衍射角位置在约20.4-21.6°，第五强峰的衍射角位置在约11.8-12.8°。
A20、根据项目A19所述的加氢裂化催化剂，其中在所述含磷高硅分子筛的XRD谱图中，第四强峰的衍射角位置在约20.8-21.4°，第五强峰的衍射角位置在约12.1-12.6°；和/或，
I 4/I 23.5-24.5。为约1.0-4.0，I 5/I 23.5-24.5。为约1.0-2.0，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
A21、根据项目A16到A20中任一项所述的加氢裂化催化剂，其中所述含磷高硅分子筛通过包括如下步骤的方法制备得到：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-8.0MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％，硅含量为约70-85重量％，铝含量为约16.0-21.0重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水打浆，得到 第一浆液，将该第一浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.5-4，然后恒温反应约0.5-20h，收集第一固体产物；以及
c)将步骤b)得到的所述第一固体产物加水打浆，得到第二浆液，将该第二浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约1.0-2.0，然后恒温反应约0.5-20h，收集第二固体产物。
A22、根据项目A21所述的加氢裂化催化剂，其中在步骤a)中，所述含磷分子筛原料为含磷的Y型分子筛，所述含磷的Y型分子筛的晶胞常数为约2.425-2.47nm，比表面积为约250-750m 2/g，孔容为约0.2-0.95mL/g。
A23、根据项目A21或A22所述的加氢裂化催化剂，其中在步骤b)中，所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例为约14∶1至约5∶1。
A24、根据项目A21到A23中任一项所述的加氢裂化催化剂，其中在步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例为约0.5∶1至约20∶1。
A25、根据项目A21到A24中任一项所述的加氢裂化催化剂，其中在步骤c)中，加入所述第二酸溶液的方式为：以1L所述第二浆液为基准，以H +计，按照约0.05-15mol/h，优选约0.05-10mol/h，更优选约2-8mol/h的速度将所述第二酸溶液加入到所述第二浆液中。
A26、根据项目A21到A25中任一项所述的加氢裂化催化剂，其中在步骤b)中，所述第一酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第一酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸；和/或，
步骤c)中，所述第二酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第二酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸。
A27、根据项目A21到A26中任一项所述的加氢裂化催化剂，其中所述含磷高硅分子筛的制备步骤进一步包括：收集所述第二固体产物，然后水洗、干燥，得到所述含磷高硅分子筛的步骤；优选地，所述干燥的条件为：温度约50-350℃，优选约70-200℃；时间约1-24h，优选约2-6h。
A28、根据项目A21到A27中任一项所述的加氢裂化催化剂，其中所述耐热无机氧化物为氧化铝、氧化硅、氧化钛、氧化锆、氧化镁、氧化钍、氧化铍、氧化硼或氧化镉，或者它们中的两种或更多种的组合；和/或，
所述第一金属组分为钼组分和/或钨组分；所述第二金属组分为铁组分、镍组分或钴组分，或者它们中的两种或更多种的组合。
A29、制备项目A16到A28中任一项所述的加氢裂化催化剂的方法，该方法包括：使含有第一金属前驱物和第二金属前驱物的浸渍液与载体接触进行浸渍的步骤，其中所述载体包含所述含磷高硅分子筛和耐热无机氧化物。
A30、根据项目A29所述的方法，进一步包括将所述含磷高硅分子筛与耐热无机氧化物混合，然后成型、干燥、焙烧，得到所述载体的步骤。
A31、根据项目A29或A30所述的方法，其中所述第一金属前驱物为第一金属的无机酸、第一金属的无机盐或第一金属有机化合物；所述无机盐为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中是至少一种；所述第一金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种；和/或，
所述第二金属前驱物为第二金属的无机酸、第二金属的无机盐或第二金属有机化合物；所述无机盐为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中的至少一种；所述第二金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种。
A32、根据项目A29到A31中任一项所述的方法，进一步包括将浸渍后得到的物料干燥、焙烧的步骤；
优选地，所述干燥的条件为：温度约80-350℃，优选约100-300℃， 时间约0.5-24h，优选约1-12h；和/或，
优选地，所述焙烧的条件为：温度约350-600℃，优选约400-550℃，时间约0.2-12h，优选约1-10h。
A33、项目A16到A28中任一项所述的加氢裂化催化剂在烃类原料的加氢裂化反应中的应用。
A34、根据项目A33所述的应用，其中所述烃类原料为直馏瓦斯油、减压瓦斯油、脱金属油、常压渣油、脱沥青减压渣油、焦化馏出油、催化裂化馏出油、页岩油、沥青砂油或煤液化油，或者它们中的两种或更多种的组合；和/或，
所述加氢裂化反应的条件为：反应温度约200-650℃，优选约300-510℃；反应压力约3-24MPa，优选约4-15MPa；液时空速约0.1-50h -1，优选约0.2-30h -1；氢油体积比约100-5000。
B1、一种含磷高硅分子筛，其特征在于，所述分子筛的孔容为约0.20-0.50mL/g，比表面积为约260-600m 2/g，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛的硅含量为约90-99.8重量％，铝含量为约0.1-9.0重量％，磷含量为约0.01-2.5重量％；
所述分子筛的XRD谱图中，第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°。
B2、根据项目B1所述的分子筛，其中所述分子筛的XRD谱图中，第一强峰的衍射角位置在约6.1-6.8°，第二强峰的衍射角位置在约10.2-10.7°，第三强峰的衍射角位置在约15.8-16.5°。
B3、根据项目B1或B2所述的分子筛，其中所述分子筛的XRD谱图中，I 1/I 23.5-24.5。为约3.0-11.0，I 2/I 23.5-24.5。为约2.9-7.0，I 3/I 23.5-24.5。为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
B4、根据项目B1或B2所述的分子筛，其中所述分子筛的XRD谱图中，第四强峰的衍射角位置在约20.4-21.6°，第五强峰的衍射角位置在约11.8-12.8°。
B5、根据项目B4所述的分子筛，其中所述分子筛的XRD谱图中，第四强峰的衍射角位置在约20.8-21.4°，第五强峰的衍射角位置在约 12.1-12.6°；和/或，
I 4/I 23.5-24.5。为约1.0-4.0，I 5/I 23.5-24.5。为约1.0-2.0，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
B6、一种制备项目B1到B5中任一项所述的含磷高硅分子筛的方法，包括以下步骤：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-2MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水打浆，得到第一浆液，将该第一浆液加热至约40-95℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.5-4，然后恒温反应约0.5-20h，收集第一固体产物；
c)将步骤b)得到的所述第一固体产物加水打浆，得到第二浆液，将该第二浆液加热至约40-95℃，然后保持温度并连续向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约1.0-2.0，然后恒温反应约0.5-20h，收集第二固体产物。
B7、根据项目B6所述的方法，其中步骤a)中，所述含磷分子筛原料为含磷的Y型分子筛，所述含磷的Y型分子筛的晶胞常数为约2.425-2.47nm，比表面积为约250-750m 2/g，孔容为约0.2-0.95mL/g。
B8、根据项目B6所述的方法，其中步骤b)中，所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例为约14∶1至约5∶1。
B9、根据项目B6所述的方法，其中步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例为约0.5∶1至约20∶1。
B10、根据项目B6所述的方法，其中步骤c)中，加入所述第二酸溶液的方式为：以1L所述第二浆液为基准，以H +计，按照约0.05-10mol/h的速度将所述第二酸溶液加入到所述第二浆液中。
B11、根据项目B6所述的方法，其中步骤b)中，所述第一酸溶液的酸浓度为约0.01-15.0mol/L，所述第一酸溶液中的酸为选自磷酸、硫 酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种；和/或，
步骤c)中，所述第二酸溶液的酸浓度为约0.01-15.0mol/L，所述第二酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种。
B12、根据项目B6所述的方法，其中该方法还包括：收集所述第二固体产物，然后水洗、干燥，得到含磷硅铝分子筛；和/或，所述干燥的条件为：温度为约50-350℃，优选为约70-200℃；时间为约1-24h，优选为约2-6h。
B13、一种项目B1到B5中任一项所述的含磷高硅分子筛在烃类原料的加氢裂化反应中的应用。
B14、根据项目B13所述的应用，其中所述烃类原料为直馏瓦斯油、减压瓦斯油、脱金属油、常压渣油、脱沥青减压渣油、焦化馏出油、催化裂化馏出油、页岩油、沥青砂油或煤液化油，或者它们中的两种或三种的组合；和/或，
所述加氢裂化反应的条件为：反应温度为约200-650℃，优选为约300-510℃；反应压力为约3-24MPa，优选为约4-15MPa；液时空速为约0.1-50h -1，优选为约0.2-30h -1；氢油体积比为约100-5000。
C1、一种加氢裂化催化剂，其特征在于，以催化剂的干基重量为基准，该催化剂包括以干基重量计的45-90重量％的载体，以金属氧化物计的1-40重量％的第一金属组分，和以金属氧化物计的1-15重量％的第二金属组分；
所述载体包括含磷高硅分子筛和耐热无机氧化物，所述含磷高硅分子筛和耐热无机氧化物的重量比为约0.03∶1至约20∶1；所述第一金属组分为选自第VIB族金属的金属组分；所述第二金属组分为选自第VIII族金属的金属组分；
所述含磷高硅分子筛的孔容为约0.20-0.50mL/g，比表面积为约260-600m 2/g，以氧化物计并以分子筛的干基重量为基准，所述含磷高硅分子筛的硅含量为约90-99.8重量％，铝含量为约0.1-9.0重量％，磷含量为约0.01-2.5重量％；所述含磷高硅分子筛的XRD谱图中，第一强峰的衍射角位置在约5.9-6.9°，第二强峰的衍射角位置在约10.0-11.0°，第三强峰的衍射角位置在约15.6-16.7°。
C2、根据项目C1所述的催化剂，其中所述含磷高硅分子筛的XRD谱图中，第一强峰的衍射角位置在约6.1-6.8°，第二强峰的衍射角位置在约10.2-10.7°，第三强峰的衍射角位置在约15.8-16.5°。
C3、根据项目C1或C2所述的催化剂，其中所述含磷高硅分子筛的XRD谱图中，I 1/I 23.5-24.5。为约3.0-11.0，I 2/I 23.5-24.5。为约2.9-7.0，I 3/I 23.5-24.5。为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
C4、根据项目C1或C2所述的催化剂，其中所述含磷高硅分子筛的XRD谱图中，第四强峰的衍射角位置在约20.4-21.6°，第五强峰的衍射角位置在约11.8-12.8°。
C5、根据项目C4所述的催化剂，其中所述含磷高硅分子筛的XRD谱图中，第四强峰的衍射角位置在约20.8-21.4°，第五强峰的衍射角位置在约12.1-12.6°；和/或，
I 4/I 23.5-24.5。为约1.0-4.0，I 5/I 23.5-24.5。为约1.0-2.0，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5。为衍射角位置在约23.5-24.5°的峰的峰高。
C6、根据项目C1或2所述的催化剂，其中所述含磷高硅分子筛通过包括如下步骤的方法制备得到：
a)使含磷分子筛原料在约350-700℃的温度，约0.1-2MPa的压力和水蒸汽存在下进行水热处理约0.5-10h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％，钠含量为约0.5-4.5重量％；
b)将步骤a)得到的所述经水热处理的分子筛物料加水打浆，得到第一浆液，将该第一浆液加热至约40-95℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.5-4，然后恒温反应约0.5-20h，收集第一固体产物；
c)将步骤b)得到的所述第一固体产物加水打浆，得到第二浆液，将该第二浆液加热至约40-95℃，然后保持温度并连续向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约1.0-2.0，然后恒温反应约0.5-20h，收集第二固体产 物。
C7、根据项目C6所述的催化剂，其中步骤a)中，所述含磷分子筛原料为含磷的Y型分子筛，所述含磷的Y型分子筛的晶胞常数为约2.425-2.47nm，比表面积为约250-750m 2/g，孔容为约0.2-0.95mL/g。
C8、根据项目C6所述的催化剂，其中步骤b)中，所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例为约14∶1至约5∶1。
C9、根据项目C6所述的催化剂，其中步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例为约0.5∶1至约20∶1。
C10、根据项目C6所述的催化剂，其中步骤c)中，加入所述第二酸溶液的方式为：以1L所述第二浆液为基准，以H +计，按照约0.05-10摩尔/h的速度将所述第二酸溶液加入到所述第二浆液中。
C11、根据项目C6所述的催化剂，其中步骤b)中，所述第一酸溶液的酸浓度为约0.01-15.0mol/L，所述第一酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种；和/或，
步骤c)中，所述第二酸溶液的酸浓度为约0.01-15.0mol/L，所述第二酸溶液中的酸为选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种。
C12、根据项目C6所述的催化剂，其中所述含磷高硅分子筛的制备步骤还包括：收集所述第二固体产物，然后水洗、干燥，得到含磷高硅分子筛；和/或，所述干燥的条件为：温度为约50-350℃，优选为约70-200℃；时间为约1-24h，优选为约2-6h。
C13、根据项目C1所述的催化剂，其中所述耐热无机氧化物为氧化铝、氧化硅、氧化钛、氧化锆、氧化镁、氧化钍、氧化铍、氧化硼或氧化镉，或者它们中的两种或三种的组合；和/或，
所述第一金属组分为钼组分和/或钨组分；所述第二金属组分为铁组分、镍组分或钴组分，或者它们中的两种或三种的组合。
C14、一种制备项目C1到C13中任一项所述的加氢裂化催化剂的方法，包括：使含有第一金属前驱物和第二金属前驱物的浸渍液与载体接触进行浸渍。
C15、根据项目C14所述的方法，其中该方法还包括：将含磷高硅分子筛和耐热无机氧化物混合，然后成型、干燥、焙烧，得到所述载 体。
C16、根据项目C14所述的方法，其中所述第一金属前驱物为第一金属的无机酸、第一金属的无机盐或第一金属有机化合物；所述无机盐为硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐或氯化物；所述第一金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基、烷基中的至少一种；和/或，
所述第二金属前驱物为第二金属的无机酸、第二金属的无机盐或第二金属有机化合物；所述无机盐为硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐或氯化物；所述第二金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基、烷基中的至少一种。
C17、根据项目C14所述的方法，其中该方法还包括将浸渍后得到的物料干燥、焙烧的步骤；和/或，
所述干燥的条件为：温度为约80-350℃，时间为约0.5-24h；和/或，
所述焙烧的条件为：温度为约350-600℃，时间为约0.2-12h。
C18、一种项目C1-13中任一项所述的加氢裂化催化剂在烃类原料的加氢裂化反应中的应用。
C19、根据项目C18所述的应用，其中所述烃类原料为直馏瓦斯油、减压瓦斯油、脱金属油、常压渣油、脱沥青减压渣油、焦化馏出油、催化裂化馏出油、页岩油、沥青砂油或煤液化油，或者它们中的两种或三种的组合；和/或，
所述加氢裂化反应的条件为：反应温度为约200-650℃，优选为约300-510℃；反应压力为约3-24MPa，优选为约4-15MPa；液时空速为约0.1-50h -1，优选为约0.2-30h -1；氢油体积比为约100-5000。
实施例
下面通过实施例对本申请做进一步的说明，但并不因此而限制本申请的内容。
仪器和方法
在以下实施例和对比例中，分子筛的孔容和比表面积采用美国Micromertics仪器公司的ASAP 2400型自动吸附仪，通过静态低温吸 附容量法测定(按照国标GB/T5816-1995的方法)，具体方法为：将待测分子筛在250℃、1.33Pa下抽真空脱气4h，在-196℃下使其与作为吸附质的氮气接触，静态吸附达到吸附平衡；由氮气进气量与吸附后残存于气相中的差值计算出吸附剂吸附氮气的量，然后用BJH公式计算孔径分布，用BET公式计算比表面积和孔容。
分子筛的晶体结构采用德国西门子公司的D5005型X射线衍射仪测定，按照行业标准SH/T0339-92的方法。实验条件为：Cu靶，kα辐射，固体探测器，管电压40kV，管电流40mA，步进扫描，步幅0.02°，预制时间2s，扫描范围5°-70°。衍射角位置是指衍射峰出峰最高值的2θ角数值。
分子筛的硅含量、铝含量、磷含量和钠含量采用日本理学电机工业株式会社的3271E型X射线荧光光谱仪测定，测定方法为：粉末样品压片成型，铑靶，激光电压50kV，激光电流50mA，以闪烁计数器和正比计数器探测各元素谱线强度，用外标法对元素含量进行定量和半定量分析。
分子筛制备实施例
制备实施例1-2用于说明根据本申请的含磷高硅分子筛及其制备方法。
制备实施例1
取含磷分子筛(中国石化催化剂长岭分公司生产的USY分子筛，晶胞常数为2.456nm，比表面积为672m 2/g，孔容为0.357mL/g，Na 2O含量为1.44重量％，P 2O 5含量为1.37重量％、SiO 2含量为76.7重量％和Al 2O 3含量为20.5重量％)500g置入水热釜中，通入100％水蒸汽，在560℃、0.8MPa下进行水热处理3h，随后将经水热处理的分子筛物料取出。
取上述经水热处理的分子筛物料50g(干基)，加入500mL去离子水，搅拌打浆，得到第一浆液。将其升温至80℃，加入2.0mol/L的硫酸溶液，检测加酸后的第一浆液的pH值为2.8时停止加酸，然后恒温反应4h，过滤，得到40g第一固体产物。
将上述第一固体产物加入400mL去离子水，搅拌打浆，得到第二浆液。将其升温至80℃，以1L第二浆液为基准，以H +计，按照5mol/h 的速度将2mol/L的硫酸溶液加入到第二浆液中，检测加酸后的第二浆液的pH值为1.4时停止加酸，然后恒温反应3h，过滤，收集第二固体产物。
将所得固体产物在180℃干燥3h，得到含磷高硅分子筛Y-1，其XRD谱图如图1所示。所得分子筛的XRD衍射峰位置列于表1，衍射峰峰高列于表2，其他性质列于表3。
制备实施例2
按照制备实施例1的方法制备含磷高硅分子筛，区别在于，加入第二酸溶液时，按照15mol/h的速度加入。制备得到含磷高硅分子筛Y-2，其XRD谱图如图1所示。所得分子筛的XRD衍射峰位置列于表1，衍射峰峰高列于表2，其他性质列于表3。
制备对比例1-3用于说明非本申请的分子筛及其制备方法。
制备对比例1
参考中国专利ZL98117286.5的实施例1制备得到PSRY分子筛，记为分子筛DY-1，其XRD谱图如图1所示。所得分子筛的XRD衍射峰位置列于表1，衍射峰峰高列于表2，其他性质列于表3。
制备对比例2
取不含磷的HY分子筛(中石化催化剂长岭分公司生产，商品名HY，晶胞常数为2.465nm，比表面积为580m 2/g，孔容为0.33mL/g，Na 2O含量为0.3重量％，SiO 2含量为77.7重量％、Al 2O 3含量为22重量％)500g置入水热釜中，通入100％水蒸汽，在500℃、2.0MPa下进行水热处理1h，随后将经水热处理的分子筛物料取出。
取上述经水热处理的分子筛物料80g(干基)，加入500mL去离子水，搅拌打浆，得到第一浆液。将其升温至80℃，加入1.0mol/L的硫酸溶液，检测加酸后的第一浆液pH值为3.0时停止加酸，然后恒温反应约4h，过滤，得到65g第一固体产物。
将上述第一固体产物加入600mL去离子水，搅拌打浆，得到第二浆液。将其升温至80℃，以1L第二浆液为基准，以H +计，按照2mol/h的速度将1.0mol/L的磷酸溶液加入到第二浆液中，检测加酸后的第二 浆液pH值为1.4时停止加酸，然后恒温反应约3h，过滤，收集第二固体产物。将所得固体产物在180℃干燥3h，得到含磷硅铝分子筛DY-2，其XRD谱图如图1所示。所得分子筛的XRD衍射峰位置列于表1，衍射峰峰高列于表2，其他性质列于表3。
制备对比例3
取含磷分子筛(同实施例1)500g置入水热釜中，通入100％水蒸汽，在560℃、0.8MPa下进行水热处理3h，随后将经水热处理的分子筛物料取出。
取上述经水热处理的分子筛物料60g(干基)，加入500mL去离子水，搅拌打浆，得到第一浆液。将其升温至90℃，加入2.0mol/L的硫酸溶液，检测加酸后的第一浆液pH值为2.5时停止加酸，然后恒温反应约4h，过滤，得到60g第一固体产物。将所得固体产物在180℃干燥3h，得到含磷硅铝分子筛DY-3，其XRD谱图如图1所示。所得分子筛的XRD衍射峰位置列于表1，衍射峰峰高列于表2，其他性质列于表3。
表1制备实施例1-2和制备对比例1-3所得分子筛的XRD衍射峰位置
Figure PCTCN2019102008-appb-000001
表2制备实施例1-2和制备对比例1-3所得分子筛的XRD衍射峰峰高
Figure PCTCN2019102008-appb-000002
表3制备实施例1-2和制备对比例1-3所得分子筛的其他性质
Figure PCTCN2019102008-appb-000003
催化剂实施例
实施例1-6用于说明根据本申请的加氢裂化催化剂及其制备方法。对比例1-3用于说明非本申请的加氢裂化催化剂及其制备方法。
实施例1
将干基计80g分子筛Y-1与28.8g拟薄水铝石(中石化催化剂长岭分公司，商品名PB90，干基70重量％，其中干基条件为将样品在600℃焙烧3h后，所得样品占初始样品的重量比例，下同)混合，挤出成外接圆直径为1.6毫米的三叶形条，120℃干燥3h，600℃温度下焙烧3h，得载体CS-1。
降温至室温后，取100g CS-1载体用含34.65g偏钨酸铵(四川自贡硬质合金厂，氧化钨含量为82重量％)和24.37g硝酸镍(北京新光化学试剂厂，氧化镍含量为27.85重量％)的70mL水溶液浸渍，120℃ 干燥3h，480℃焙烧4h，得到加氢裂化催化剂，其组成见表4。
实施例2
按照实施例1的方法制备催化剂，区别在于，用分子筛Y-2替代分子筛Y-1。所得催化剂组成见表4。
实施例3
将干基计95g分子筛Y-1与7.2g拟薄水铝石混合，挤出成外接圆直径为1.6毫米的三叶形条，120℃干燥3h，600℃温度下焙烧3h，得载体CS-3。
降温至室温后，取100g CS-3载体用含13.86g偏钨酸铵和8.16g硝酸镍的45mL水溶液浸渍，120℃干燥3h，480℃焙烧4h，得到加氢裂化催化剂，其组成见表4。
实施例4
将干基计5g分子筛Y-1与135.7g拟薄水铝石混合，挤出成外接圆直径为1.6毫米的三叶形条，120℃干燥3h，600℃温度下焙烧3h，得载体CS-4。
降温至室温后，取100g CS-4载体用含74g偏钨酸铵和43g硝酸镍的70mL水溶液浸渍，120℃干燥3h，480℃焙烧4h，得到加氢裂化催化剂，其组成见表4。
实施例5
将干基计50g分子筛Y-1与干基计10g二氧化钛(北京化学试剂厂，纯度99％)和57.1g拟薄水铝石混合，挤出成外接圆直径为1.6毫米的三叶形条，120℃干燥3h，600℃温度下焙烧3h，得载体CS-5。
降温至室温后，取100g CS-5载体用含69g偏钨酸铵和17g硝酸镍的80mL水溶液浸渍，120℃干燥3h，480℃焙烧4h，得到加氢裂化催化剂，其组成见表4。
实施例6
将干基计30g分子筛Y-1与160g硅溶胶(北京飞龙马经贸有限公 司，商品名JN-25，二氧化硅含量25％，二氧化硅颗粒直径9-11nm)和42.9g拟薄水铝石(中石化催化剂长岭分公司，商品名PB90，干基70重量％)混合，挤出成外接圆直径为1.6毫米的三叶形条，120℃干燥3h，600℃温度下焙烧3h，得载体CS-6。
降温至室温后，取100g CS-6载体用含29g三氧化钼(洛阳金堆城钼业，纯度99.6％)、67g硝酸钴(北京新光化学试剂厂，氧化钴含量为27.85重量％)和11.8g磷酸(北京化学试剂厂，纯度85％)的95mL水溶液浸渍，120℃干燥3h，480℃焙烧4h，得到加氢裂化催化剂，其组成见表4。
对比例1-3
按照实施例1的方法制备催化剂，区别在于，分别用分子筛DY-1、DY-2和DY-3替代分子筛Y-1。所得催化剂组成见表4。
表4实施例和对比例中得到的催化剂的性质
Figure PCTCN2019102008-appb-000004
测试实施例
本测试实施例用于测试实施例1-3和对比例1-3的催化剂用于加氢 裂化反应的催化活性。
以含5.61％四氢萘和0.29％吡啶的正辛烷为原料，在小型固定床加氢裂化装置上评价催化剂的加氢裂化活性，催化剂装量为0.2毫升，反应温度为320℃，反应压力为4.0MPa，氢油体积比为3600，液时空速为30h -1，反应进料稳定4h后，以产物组成中转化的四氢萘百分比代表催化剂的活性，评价结果见表5。
表5实施例1-3和对比例1-3的催化剂的测试结果
催化剂 转化率(％)
实施例1 78.0
实施例2 71.2
实施例3 76.3
对比例1 54.3
对比例2 63.2
对比例3 58.3
从表5的结果可以看出，在可比条件下，与包含非本申请的含磷硅铝分子筛的催化剂相比，含有本申请提供的含磷高硅分子筛的催化剂在高含氮物质(如吡啶)存在下的加氢裂化催化活性提高了至少7％以上。
以上结合附图详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (15)

  1. 一种含磷高硅分子筛，以氧化物计并以所述分子筛的干基重量为基准，所述分子筛包含约86.5-99.8重量％、优选约90-99.8重量％的硅，约0.1-13.5重量％、优选约0.1-9.0重量％的铝和约0.01-6重量％、优选约0.01-2.5重量％的磷，
    所述分子筛的XRD谱图中具有至少三个衍射峰，其中第一强峰的衍射角位置在约5.9-6.9°，优选在约6.1-6.8°；第二强峰的衍射角位置在约10.0-11.0°，优选在约10.2-10.7°；且第三强峰的衍射角位置在约15.6-16.7°，优选在约15.8-16.5°，
    优选地，所述分子筛的孔容为约0.20-0.50mL/g、优选约0.30-0.45mL/g，比表面积为约250-670m 2/g、优选约260-600m 2/g。
  2. 根据权利要求1所述的分子筛，其中在所述分子筛的XRD谱图中，I 1/I 23.5-24.5°为约3.0-11.0，I 2/I 23.5-24.5°为约2.9-7.0，且I 3/I 23.5-24.5°为约1.0-4.0，其中I 1为所述第一强峰的峰高，I 2为所述第二强峰的峰高，I 3为所述第三强峰的峰高，I 23.5-24.5°为衍射角位置在约23.5-24.5°的峰的峰高。
  3. 根据前述权利要求中任一项所述的分子筛，其中所述分子筛的XRD谱图中具有至少五个衍射峰，其中第四强峰的衍射角位置在约20.4-21.6°，优选在约20.8-21.4°；且第五强峰的衍射角位置在约11.8-12.8°，优选在约12.1-12.6°，
    优选地，在所述分子筛的XRD谱图中，I 4/I 23.5-24.5°为约1.0-4.0，且I 5/I 23.5-24.5°为约1.0-2.0，其中I 4为所述第四强峰的峰高，I 5为所述第五强峰的峰高，I 23.5-24.5°为衍射角位置在约23.5-24.5°的峰的峰高。
  4. 制备含磷高硅分子筛的方法，包括以下步骤：
    a)使含磷分子筛原料在约350-700℃、优选约400-650℃的温度，约0.1-8.0MPa、优选约0.5-5MPa的压力和水蒸汽存在下进行水热处理约0.5-10h、优选约1-7h，得到经水热处理的分子筛物料；以氧化物计并以含磷分子筛原料的干基重量为基准，所述含磷分子筛原料的磷含量为约0.1-15重量％、优选约0.1-6重量％，钠含量为约0.5-4.5重量％、优选约0.5-3.0重量％，硅含量为约70-85重量％、优选约70-80重量％，铝含量为约16.0-21.0重量％、优选约18.0-21.0重量％；
    b)将步骤a)得到的所述经水热处理的分子筛物料加水制成第一浆液，将该第一浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第一浆液中加入第一酸溶液，所述第一酸溶液的加入量使所得的加酸后的第一浆液的pH值为约2.3-4.0、优选约2.5-4.0，然后恒温反应约0.5-20h、优选约1-10h，收集第一固体产物；以及
    c)将步骤b)得到的所述第一固体产物加水制成第二浆液，将该第二浆液加热至约40-95℃，优选约50-85℃，然后保持温度并向该第二浆液中加入第二酸溶液，所述第二酸溶液的加入量使所得的加酸后的第二浆液的pH值为约0.8-2.0、优选约1.0-2.0，然后恒温反应约0.5-20h、优选约1-10h，收集第二固体产物。
  5. 根据权利要求4所述的方法，其中步骤a)中，所述含磷分子筛原料为含磷的Y型分子筛，所述含磷的Y型分子筛的晶胞常数为约2.425-2.47nm，比表面积为约250-750m 2/g，孔容为约0.2-0.95mL/g。
  6. 根据权利要求4或5所述的方法，其中步骤b)中，所述第一浆液中水的重量与含磷分子筛原料的干基重量的比例为约14∶1至约5∶1；和/或
    步骤c)中，所述第二浆液中水的重量与含磷分子筛原料的干基重量的比例为约0.5∶1至约20∶1。
  7. 根据权利要求4-6中任一项所述的方法，其中步骤c)中，加入所述第二酸溶液的方式为：以1L所述第二浆液为基准，以H +计，按照约0.05-15mol/h，优选约0.05-10mol/h，更优选约2-8mol/h的速度将所述第二酸溶液加入到所述第二浆液中。
  8. 根据权利要求4-7中任一项所述的方法，其中步骤b)中，所述第一酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第一酸溶液中的酸选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸；和/或
    步骤c)中，所述第二酸溶液的酸浓度为约0.01-15.0mol/L，优选约0.1-5.0mol/L，所述第二酸溶液中的酸选自磷酸、硫酸、硝酸、盐酸、醋酸、柠檬酸、酒石酸、甲酸和乙酸中的至少一种，优选选自硫酸和硝酸。
  9. 根据权利要求4-8中任一项所述的方法，进一步包括：收集所述第二固体产物，然后水洗、干燥，得到所述含磷高硅分子筛的步骤； 优选地，所述干燥的条件为：温度约50-350℃，优选约70-200℃；时间约1-24h，优选约2-6h。
  10. 一种加氢裂化催化剂，以催化剂的干基重量为基准，该催化剂包含以干基重量计约45-90重量％的载体，以金属氧化物计约1-40重量％的第一金属组分，和以金属氧化物计约1-15重量％的第二金属组分；
    所述载体包含含磷高硅分子筛和耐热无机氧化物，所述含磷高硅分子筛和耐热无机氧化物的重量比为约0.03∶1至约20∶1；
    其中，所述第一金属组分包含第VIB族金属，所述第二金属组分包含第VIII族金属，且所述含磷高硅分子筛为权利要求1-3中任一项所述的含磷高硅分子筛或者根据权利要求4-9中任一项所述的方法制备的含磷高硅分子筛。
  11. 根据权利要求10所述的加氢裂化催化剂，其中所述耐热无机氧化物选自氧化铝、氧化硅、氧化钛、氧化锆、氧化镁、氧化钍、氧化铍、氧化硼、氧化镉，和它们的任意组合，优选选自氧化硅和氧化铝；
    所述第一金属组分选自钼组分、钨组分和它们的任意组合；和/或
    所述第二金属组分选自铁组分、镍组分、钴组分，和它们的任意组合。
  12. 制备权利要求10-11中任一项所述的加氢裂化催化剂的方法，包括如下步骤：
    i)将权利要求1-3中任一项所述的含磷高硅分子筛或者根据权利要求4-9中任一项所述的方法制备的含磷高硅分子筛与耐热无机氧化物混合制成载体；以及
    ii)使含有第一金属前驱物和第二金属前驱物的浸渍液与所述载体接触进行浸渍，
    优选地，所述第一金属前驱物为第一金属的无机酸、第一金属的无机盐、第一金属的氧化物或第一金属有机化合物；所述无机盐为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中的至少一种；所述第一金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种；和/或
    优选地，所述第二金属前驱物为第二金属的无机酸、第二金属的 无机盐、第二金属的氧化物或第二金属有机化合物；所述无机盐为选自硝酸盐、碳酸盐、碱式碳酸盐、次磷酸盐、磷酸盐、硫酸盐和氯化物中的至少一种；所述第二金属有机化合物中的有机取代基为选自羟基、羧基、胺基、酮基、醚基和烷基中的至少一种。
  13. 根据权利要求12所述的方法，进一步包括将浸渍后得到的物料干燥、焙烧的步骤；
    优选地，所述干燥的条件为：温度约80-350℃，优选约100-300℃，时间约0.5-24h，优选约1-12h；和/或
    优选地，所述焙烧的条件为：温度约350-600℃，优选约400-550℃，时间约0.2-12h，优选约1-10h。
  14. 权利要求10-11中任一项所述的加氢裂化催化剂或者根据权利要求12-13中任一项所述的方法制备的加氢裂化催化剂在烃类原料的加氢裂化反应中的应用，包括使烃类原料与所述加氢裂化催化剂接触。
  15. 根据权利要求14所述的应用，其中所述烃类原料选自直馏瓦斯油、减压瓦斯油、脱金属油、常压渣油、脱沥青减压渣油、焦化馏出油、催化裂化馏出油、页岩油、沥青砂油、煤液化油，和它们的任意组合；和/或，
    所述加氢裂化反应的条件为：反应温度约200-650℃，优选约300-510℃；反应压力约3-24MPa，优选约4-15MPa；液时空速约0.1-50h -1，优选约0.2-30h -1；氢油体积比约100-5000。
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