WO2020038347A1 - 改性y型分子筛、包含它的催化裂化催化剂、及其制备和应用 - Google Patents

改性y型分子筛、包含它的催化裂化催化剂、及其制备和应用 Download PDF

Info

Publication number
WO2020038347A1
WO2020038347A1 PCT/CN2019/101513 CN2019101513W WO2020038347A1 WO 2020038347 A1 WO2020038347 A1 WO 2020038347A1 CN 2019101513 W CN2019101513 W CN 2019101513W WO 2020038347 A1 WO2020038347 A1 WO 2020038347A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular sieve
modified
type molecular
content
rare earth
Prior art date
Application number
PCT/CN2019/101513
Other languages
English (en)
French (fr)
Inventor
沙昊
周灵萍
袁帅
张蔚琳
陈振宇
许明德
田辉平
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201810948782.XA external-priority patent/CN110841691B/zh
Priority claimed from CN201810949445.2A external-priority patent/CN110841695B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to US17/268,371 priority Critical patent/US11130917B2/en
Priority to SG11202012300PA priority patent/SG11202012300PA/en
Priority to AU2019326622A priority patent/AU2019326622A1/en
Priority to JP2021509150A priority patent/JP7394116B2/ja
Publication of WO2020038347A1 publication Critical patent/WO2020038347A1/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J2029/081—Increasing the silica/alumina ratio; Desalumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0054—Drying of aerosols

Definitions

  • the present disclosure relates to the technical field of molecular sieves and catalytic cracking, and more particularly to a modified Y-type molecular sieve, a catalytic cracking catalyst including the same, and a method for preparing and using the same.
  • Light aromatic hydrocarbons such as benzene, toluene, and xylene (BTX) are important basic organic chemical raw materials. They are widely used in the production of polyester, chemical fiber, and so on. Demand has been strong in recent years. Light aromatics such as benzene, toluene and xylene are mainly derived from catalytic reforming and steam cracking processes using naphtha as raw materials. Due to the shortage of naphtha raw materials, there is a large market gap for light aromatics.
  • Catalytic cracking light cycle oil is an important by-product of catalytic cracking. It is large in quantity, rich in aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons, and belongs to inferior diesel oil fractions. With the development and change of market demand and environmental protection requirements, LCO as a diesel blending component has been greatly restricted.
  • the hydrocarbon composition of LCO includes paraffins, naphthenes (containing a small amount of olefins), and aromatics. Depending on the FCC feedstock and the severity of the operation, the hydrocarbon composition of LCOs varies widely, but aromatics are their main components. The mass fraction is greater than 70%, and some even reach about 90%, and the rest are paraffins and naphthenes.
  • the highest content of bicyclic aromatic hydrocarbons in LCO belongs to its typical components, and it is also a key component that affects the production of light aromatics by catalytic cracking.
  • polycyclic aromatic hydrocarbons are difficult to be ring-opened and cracked into light aromatics.
  • polycyclic aromatic hydrocarbons are more likely to be saturated with alkylbenzenes and cycloalkylbenzenes (indanes, tetrahydronaphthalenes). And indene) and other heavy monocyclic aromatic hydrocarbons.
  • Such heavy monocyclic aromatic hydrocarbons are potential components for catalytic cracking to produce light aromatics, and can be cracked into light aromatics under the conditions of catalytic cracking. Therefore, LCO is a potential and cheap resource for the production of light aromatics.
  • the production of light aromatics through the hydrotreating-catalytic cracking technology route has important research value.
  • Y-type molecular sieve has been the main active component of catalytic cracking (FCC) catalyst since it was first used in the 1960s.
  • FCC catalytic cracking
  • the content of polycyclic compounds in the FCC feedstock increased significantly, and its diffusion ability in the zeolite pores decreased significantly.
  • the pore size of Y-type molecular sieve is only 0.74nm, which is directly used to process heavy fractions such as residual oil.
  • the accessibility of the active center of the catalyst will become a major obstacle to the cracking of polycyclic compounds contained therein.
  • the pore structure of the molecular sieve is closely related to the cracking reaction performance.
  • the secondary pores of the molecular sieve can increase the accessibility of the residue macromolecules and their active centers, thereby improving the cracking ability of the residue.
  • Hydrothermal dealumination is one of the most widely used industrial methods for the preparation of ultra-stable molecular sieves with secondary pores.
  • This method first exchanges NaY molecular sieves with an aqueous solution of ammonium ions to reduce the sodium ion content in the molecular sieve. Then, The ammonium ion-exchanged molecular sieve is calcined at 600-825 ° C in a water vapor atmosphere to make it super-stabilized.
  • the method is low in cost and easy for industrialized large-scale production.
  • the obtained ultra-stable Y-type molecular sieve has rich secondary pores, but the crystallinity of the ultra-stable Y-type molecular sieve is seriously lost.
  • ultra-stable Y-type molecular sieves are generally an improvement on the above-mentioned hydrothermal roasting process.
  • the method of two exchanges and two roasts is adopted.
  • the purpose is to adopt milder roasting conditions in steps to solve the harsh roasting conditions.
  • the prepared ultra-stable Y molecular sieve also has a certain amount of secondary pores. However, the proportion of secondary pores with larger pores in the total secondary pores is lower.
  • the specific surface and crystallinity of superstable molecular sieves need to be further improved.
  • the purpose of the present invention is to develop a modified molecular sieve with high stability that has both strong cracking ability and weak hydrogen transfer performance as a new active group.
  • This new active component further develops a catalytic cracking catalyst for the production of BTX light aromatics suitable for hydrocracking LCO catalytic cracking, strengthens the cracking reaction, controls the hydrogen transfer reaction, and further improves the conversion efficiency of the hydrohydro LCO to maximize production.
  • One of the objectives of the present disclosure is to provide a modified Y-type molecular sieve, a catalytic cracking catalyst including the same, and a preparation method and application thereof.
  • the modified Y-type molecular sieve is used as an active component to prepare a catalytic cracking catalyst for processing.
  • hydrogen light cycle oil LCO
  • it has higher hydrogenation LCO conversion efficiency, lower coke selectivity, higher gasoline yield, and higher total ethylene and propylene yield.
  • the present disclosure provides a modified Y-type molecular sieve. Based on the dry basis weight of the modified Y-type molecular sieve, the rare earth content of the modified Y-type molecular sieve is about 4-11 wt% based on the rare earth oxide.
  • the sodium content is not more than about 0.7 wt% based on sodium oxide
  • the zinc content is about 0.5-5 wt% based on zinc oxide
  • the phosphorus content is about 0.05-10 wt% based on phosphorus pentoxide
  • the framework silicon-aluminum ratio is SiO 2 / Al 2 O 3 molar ratio is about 7-14
  • the percentage of non-framework aluminum content in the total aluminum content is not higher than about 20%
  • the percentage of the pore volume of the secondary pores with a pore size of 2-100 nm to the total pore volume is About 15-30%.
  • the present disclosure provides a method for preparing a modified Y-type molecular sieve, including the following steps:
  • the hydrothermal ultra-stable modification treatment of step (2) is performed by firing at a temperature of about 350-480 ° C. and about 30-90 vol% water vapor atmosphere for about 4.5-7 hours.
  • the present disclosure provides a catalytic cracking catalyst based on a dry basis weight of the catalyst, the catalyst comprising about 10-50 wt% of a modified Y-type molecular sieve, a binder, and clay; wherein the modified Y-type molecular sieve is a modified Y-type molecular sieve according to the present disclosure or a modified Y-type molecular sieve prepared by a method of the present disclosure.
  • the present disclosure provides an application of a modified Y-type molecular sieve according to the present disclosure in a catalytic cracking reaction of a hydrocarbon feedstock, particularly a hydrogenated light cycle oil, including making the hydrocarbon feedstock under catalytic cracking conditions.
  • a catalytic cracking catalyst comprising the modified Y-type molecular sieve.
  • the modified Y-type molecular sieve provided by the present disclosure contains phosphorus, rare earth and zinc modified components, has high crystallinity and a secondary pore structure, and has high thermal and hydrothermal stability.
  • the modified Y-type molecular sieve of the present disclosure can be used as an active component of a catalytic cracking catalyst for catalytic cracking of hydrogenated LCO.
  • a catalytic cracking catalyst using this molecular sieve as the active component is used to process hydrogenated LCO, it can not only improve the conversion efficiency of hydrogenated LCO, but also have lower coke selectivity and higher gasoline production rich in BTX light aromatics. Yields, and higher overall ethylene and propylene yields.
  • any specific numerical value (including the end of the numerical range) disclosed herein is not limited to the exact value of the value, but should be understood to also encompass values close to the exact value, such as within the range of ⁇ 5% of the exact value All possible values. And, for the disclosed numerical range, one or more new ones can be obtained by arbitrarily combining between the endpoint values of the range, between the endpoint values and the specific point values within the range, and between the specific point values. Numerical ranges, these new numerical ranges should also be considered as specifically disclosed herein.
  • any matter or matter not mentioned applies directly to those known in the art without any change.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention, and should not be It is considered to be something new that has not been disclosed or anticipated herein unless the person skilled in the art believes that the combination is obviously unreasonable.
  • RIPP Test Method for the RIPP test method involved in the present invention, please refer to "Petrochemical Analysis Method (RIPP Test Method)", edited by Yang Cuiding, Science Press, the first edition in September 1990, ISBN: 7-03-001894-X, Pages 263-268, 412-415, and 424-426, which are incorporated herein by reference in their entirety.
  • Y molecular sieve and “Y zeolite” are used interchangeably, and the terms “NaY molecular sieve” and “NaY zeolite” are also used interchangeably.
  • second pore refers to pores having a pore size (referring to a diameter) in the molecular sieve of 2-100 nm.
  • rare earth solution and “rare earth salt solution” are used interchangeably, preferably an aqueous solution of a rare earth salt.
  • Y-type molecular sieve of conventional unit cell size means that the unit cell constant of the Y-type molecular sieve is in the range of the unit cell constant of conventional NaY molecular sieves, preferably in the range of about 2.465 nm to about 2.472 nm.
  • normal pressure means a pressure of about 1 atm.
  • the dry basis weight of a substance refers to the weight of a solid product obtained by firing the substance at 800 ° C for 1 hour.
  • the mass of the various molecular sieves involved is on a dry basis; the mass (content) of rare earth salts and rare earths are all based on the mass (content) of rare earth oxides.
  • the mass (content) of rare earth oxide is based on the mass (content) of sodium oxide, which can also be referred to as the mass (content) of sodium oxide; the mass (content) of zinc and zinc salts are all based on zinc oxide
  • this article may also be referred to as zinc oxide mass (content); phosphorus mass (content) is based on the mass (content) of phosphorus pentoxide, and this article may also be referred to as P 2 O 5 mass (content) ).
  • the present disclosure provides a modified Y-type molecular sieve, based on the dry basis weight of the modified Y-type molecular sieve, the rare earth content of the modified Y-type molecular sieve is about 4- 11% by weight, sodium content not more than about 0.7% by weight based on sodium oxide, zinc content by about 0.5-5% by weight based on zinc oxide, phosphorus content by about 0.05-10% by weight based on phosphorus pentoxide, and the framework silicon-aluminum ratio by The SiO 2 / Al 2 O 3 molar ratio is about 7-14, the percentage of non-skeletal aluminum content in the total aluminum content is not higher than about 20%, and the pore volume of the secondary pores with a pore diameter of 2-100 nm accounts for the total pore volume. The percentage is about 15-30%.
  • the framework silicon-aluminum ratio (SiO 2 / Al 2 O 3 molar ratio) of the modified Y-type molecular sieve may be about 7.3-14, and may further be about 8.5-12.6, for example, about 8.79, 10.87 , 11.95, etc.
  • the rare earth content (content of the rare earth oxide) of the modified Y-type molecular sieve may be about 4.5-10% by weight, for example, about 5.6% by weight, 6.3% by weight, 8.4% by weight, and the like.
  • the kind and composition of the rare earth are not particularly limited.
  • the rare earth may include La, Ce, Pr, or Nd, or a combination of two, three, or four of them; optionally, the rare earth may further include La, Ce, Pr, and Nd. Of other rare earth elements.
  • the sodium content (content of sodium oxide) of the modified Y-type molecular sieve may be about 0.1-0.7 wt%, further may be about 0.3-0.7 wt%, and still further may be about 0.35. -0.6wt%, and can still be about 0.4-0.55wt%, such as about 0.44wt%, 0.49wt%, 0.57wt%, etc.
  • the zinc content (content based on zinc oxide) of the modified Y-type molecular sieve may be about 1-4 wt%, for example, may be about 1 wt%, 2 wt%, 4 wt%, and the like.
  • the phosphorus content of the modified Y-type molecular sieve may be about 0.1 to 6 wt%, and further may be about 0.1 to 5 wt%, such as about 0.95 wt%. , 2.21wt%, 3.68wt%, etc.
  • the non-framework aluminum content of the modified Y-type molecular sieve can be about 13-19%, such as about 13.2%, 16.5%, 18.5%, and the like.
  • the cell constant of the modified Y-type molecular sieve may be about 2.440-2.455 nm, preferably about 2.440-2.453 nm, and further preferably about 2.442-2.453 nm, such as about 2.443 nm, 2.445 nm. , 2.45nm, etc.
  • the total pore volume of the modified Y-type molecular sieve may be about 0.33-0.39 mL / g, preferably about 0.35-0.39 mL / g, and further preferably about 0.36-0.375 mL / g, for example About 0.355 mL / g, 0.364 mL / g, 0.373 mL / g, etc.
  • the pore structure of the modified Y-type molecular sieve can be further optimized to obtain more suitable catalytic cracking reaction performance.
  • the percentage of the pore volume of the secondary pores having a pore diameter (diameter) of 2.0-100 nm to the total pore volume may be about 20% -30%, preferably about 17% -21%, such as about 17.96% , 19.78%, 20.85%, etc.
  • the specific surface area of the modified Y-type molecular sieve may be about 600-670m 2 / g, preferably about 610-660m 2 / g, such as about 633m 2 / g, 640m 2 / g, 652m 2 / g and so on.
  • the lattice collapse temperature of the modified Y-type molecular sieve is not less than about 1050 ° C, and may be about 1055 ° C to 1080 ° C, preferably about 1056 to 1075 ° C, such as about 1055 ° C, 1061 ° C. , 1068 °C and so on.
  • the strong acid amount of the modified Y-type molecular sieve is measured by a pyridine adsorption infrared method at 350 ° C.
  • the ratio of the amount of B acid to the amount of L acid is not less than about 3.50, for example, it may be about 3.6-5.0, preferably about 3.7-4.3, and specifically may be about 3.76, 4.21, 4.95, and the like.
  • the relative crystallinity retention rate of the modified Y-type molecular sieve after aging for 17 hours at 800 ° C., atmospheric pressure, and 100% by volume of water vapor atmosphere is about 35% or more, for example, it may be about 38- 48% or about 35-45%, such as about 38.95%, 40.55%, 43.45%, and the like.
  • the relative crystallinity of the modified Y-type molecular sieve is not less than about 60%, for example, about 60-70%, preferably about 60-66%, and specifically about 60.4%, 62.7%, 65.3%, etc.
  • the modified Y-type molecular sieve provided by the present disclosure has both strong cracking ability and weak hydrogen transfer performance, and can be used as an active component of a catalytic cracking catalyst for catalytic cracking of hydrogenated LCO; using the molecular sieve as an active component
  • the FCC catalyst When used in the processing of hydrogenated LCO, the FCC catalyst has high LCO conversion efficiency, lower coke selectivity, higher yield of BTX-rich gasoline, and more ethylene and propylene in the gas product.
  • the present disclosure provides a method for preparing a modified Y-type molecular sieve, including the following steps:
  • the method of the present disclosure includes the following steps:
  • step (1) hydrothermal calcining the Y-type molecular sieve with a rare earth-containing conventional cell size and reduced sodium oxide content obtained in step (1), preferably at a temperature of about 350-480 ° C and a steam atmosphere of about 30-90 vol% Baking for about 4.5-7h to obtain a Y-type molecular sieve with a reduced cell constant;
  • step (3) contacting the Y-type molecular sieve having the reduced cell constant obtained in step (2) with a phosphorus compound for phosphorus modification treatment, introducing phosphorus into the molecular sieve to obtain a phosphorus modified molecular sieve;
  • step (3) (4) contacting the phosphorus-modified molecular sieve obtained in step (3) with gaseous SiCl 4 to carry out dealumination and silicon supplementation to obtain a gas-phase ultra-stable modified Y-type molecular sieve;
  • step (4) The gas-phase ultra-stable modified Y-type molecular sieve obtained in step (4) is impregnated with a zinc salt solution and calcined to obtain the modified Y-type molecular sieve.
  • the step (1) includes contacting a NaY molecular sieve with a rare earth salt solution for an ion exchange reaction, filtering, washing, and drying to obtain a rare earth-containing Y-type molecular sieve with a reduced sodium oxide content.
  • the cell constant of the NaY molecular sieve used in step (1) is about 2.465-2.472 nm
  • the framework silicon-aluminum ratio (SiO 2 / Al 2 O 3 molar ratio) is about 4.5-5.2
  • the relative crystallinity It is about 85% or more, for example, about 85-95%
  • the sodium oxide content is about 13.0-13.8 wt%.
  • the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content obtained in step (1) has a cell constant of about 2.465-2.472 nm, a sodium content of not more than about 9.5% by weight based on sodium oxide, and a rare earth content. Based on RE 2 O 3 (rare earth oxide), it is about 4.5-13% by weight.
  • the sodium oxide content of the rare earth-containing Y-type molecular sieve with reduced sodium oxide content obtained in step (1) may be about 5.5-9.5 wt%, preferably about 5.5-8.5 wt%, such as about 7.5% ;
  • the rare earth oxide content may be about 5.5-13 wt%, preferably about 5.5-12 wt% or 4.5-11.5 wt%.
  • the step (1) further comprises contacting the NaY molecular sieve with a rare earth salt in an aqueous solution for an ion exchange reaction, wherein the NaY molecular sieve (on a dry basis), the rare earth salt (on a rare earth oxide),
  • the mass ratio is about 1: (0.01-0.18): (5-15), and the water may be deionized water.
  • the rare earth salt is rare earth chloride and / or rare earth nitrate.
  • the rare earth may be any kind of rare earth, and there is no particular limitation on the kind and composition thereof, such as one or more of La, Ce, Pr, Nd, and mixed rare earth.
  • the mixed rare earth contains La Or more, or may further contain at least one of rare earths other than La, Ce, Pr, and Nd.
  • the exchange temperature of the ion exchange reaction in step (1) may be about 15-95 ° C, preferably about 65-95 ° C, such as about 90-95 ° C; the exchange time may be about 30-120 minutes , Preferably about 45-90 minutes.
  • the NaY molecular sieve, the rare earth salt and water are formed into a mixture, which may be first forming a slurry of the NaY molecular sieve and water, and then adding a rare earth salt and / or a rare earth salt to the slurry. Water solution.
  • the step (1) further comprises: mixing NaY molecular sieve with water, adding a rare earth salt and / or a rare earth salt solution under stirring to exchange rare earth ions with sodium ions, filtering, and washing; wherein, washing The purpose is to wash out the exchanged sodium ions, which can be washed with deionized water.
  • the NaY molecular sieve according to a ratio of NaY molecular sieve: rare earth salt: H 2 O mass ratio of about 1: (0.01-0.18) :( 5-15),
  • the rare earth salt and water form a mixture, and the rare earth ion and sodium ion are exchanged by stirring at a temperature of about 15-95 ° C for about 30-120 minutes.
  • the hydrothermal ultra-stable modification / hydrothermal roasting treatment of step (2) includes subjecting the ion-exchanged molecular sieve at a temperature of about 350-480 ° C and a water vapor atmosphere of about 30-90 vol% (Also called 30-90 vol% water vapor atmosphere or 30-90% water vapor atmosphere) Calcination is about 4.5-7 hours.
  • the ion-exchanged molecular sieve is calcined at a temperature of about 380-460 ° C and a water vapor atmosphere of about 40-80% by volume for about 5-6 hours.
  • the baking treatment may be performed at a temperature of about 390 ° C, about 450 ° C, or about 470 ° C, and about 50 vol%, about 70 vol%, or about 80 vol% water vapor atmosphere.
  • the water vapor atmosphere in step (2) may further contain other gases, such as one or more of air, helium, or nitrogen.
  • the cell constant of the molecular sieve treated in step (2) is reduced to about 2.450-2.462 nm, and the water content is less than about 1 wt%.
  • the step (3) further comprises drying the molecular sieve obtained in the step (2) so that the water content in the Y-type molecular sieve with a reduced cell constant does not exceed about 1% by weight.
  • the drying may Use air drying, drying, flash drying and other methods.
  • the step (3) further comprises contacting a Y-type molecular sieve having a reduced cell constant obtained in the step (2) with a solution containing a phosphorus compound.
  • the phosphorus compound used in step (3) may be one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the like.
  • the mass ratio of the mass of water in the solution to the mass of the molecular sieve is about (2-5): 1, preferably about (3). -4): 1.
  • the mass ratio of phosphorus (as P 2 O 5 ) to the molecular sieve is about (0.0005-0.10): 1, preferably (0.001-0.05): 1.
  • the temperature of the phosphorus modification treatment may be about 15-100 ° C, preferably about 30-95 ° C, and the processing time may be about 10-100 minutes.
  • the step (3) further comprises reacting the molecular sieve with the solution at about 15-100 ° C. for about 10-100 minutes, and then filtering and washing; water having a molecular weight of about 5-15 times is available. , Such as deionized water for washing.
  • the mass ratio of silicon tetrachloride to phosphorus-modified molecular sieve may be about (0.1-0.7): 1, preferably about (0.3-0.6): 1, for example, about 0.4: 1, 0.5: 1, 0.6: 1, and the like.
  • the reaction temperature of the molecular sieve and silicon tetrachloride may be about 200 ° C to 650 ° C, preferably about 350 ° C to 500 ° C, such as about 400 ° C, 480 ° C , 500 °C and so on.
  • the reaction time of the reaction between the molecular sieve and the silicon tetrachloride in step (4) is about 10 minutes to about 5 hours.
  • washing and filtration are performed to remove soluble by-products such as Na + , Cl ⁇ and Al 3+ remaining in the molecular sieve.
  • the washing in step (4) is performed using deionized water under the following conditions: the mass ratio of the water used to the molecular sieve may be about (5-20): 1, preferably about (6-15) : 1; washing temperature is about 30-60 ° C; the pH value of the washing liquid may be about 2.5-5.0. Typically, the washing is performed to wash the washing liquid was not detected in the free Na +, Cl - and Al 3+ plasma.
  • the zinc salt used in step (5) may be zinc nitrate or zinc chloride.
  • the step (5) further comprises formulating a zinc salt into a solution, and the weight ratio of the zinc salt (calculated as ZnO) to the molecular sieve is about (0.5-5.0): 100.
  • the concentration may be about 0.020-0.080 g / ml.
  • the immersion temperature in step (5) is about 10-60 ° C.
  • the impregnated molecular sieve may be dried at a temperature of about 130 ° C. for about 5 hours and then calcined.
  • the calcination temperature may be about 350-600 ° C. and the calcination time may be about 1-4 hours.
  • a method for preparing a modified Y-type molecular sieve includes the following steps:
  • the mass ratio of the reduced Y-type molecular sieve (on a dry basis) is about (0.1-0.7): 1, and the contact reaction is performed at a temperature of about 200-650 ° C for about 10 minutes to about 5 hours, and then washed and filtered; as well as
  • the modified Y molecular sieve obtained in step (4) is impregnated with a zinc salt solution at a temperature of about 10-60 ° C.
  • the impregnated molecular sieve is first dried at about 130 ° C for about 5 hours, and then at about 350-600
  • the modified Y molecular sieve is obtained by calcining at about 1-4 hours.
  • the preparation method of the modified Y-type molecular sieve provided by the present disclosure can prepare a high-silicon Y-type molecular sieve containing phosphorus, rare earth and zinc with a certain secondary pore structure with high crystallinity, high thermal stability and high hydrothermal stability.
  • the distribution of aluminum in the molecular sieve is uniform, and the non-framework aluminum content is small.
  • the catalytic cracking catalyst containing the modified Y-type molecular sieve prepared by the method disclosed in the present disclosure has high LCO conversion efficiency (that is, high effective LCO conversion rate), lower coke selectivity, and more when used for hydrogenated LCO catalytic cracking.
  • High and BTX-rich gasoline yields and more ethylene and propylene in the gas product.
  • the present disclosure provides a catalytic cracking catalyst based on a dry basis weight of the catalyst, the catalyst comprising about 10-50% by weight of a modified Y-type molecular sieve, a binder, and clay, wherein
  • the modified Y-type molecular sieve is a modified Y-type molecular sieve according to the present disclosure or a modified Y-type molecular sieve prepared by a method of the present disclosure.
  • the content of the modified Y-type molecular sieve of the catalyst on a dry basis may be about 10-50% by weight, preferably about 15-45% by weight, further preferably about 25-40% by weight, for example, specifically It may be about 25 wt%, 30 wt%, 40 wt%, and the like.
  • the clay may be one or more of clays suitable for use as a cracking catalyst component, such as selected from the group consisting of kaolin, kaolin, montmorillonite, diatomaceous earth, halloysite, Saponite, rector, sepiolite, attapulgite, hydrotalcite, bentonite, etc.
  • the clay content in the catalyst is about 10-80 wt%, preferably about 20-55 wt% or about 30-50 wt% on a dry basis.
  • the binder is an alumina binder.
  • the content of the alumina binder in the catalyst may be about 10-40% by weight, preferably about 20-35% by weight.
  • the alumina binder may be one or more of various forms of alumina, hydrated alumina, and aluminum sol commonly used in cracking catalysts.
  • it may be selected from ⁇ -oxidation.
  • the catalyst contains about 2-15 wt%, preferably about 3-10 wt% of an aluminum sol, based on alumina, and about 10-30 wt%, preferably about 15-25 wt%, of a pseudo-alumina. Boehmite.
  • the catalyst may further include other molecular sieves other than the modified Y-type molecular sieve.
  • the content of the other molecular sieves may be about 0-40% by weight on a dry basis. It is preferably about 0-30% by weight, and more preferably about 1-20% by weight.
  • the other molecular sieves may be molecular sieves commonly used in catalytic cracking catalysts, such as one or more of zeolites with MFI structure, Beta zeolites, other Y-type zeolites, and non-zeolite molecular sieves.
  • the mass of the other Y-type zeolite does not exceed about 40% of the mass of the catalyst on a dry basis, and may be about 0-40% by weight, preferably about 1-20% by weight.
  • the other Y-type zeolite may be, for example, one or more of REY, REHY, DASY, SOY, and PSRY;
  • the MFI structure zeolite may be, for example, one of HZSM-5, ZRP, and ZSP Or more;
  • Beta zeolites such as H ⁇ , non-zeolitic molecular sieves may be, for example, one or more of aluminum phosphate molecular sieves (AlPO molecular sieves) and silicoaluminophosphate molecular sieves (SAPO molecular sieves).
  • the catalytic cracking catalyst provided by the present disclosure contains a modified Y-type molecular sieve with high thermal and hydrothermal stability, and has high hydrothermal stability.
  • the catalytic cracking catalyst provided by the present disclosure uses a modified molecular sieve with high stability that has both strong cracking ability and weak hydrogen transfer performance as the active component, which can strengthen the cracking reaction, control the hydrogen transfer reaction, and be used for hydrogenation.
  • LCO catalytic cracking compared with existing conventional catalytic cracking catalysts containing Y-type molecular sieves, it has higher LCO conversion efficiency, lower coke selectivity, and higher yield of BTX-rich gasoline, and gas
  • the product contains more ethylene and propylene.
  • the present disclosure provides a method for preparing a catalytic cracking catalyst, comprising the steps of: providing a modified Y-type molecular sieve, forming a slurry including the modified Y-type molecular sieve, a binder, clay, and water, and Spray drying, optional washing and optional drying to obtain the catalytic cracking catalyst, wherein the providing a modified Y-type molecular sieve comprises providing a modified Y-type molecular sieve according to the present disclosure, or preparing a modified Y-type molecular sieve according to the method of the present disclosure.
  • Molecular sieve comprising the steps of: providing a modified Y-type molecular sieve, forming a slurry including the modified Y-type molecular sieve, a binder, clay, and water, and Spray drying, optional washing and optional drying to obtain the catalytic cracking catalyst, wherein the providing a modified Y-type molecular sieve comprises providing a modified Y-type molecular sieve according
  • steps of the catalyst preparation method of the present disclosure may refer to existing methods, for example, according to the methods described in Chinese Patent Application Publications CN1098130A and CN1362472A.
  • the spray drying, washing, and drying can adopt the prior art, and the present invention has no special requirements.
  • the present disclosure provides an application of a modified Y-type molecular sieve according to the present disclosure in a catalytic cracking reaction of a hydrocarbon feedstock, in particular a hydrogenated light cycle oil, including making the hydrocarbons under catalytic cracking conditions.
  • the raw material is contacted with a catalytic cracking catalyst comprising the modified Y-type molecular sieve.
  • the present disclosure provides an application of a catalytic cracking catalyst according to the present disclosure in a catalytic cracking reaction of a hydrocarbon feedstock, particularly a hydro-recycling light cycle oil, including the step of catalytically cracking the hydrocarbon feedstock with a catalytic cracking condition.
  • the catalytic cracking catalyst is contacted.
  • the present disclosure provides a catalytic cracking method for processing a hydrogenated light cycle oil (hydrogenated LCO), comprising, under catalytic cracking conditions, causing the hydrogenated LCO and the catalytic cracking catalyst of the present disclosure or A step of contacting a catalytic cracking catalyst comprising a modified Y-type molecular sieve of the present disclosure.
  • hydrogenated LCO hydrogenated light cycle oil
  • the catalytic cracking conditions may include: a reaction temperature of about 500-610 ° C., a weight hourly space velocity of about 2-16 h -1 , and a weight ratio of agent to oil of about 3-10.
  • the hydrogenated LCO has the following properties: a density (20 ° C) of about 0.850-0.920 g / cm 3 , an H content of about 10.5-12 wt%, an S content of ⁇ 50 ⁇ g / g, and an N content of ⁇ 10 ⁇ g / g, total aromatics content is about 70-85% by weight, and polycyclic aromatics content is ⁇ 15% by weight.
  • the present disclosure provides the following technical solutions:
  • a modified Y-type molecular sieve wherein the rare earth content is about 4-11 wt% based on rare earth oxide, the sodium content is not more than about 0.7 wt% based on sodium oxide, and the zinc content is about 0.5-5 wt% based on zinc oxide %, phosphorus pentoxide content of from about 0.05-10 wt%, the skeleton alumina ratio 2 / Al 2 O 3 molar ratio of SiO amount of about 7-14 weight percentage of the total non-framework aluminum of the aluminum mass is not Above about 20%, the percentage of the pore volume of the secondary pores with a pore size of 2-100 nm to the total pore volume is about 15-30%.
  • the constant is about 2.440-2.453nm, and the framework silicon-aluminum ratio is about 8.5-12.6.
  • a method for preparing a modified Y molecular sieve including the following steps:
  • step (4) The molecular sieve after the reaction in step (4) is impregnated with a zinc salt solution.
  • the ion exchange temperature is about 15-95 ° C, and the exchange time is about 30-120 minutes, the NaY molecular sieve, rare earth salt, water
  • the mass ratio is about 1: (0.01-0.18): (5-15)
  • the mass of the NaY molecular sieve is on a dry basis
  • the mass of the rare earth salt is based on a rare earth oxide.
  • step (2) is performed in an atmosphere of 350-480 ° C and a water vapor content of about 30-90 vol%, and the baking time is about 4.5-7 hours.
  • the phosphorus compound used for the phosphorus modification treatment is selected from one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate. Or more.
  • reaction temperature is about 200 ° C to 650 ° C
  • reaction time is about 10 minutes to about 5 hours.
  • the silicon tetrachloride and the silicon tetrachloride The mass ratio of the molecular sieve after the phosphorus modification treatment is about (0.1-0.7): 1, and the mass of the calcined molecular sieve is on a dry basis.
  • step (5) comprises roasting the impregnated molecular sieve, the soaking temperature is about 10-60 ° C, the roasting temperature is about 350-600 ° C, and the roasting time is about 1 -4 hours.
  • a catalytic cracking catalyst for processing hydrogenated LCO comprising a modified Y-type molecular sieve; in the modified Y-type molecular sieve, the rare earth content is about 4-11 wt% based on the rare earth oxide, and the sodium content is based on sodium oxide counted no more than about 0.7wt%, the content of zinc as zinc oxide is about 0.5-5wt%, a phosphorus pentoxide content of from about 0.05-10wt%, backbone alumina ratio SiO 2 / Al 2 O 3 molar The ratio is about 7-14, the percentage of the mass of non-framework aluminum to the total aluminum mass is not higher than about 20%, and the pore volume of the secondary pores with a pore size of 2-100 nm of the modified Y-type molecular sieve accounts for the modified The percentage of the total pore volume of the sex Y molecular sieve is about 15-30%.
  • the rare earth content is about 4.5-10 wt%
  • the sodium content is about 0.4-0.6 wt%
  • the phosphorus content is About 0.1-6 wt%
  • the unit cell constant is about 2.440-2.453nm
  • the framework silicon-aluminum ratio is about 8.5-12.6.
  • the catalyst according to item B1 comprising about 10-50% by weight of the modified Y-type molecular sieve, a binder, and clay.
  • a method for preparing a catalytic cracking catalyst for processing hydrogenated LCO comprising the steps of preparing an active component modified Y-type molecular sieve, the step of preparing an active component modified Y-type molecular sieve comprising:
  • step (4) The molecular sieve after the reaction in step (4) is impregnated with a zinc salt solution.
  • step (2) The method according to item B8, wherein the baking in step (2) is performed in an atmosphere of 350-480 ° C and a water vapor content of about 30-90 vol%, and the baking time is about 4.5-7 hours.
  • the phosphorus compound used for the phosphorus modification treatment is selected from the group consisting of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate. Or more.
  • step (5) comprises roasting the impregnated molecular sieve, the soaking temperature is about 10-60 ° C, the roasting temperature is about 350-600 ° C, and the roasting time is about 1 -4 hours.
  • a catalytic cracking method for processing hydro-LCO comprising the step of contacting the hydro-LCO with the catalyst according to any one of items B1 to B7 under catalytic cracking conditions; wherein the catalytic cracking conditions include:
  • the reaction temperature is about 500-610 ° C.
  • the weight hourly space velocity is about 2-16 h -1
  • the agent-to-oil weight ratio is about 3-10
  • the agent-to-oil ratio is a weight ratio.
  • the NaY molecular sieve also known as NaY zeolite
  • NaY zeolite used was provided by Qilu Branch of Sinopec Catalyst Co., Ltd., its sodium oxide content was 13.5% by weight, and the framework silicon-aluminum ratio (SiO 2 / Al The 2 O 3 molar ratio) was 4.6, the unit cell constant was 2.470 nm, and the relative crystallinity was 90%.
  • Rare earth chloride and rare earth nitrate are chemically pure reagents produced by Beijing Chemical Plant; zinc nitrate and zinc chloride are chemically pure reagents produced by Beijing Chemical Plant; boehmite is an industrial product produced by Shandong Aluminum Plant with a solid content of 61% by weight; Kaolin is a special kaolin for cracking catalyst produced by Suzhou China Kaolin Company, with a solid content of 76% by weight; aluminum sol is provided by Qilu Branch of Sinopec Catalyst Co., Ltd., with alumina content of 21% by weight.
  • the element content of the molecular sieve was determined by X-ray fluorescence spectroscopy.
  • the cell constant and relative crystallinity of molecular sieves are determined by X-ray powder diffraction (XRD) using RIPP145-90 and RIPP146-90 standard methods (see “Analytical Methods for Petrochemical Engineering (RIPP Test Method)", edited by Yang Cuiding, etc., Science Press (Published in 1990, pp. 412-415).
  • the skeletal silica-alumina ratio of the molecular sieve is calculated from the following formula:
  • a 0 is the unit cell constant and the unit is nm.
  • the total silicon-aluminum ratio of the molecular sieve is calculated based on the Si and Al element content determined by X-ray fluorescence spectrometry.
  • the ratio of the framework silicon-aluminum measured by the XRD method and the total silicon-aluminum ratio measured by the XRF can calculate the ratio of the framework Al to the total Al. Furthermore, the ratio of non-framework Al to total Al was calculated.
  • the lattice collapse temperature was measured by differential thermal analysis (DTA).
  • the type of acid center of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption.
  • Experimental instrument Bruker's IFS113V FT-IR (Fourier transform infrared) spectrometer. The amount of acid was measured by a pyridine adsorption infrared method at 350 ° C.
  • Experimental method The sample is self-supporting and compressed, placed in an in-situ cell of an infrared spectrometer and sealed; the temperature is raised to 400 ° C, and the vacuum is evacuated to 10 -3 Pa, and the temperature is maintained for 2 hours to remove the gas molecules adsorbed by the sample; The introduction pressure is 2.67Pa.
  • Pyridine vapor is used to keep the adsorption equilibrium for 30min. Then the temperature is raised to 350 ° C, the vacuum is desorbed to 10 -3 Pa for 30min, and the temperature is reduced to room temperature.
  • the scanning wave number range is 1400-1700cm -1 .
  • Infrared spectrum of pyridine adsorption desorbed at °C. The intensity of the peak adsorption of pyridine adsorption infrared spectra characteristics 1540cm -1 and 1450cm -1, to obtain the molecular sieve BrOnsted strong acid sites (B acid sites) and the relative amount of Lewis acid sites (L acid center).
  • the method for measuring the secondary pore volume is as follows: in accordance with the RIPP 151-190 standard method (see “Petrochemical Analysis Method (RIPP Test Method)", edited by Yang Cuiding, etc., Science Press, 1990 Publication, pp. 424-426) Determine the total pore volume of the molecular sieve according to the adsorption isotherm, and then determine the micropore volume of the molecular sieve from the adsorption isotherm according to the T-drawing method. Subtract the micropore volume from the total pore volume to obtain the second level. Well volume.
  • Examples 1-3 are preparation examples of the modified Y-type molecular sieve and the catalytic cracking catalyst according to the present invention.
  • the molecular sieve was calcined in an atmosphere containing 50% by volume of water vapor and 50% by volume of air at a temperature of 390 ° C. for 6 hours to obtain a Y-type molecular sieve having a cell constant of 2.455 nm.
  • a Y-type molecular sieve having a cell constant of 2.455 nm was added to 6 liters of an aqueous solution in which 35 g of phosphoric acid was dissolved, the temperature was raised to 90 ° C., and a phosphorus modification treatment was performed for 30 minutes. Then, the molecular sieve was filtered and washed, The filter cake is dried so that its water content is less than 1% by weight.
  • the SC1 catalyst obtained contained 30% by weight of SZ1 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • the molecular sieve was calcined at a temperature of 450 ° C. and 80% water vapor for 5.5 hours to obtain a Y-type molecular sieve having a cell constant of 2.461 nm.
  • a Y-type molecular sieve having a cell constant of 2.461 nm was added to 6 liters of an aqueous solution in which 268 g of ammonium phosphate was dissolved, the temperature was raised to 60 ° C, and a phosphorus modification treatment was performed for 50 minutes. After that, the molecular sieve was filtered and washed, and The filter cake is dried so that its water content is less than 1% by weight.
  • the modified Y molecular sieve is designated as SZ2, and its physical and chemical properties are listed in Table 1.
  • the SC2 catalyst obtained contained 30% by weight of SZ2 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • the molecular sieve was calcined at a temperature of 470 ° C. and 70% by volume of water vapor for 5 hours to obtain a Y-type molecular sieve having a cell constant of 2.458 nm.
  • a Y-type molecular sieve having a cell constant of 2.458 nm was added to 6 liters of an aqueous solution in which 95 g of diammonium hydrogen phosphate was dissolved, the temperature was raised to 40 ° C, and a phosphorus modification treatment was performed for 80 minutes. Then, the molecular sieve was filtered and washed. And drying the filter cake so that its water content is less than 1% by weight.
  • the SiCl 4 gas heated and vaporized was introduced into the molecular sieve after the phosphorus modification treatment, and the reaction was carried out at a temperature of 500 ° C. for 1 hour. Wash with 20 liters of deionized water and filter.
  • the SC3 catalyst obtained contained 30% by weight of SZ3 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • Comparative Examples 1-3 are preparation examples of the modified Y-type molecular sieve and the catalytic cracking catalyst which are not the present invention.
  • the filter cake was dried at 120 ° C and calcined at 650 ° C and 100% water vapor for 5 hours for hydrothermal modification treatment. After that, it was added to 20 liters of deionized water and stirred to make the mixture uniform, and 1000 g (NH 4 ) 2 was added. SO 4 , stir, heat to 90-95 ° C for 1 hour, then filter and wash.
  • the filter cake was dried at 120 ° C for 5 hours at a temperature of 650 ° C and 100% water vapor for a second hydrothermal modification treatment.
  • Two ion exchanges and two hydrothermal ultra-stable hydrothermal ultra-stable super-stable hydrothermal ultra-stable were obtained.
  • Y-type molecular sieve, denoted as DZ1, and its physical and chemical properties are listed in Table 1.
  • DZ1 molecular sieve, kaolin, water, pseudo-boehmite binder and aluminum sol were formed into a slurry according to the conventional preparation method of catalytic cracking catalyst, and spray-dried to prepare a microsphere catalyst.
  • the prepared catalytic cracking catalyst was recorded as DC1 (reference Preparation method of Example 1).
  • the obtained DC1 catalyst contains 30% by weight of DZ1 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • the filter cake was dried at 120 ° C and then subjected to hydrothermal modification treatment.
  • the temperature of the hydrothermal modification treatment was calcined under 100% water vapor for 5 hours, and then added to 20 liters of deionized water and stirred to make the mixture uniform.
  • the filter cake was dried at 120 ° C and then subjected to a second hydrothermal modification treatment (temperature 650 ° C, baking at 100% water vapor for 5 hours) to obtain two ion exchanges and two hydrothermal superstabilities.
  • Y-type molecular sieve denoted as DZ2
  • DZ2 Y-type molecular sieve
  • the DZ2 molecular sieve, kaolin, water, pseudo-boehmite binder and aluminum sol were formed into a slurry according to the conventional preparation method of catalytic cracking catalyst, and spray-dried to prepare a microsphere catalyst.
  • the prepared catalytic cracking catalyst was referred to as DC2 (reference Preparation method of Example 1).
  • the DC2 catalyst obtained contained 30% by weight of DZ2 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • the filter cake was dried at 120 ° C to obtain a Y-type molecular sieve having a cell constant of 2.471 nm, a sodium oxide content of 7.5% by weight, and a rare earth content of 8.5% by weight based on RE 2 O 3. Then, the molecular sieve was added to 95 g of the dissolved molecular sieve. In a 6 liter aqueous solution of diammonium hydrogen phosphate, the temperature was raised to 40 ° C., and a phosphorus modification treatment was performed for 80 minutes. After that, the molecular sieve was filtered and washed, and the filter cake was dried to reduce the water content to less than 1% by weight.
  • SiCl 4 gas heated and vaporized was passed in and reacted at a temperature of 580 ° C. for 1.5 hours, and then washed with 20 liters of deionized water. It was then filtered to obtain a modified Y-type molecular sieve, which was designated as DZ3, and its physical and chemical properties are listed in Table 1.
  • DZ3 molecular sieve, kaolin, water, pseudo-boehmite binder and aluminum sol were formed into a slurry according to the conventional preparation method of catalytic cracking catalyst, and spray-dried to prepare a microsphere catalyst.
  • the prepared catalytic cracking catalyst was referred to as DC3 (reference Preparation method of Example 1).
  • the obtained DC3 catalyst contains 30% by weight of DZ3 molecular sieve, 42% by weight of kaolin, 25% by weight of pseudoboehmite, and 3% by weight of aluminum sol.
  • Example 3 After the catalysts SC1, SC2, and SC3 prepared in Examples 1-3 were aged at 800 ° C and 100% water vapor for 4 hours or 17 hours, the light oil microreactivity was evaluated. The evaluation results are shown in Table 3.
  • the test example numbers corresponding to SC1, SC2, and SC3 are test example 1, test example 2, and test example 3.
  • the standard method of RIPP 92-90 (see “Analytical Method of Petrochemical Engineering (RIPP Test Method)", edited by Yang Cuiding, et al., Science Press, 1990, pp. 263-268, was used to evaluate the micro-reactive activity of each catalyst.
  • the catalyst loading is 5.0g
  • the reaction temperature is 460 ° C
  • the feedstock oil is Dagang light diesel oil with a distillation range of 235-337 ° C.
  • the product composition is analyzed by gas chromatography, and the light oil microinverse activity is calculated based on the product composition.
  • Light oil microinverse activity (MA) (gasoline production below 216 ° C + gas production + coke production) in the product / total feed ⁇ 100%.
  • the test comparative numbers corresponding to the catalysts DC1, DC2, and DC3 are test comparative example 1, test comparative example 2, and test comparative example 3, respectively.
  • the DC1, DC2, DC3 catalysts and the HAC catalysts used in the examples of Chinese Patent Application Publication No. CN 104560187A were aged at 800 ° C and 100% water vapor atmosphere for 12 hours, and then were used in a small fixed fluidized bed reactor (ACE).
  • ACE small fixed fluidized bed reactor
  • the performance of the catalytic cracking reaction for processing hydrogenated LCO was evaluated.
  • the evaluation method is shown in the application example.
  • the raw material properties of the ACE experiment are shown in Table 4.
  • the evaluation results are shown in Table 5.
  • DC1, DC2, DC3 catalyst and HAC catalyst corresponding application comparative numbers are respectively applied comparative example 1, applied comparative example 2, applied comparative example 3, and applied comparative example 4.
  • the modified Y-type molecular sieve containing phosphorus, rare earth and zinc provided by the present disclosure also has the following advantages: low sodium oxide content, less non-framework aluminum content when the silicon-aluminum ratio is high, and the pore size is 2.0-100nm
  • the pore volume of the secondary pores accounts for a higher percentage of the total pore volume, and the B acid / L acid (the ratio of the strong B acid acid to the L acid acid) is higher, and the rare earth content is smaller when the cell constant of the molecular sieve is smaller.
  • the crystallinity value measured at high time is high, and it has high thermal stability.
  • modified Y-type molecular sieves containing phosphorus, rare earth and zinc provided by the present disclosure have high relative crystallinity retention after exposed to aging under the severe conditions of 800 ° C and 17 hours in the bare state. It is shown that the modified Y-type molecular sieve provided by the present disclosure has high hydrothermal stability.
  • the catalyst provided by the present disclosure has high hydrothermal stability, significantly lower coke selectivity, significantly higher gasoline yield, and BTX in gasoline ( The yield of benzene + toluene + xylene was significantly increased, and the total yield of ethylene and propylene in the gas product was significantly improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

一种改性Y型分子筛、包含它的催化裂化催化剂、及其制备和应用，该改性Y型分子筛中，稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝含量占总铝含量的百分比不高于约20％，孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约15-30％。改性Y型分子筛具有高结晶度及二级孔结构，热和水热稳定性高；包含改性Y型分子筛的催化裂化催化剂，用于加氢轻循环油(LCO)催化裂化时，具有较高的加氢LCO转化效率、较低的焦炭选择性、更高的汽油产率。

Description

改性Y型分子筛、包含它的催化裂化催化剂、及其制备和应用
相关申请的交叉引用
本申请要求申请人于2018年8月20日向中国专利局提交的申请号为201810949445.2、名称为“一种改性Y型分子筛及其制备方法”的专利申请的优先权；以及，申请人2018年8月20日向中国专利局提交的申请号为201810948782.X、名称为“一种用于加工加氢LCO的催化裂化催化剂及其制备方法”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
本公开涉及分子筛和催化裂化的技术领域，更具体地涉及一种改性Y型分子筛、包含它的催化裂化催化剂、它们的制备方法和应用。
背景技术
苯、甲苯及二甲苯(BTX)等轻质芳烃是重要的基本有机化工原料，广泛用于生产聚酯、化纤等，近年来需求强劲。苯、甲苯及二甲苯等轻质芳烃主要来自以石脑油为原料的催化重整和蒸汽裂解工艺过程。由于石脑油原料紧缺，致使轻质芳烃存在较大的市场缺口。
催化裂化轻循环油(LCO)是催化裂化的重要副产物，数量大，富含芳烃，尤其是多环芳烃，属于劣质柴油馏分。随着市场需求和环保要求的发展变化，LCO作为柴油调合组分受到较大限制。LCO的烃类组成包括链烷烃、环烷烃(含少量烯烃)和芳烃，随催化裂化原料油不同和操作苛刻度不同，LCO的烃类组成差异较大，但芳烃均为其主要组分，通常质量分数大于70％，有的甚至达到90％左右，其余为链烷烃和环烷烃。
LCO中的双环芳烃含量最高，属于其典型组分，也是影响催化裂化生产轻质芳烃的关键组分。在催化裂化反应条件下，多环芳烃难以开环裂化为轻质芳烃，而在加氢处理条件下，多环芳烃比较容易饱和为烷基苯和环烃基苯(茚满类、四氢萘类和茚类)等重质单环芳烃。此类重质单环芳烃是催化裂化生产轻质芳烃的潜在组分，在催化裂化条件下能够裂化为轻质芳烃。因此，LCO是生产轻质芳烃的潜在且廉 价的资源，通过加氢处理-催化裂化技术路线生产轻质芳烃具有重要的研究价值。
中国专利申请公开Nos.CN103923698A、CN104560185A和CN104560187A记载的现有技术中，采用LCO适度加氢，先将其中的大部分多环芳烃饱和成含有环烷环和一个芳环的氢化芳烃，然后，在催化裂化催化剂存在下进行裂化反应生产BTX轻质芳烃。但是，LCO加氢得到的氢化芳烃的裂化性能比常规催化裂化原料差，而氢转移性能远高于一般催化裂化原料，因此，现有技术中所用的常规的催化裂化催化剂不能满足加氢LCO催化裂化的需要。
Y型分子筛自上世纪60年代首次使用以来，一直是催化裂化(FCC)催化剂的主要活性组元。然而，随着原油重质化的加剧，FCC原料中的多环化合物含量显著增多，其在沸石孔道中的扩散能力却显著下降。而作为主要活性组元的Y型分子筛的孔径仅有0.74nm，直接用来加工渣油等重质馏分，催化剂活性中心的可接近性将成为其中所含多环化合物裂化的主要障碍。分子筛孔结构与裂化反应性能关系密切，特别是对渣油裂化催化剂，分子筛的二级孔能增加渣油大分子与其活性中心的可接近性，进而提高对渣油的裂解能力。
水热脱铝法是工业上应用最广泛的制备具有二级孔的超稳分子筛的方法之一，该方法先将NaY分子筛用铵离子的水溶液交换，以降低分子筛中的钠离子含量，然后，于600-825℃在水蒸气气氛下焙烧铵离子交换后的分子筛，使其超稳化。该方法成本低且易于工业化大规模生产，得到的超稳Y型分子筛具有较丰富的二级孔，但超稳Y分子筛结晶度损失严重。
目前，工业上生产超稳Y型分子筛一般是对上述水热焙烧工艺的改进，采用两次交换两次焙烧的方法，其目的是分步采取较温和的焙烧条件，以解决在苛刻的焙烧条件下所发生的结晶度严重损失的问题，所制备的超稳Y分子筛也具有一定量的二级孔，但是，较大孔径的二级孔在总的二级孔里的比例较低，另外，超稳分子筛的比表面和结晶度还有待进一步提高。
为了更好地满足加氢LCO催化裂化多产BTX轻质芳烃的需要，本发明的目的是开发同时具备强的裂化能力及较弱的氢转移性能的高稳定性的改性分子筛作为新活性组元，以此新活性组元进一步开发适 合加氢LCO催化裂化的多产BTX轻质芳烃的催化裂化催化剂，强化裂化反应，控制氢转移反应，进一步提高加氢LCO的转化效率，最大程度地生产富含苯、甲苯和二甲苯(BTX)的催化汽油。
发明内容
本公开的目的之一是提供一种改性Y型分子筛、包含它的催化裂化催化剂、它们的制备方法和应用，以该改性Y型分子筛作为活性组元制备的催化裂化催化剂，用于加氢轻循环油(LCO)催化裂化时，具有较高的加氢LCO转化效率、较低的焦炭选择性、更高的汽油产率，以及更高的乙烯和丙烯总产率。
一方面，本公开提供了一种改性Y型分子筛，以所述改性Y型分子筛的干基重量为基准，所述改性Y型分子筛的稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝含量占总铝含量的百分比不高于约20％，孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约15-30％。
另一方面，本公开提供了一种改性Y型分子筛的制备方法，包括以下步骤：
(1)使NaY分子筛与稀土盐溶液接触进行离子交换反应，得到离子交换后的分子筛；
(2)对所述离子交换后的分子筛进行水热超稳改性处理，得到水热超稳改性的分子筛；
(3)使所述水热超稳改性的分子筛与磷化合物接触进行磷改性处理，得到磷改性分子筛；
(4)使所述磷改性分子筛与气态SiCl 4接触反应进行气相超稳改性，得到气相超稳改性的分子筛；以及
(5)将所述气相超稳改性的分子筛用锌盐溶液浸渍，得到所述改性Y型分子筛。
优选地，所述步骤(2)的水热超稳改性处理通过在约350-480℃的温度和约30-90体积％水蒸汽气氛下焙烧约4.5-7h来进行。
再一方面，本公开提供了一种催化裂化催化剂，以所述催化剂的 干基重量为基准，所述催化剂包含约10-50wt％的改性Y型分子筛、粘结剂和粘土；其中所述改性Y型分子筛为根据本公开的改性Y型分子筛或者通过本公开的方法制备得到的改性Y型分子筛。
又一方面，本公开提供了根据本公开的改性Y型分子筛在烃类原料，特别是加氢轻循环油，的催化裂化反应中的应用，包括在催化裂化条件下使所述烃类原料与包含所述改性Y型分子筛的催化裂化催化剂接触。
本公开提供的改性Y型分子筛，含有磷、稀土及锌改性组分，具有高结晶度及二级孔结构，热和水热稳定性高。
本公开的改性Y型分子筛可以用作催化裂化催化剂的活性组元，用于加氢LCO的催化裂化。以此分子筛为活性组元的催化裂化催化剂用于加工加氢LCO时，不仅能够提高加氢LCO的转化效率，还具有较低的焦炭选择性、更高的富含BTX轻质芳烃的汽油产率，以及更高的乙烯和丙烯总产率。
具体实施方式
以下对本公开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公开，并不用于限制本公开。
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。
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发明原始公开或原始记 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。
本发明中涉及的RIPP试验方法具体可参见《石油化工分析方法(RIPP试验方法))》，杨翠定等编，科学出版社，1990年9月第一版，ISBN：7-03-001894-X，第263-268、412-415和424-426页，其经此引用全文并入本文。
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。
在本申请中，术语“Y型分子筛”和“Y型沸石”可互换使用，且术语“NaY分子筛”和“NaY沸石”也可互换使用。
在本文中，术语“二级孔”是指分子筛中孔径(指直径)为2-100nm的孔。
在本文中，术语“稀土溶液”和“稀土盐溶液”可互换使用，优选为稀土盐的水溶液。
在本文中，表述“常规晶胞大小的Y型分子筛”表示该Y型分子筛的晶胞常数在常规NaY分子筛的晶胞常数的范围内，优选在约2.465nm至约2.472nm的范围内。
在本申请中，术语“常压”表示压力为约1atm。
在本申请中，物质的干基重量是指该物质在800℃焙烧1小时得到的固体产物重量。
在本申请中，如无相反表示，所涉及的各种分子筛的质量，均以干基计；稀土盐、稀土的质量(含量)，均以氧化稀土的质量(含量)计，本文中也可简称氧化稀土质量(含量)；钠的质量(含量)均以氧化钠的质量(含量)计，本文中也可简称氧化钠质量(含量)；锌、锌盐的质量(含量)均以氧化锌的质量(含量)计，本文中也可简称氧化锌质量(含量)；磷的质量(含量)均以五氧化二磷的质量(含量)计，本文中也可简称P 2O 5质量(含量)。
在第一方面，本公开提供了一种改性Y型分子筛，以所述改性Y型分子筛的干基重量为基准，所述改性Y型分子筛的稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝含量占总铝含 量的百分比不高于约20％，孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约15-30％。
在优选的实施方式中，所述改性Y型分子筛的骨架硅铝比(SiO 2/Al 2O 3摩尔比)可以为约7.3-14，进一步可以为约8.5-12.6，例如约8.79、10.87、11.95等。
在优选的实施方式中，所述改性Y型分子筛的稀土含量(以氧化稀土计的含量)可以为约4.5-10wt％，例如约5.6wt％、6.3wt％、8.4wt％等。
根据本公开，所述稀土的种类和组成没有特殊限制。优选地，所述稀土可以包括La、Ce、Pr或Nd，或者它们中两者、三者或四者的组合；任选地，所述稀土中还可以包括La、Ce、Pr和Nd之外的其他稀土元素。
在优选的实施方式中，所述改性Y型分子筛的钠含量(以氧化钠计的含量)可以为约0.1-0.7wt％，进一步可以为约0.3-0.7wt％，再进一步可以为约0.35-0.6wt％，再进一步可以为约0.4-0.55wt％，例如约0.44wt％、0.49wt％、0.57wt％等。
在优选的实施方式中，所述改性Y型分子筛的锌含量(以氧化锌计的含量)可以为约1-4wt％，例如可以为约1wt％、2wt％、4wt％等。
在优选的实施方式中，所述改性Y型分子筛的磷含量(以P 2O 5计的磷含量)可以为约0.1-6wt％，进一步可以为约0.1-5wt％，例如约0.95wt％、2.21wt％、3.68wt％等。
在优选的实施方式中，所述改性Y型分子筛的非骨架铝含量占总铝含量的百分比可以为约13-19％，例如约13.2％、16.5％、18.5％等。
在优选的实施方式中，所述改性Y型分子筛的晶胞常数可以为约2.440-2.455nm，优选为约2.440-2.453nm，进一步优选为约2.442-2.453nm，例如约2.443nm、2.445nm、2.45nm等。
在优选的实施方式中，所述改性Y型分子筛的总孔体积可以为约0.33-0.39mL/g，优选为约0.35-0.39mL/g，进一步优选为约0.36-0.375mL/g，例如约0.355mL/g、0.364mL/g、0.373mL/g等。
根据本公开，所述改性Y型分子筛的孔结构可以进一步优化，以取得更适宜的催化裂化反应性能。在优选的实施方式中，孔径(直径)为2.0-100nm的二级孔的孔体积占总孔体积的百分比可以为约 20％-30％，优选为约17％-21％，例如约17.96％、19.78％、20.85％等。
在优选的实施方式中，所述改性Y型分子筛的比表面积可以为约600-670m 2/g，优选为约610-660m 2/g，例如约633m 2/g、640m 2/g、652m 2/g等。
在优选的实施方式中，所述改性Y型分子筛的晶格崩塌温度不低于约1050℃，可以为约1055℃-1080℃，优选为约1056-1075℃，例如约1055℃、1061℃、1068℃等。
根据本公开，为了保证改性Y型分子筛具有适宜的表面酸中心类型和强度，在优选的实施方式中，用吡啶吸附红外法在350℃时测定的所述改性Y型分子筛的强酸量中B酸量与L酸量的比值不低于约3.50，例如可以为约3.6-5.0，优选为约3.7-4.3，具体可以为约3.76、4.21、4.95等。
在优选的实施方式中，所述改性Y型分子筛在800℃、常压、100体积％水蒸汽气氛下老化17小时后的相对结晶度保留率为约35％以上，例如可以为约38-48％或约35-45％，例如约38.95％、40.55％、43.45％等。
在优选的实施方式中，所述改性Y型分子筛的相对结晶度为不低于约60％，例如可以为约60-70％，优选为约60-66％，具体可以为约60.4％、62.7％、65.3％等。
本公开提供的改性Y型分子筛同时具备强的裂化能力及较弱的氢转移性能，可以用作催化裂化催化剂的活性组元，用于加氢LCO的催化裂化；以此分子筛为活性组元的催化裂化催化剂用于加工加氢LCO时，具有高的LCO转化效率、较低的焦炭选择性、更高的且富含BTX的汽油收率，并且气体产物中含有较多的乙烯和丙烯。
在第二方面，本公开提供了一种改性Y型分子筛的制备方法，包括以下步骤：
(1)使NaY分子筛与稀土盐溶液接触进行离子交换反应，得到离子交换后的分子筛；
(2)对所述离子交换后的分子筛进行水热超稳改性处理，得到水热超稳改性的分子筛；
(3)使所述水热超稳改性的分子筛与磷化合物接触进行磷改性处理，得到磷改性分子筛；
(4)使所述磷改性分子筛与气态SiCl 4接触反应进行气相超稳改性，得到气相超稳改性的分子筛；以及
(5)将所述气相超稳改性的分子筛用锌盐溶液浸渍，得到所述改性Y型分子筛。
在一具体实施方式中，本公开的方法包括以下步骤：
(1)使NaY分子筛与稀土盐溶液接触进行离子交换反应，以得到氧化钠含量降低的含稀土的常规晶胞大小的Y型分子筛；
(2)对步骤(1)得到的氧化钠含量降低的含稀土的常规晶胞大小的Y型分子筛进行水热焙烧处理，优选在约350-480℃的温度和约30-90体积％水蒸汽气氛下焙烧约4.5-7h，得到晶胞常数降低的Y型分子筛；
(3)使步骤(2)得到的晶胞常数降低的Y型分子筛与磷化合物接触进行磷改性处理，在分子筛中引入磷，得到磷改性分子筛；
(4)使步骤(3)得到的磷改性分子筛与气态SiCl 4接触反应，进行脱铝补硅，得到气相超稳改性Y型分子筛；以及
(5)将步骤(4)得到的气相超稳改性Y型分子筛用锌盐溶液浸渍，并焙烧，得到所述所述改性Y型分子筛。
在优选的实施方式中，所述步骤(1)包括将NaY分子筛与稀土盐溶液接触进行离子交换反应，过滤、洗涤、干燥，得到氧化钠含量降低的含稀土的Y型分子筛。
在优选的实施方式中，步骤(1)所用的NaY分子筛的晶胞常数为约2.465-2.472nm，骨架硅铝比(SiO 2/Al 2O 3摩尔比)为约4.5-5.2，相对结晶度为约85％以上，例如为约85-95％，氧化钠含量为约13.0-13.8wt％。
在优选的实施方式中，步骤(1)得到的氧化钠含量降低的含稀土的Y型分子筛的晶胞常数为约2.465-2.472nm，钠含量以氧化钠计不超过约9.5wt％，稀土含量以RE 2O 3(氧化稀土)计为约4.5-13wt％。
在优选的实施方式中，步骤(1)得到的氧化钠含量降低的含稀土的Y型分子筛的氧化钠含量可以为约5.5-9.5wt％，优选为约5.5-8.5wt％，例如约7.5％；氧化稀土含量可以为约5.5-13wt％，优选为约5.5-12wt％或4.5-11.5wt％。
在优选的实施方式中，所述步骤(1)进一步包括使NaY分子筛与稀土盐在水溶液中接触进行离子交换反应，其中NaY分子筛(以干基计)、 稀土盐(以氧化稀土计)、水的质量比为约1∶(0.01-0.18)∶(5-15)，水可以为去离子水。
在优选的实施方式中，所述稀土盐为氯化稀土和/或硝酸稀土。所述的稀土可以为任意种类的稀土，其种类和组成没有特殊限制，例如为La、Ce、Pr、Nd以及混合稀土中的一种或多种，优选的，所述的混合稀土中含有La、Ce、Pr和Nd中的一种或多种，或还可以含有除La、Ce、Pr和Nd以外的稀土中的至少一种。
在优选的实施方式中，步骤(1)中离子交换反应的交换温度可以为约15-95℃，优选为约65-95℃，例如约90-95℃；交换时间可以为约30-120分钟，优选为约45-90分钟。
在优选的实施方式中，在所述步骤(1)中将NaY分子筛、稀土盐和水形成混合物，其可以是先将NaY分子筛和水形成浆液，然后在浆液中加入稀土盐和/或稀土盐的水溶液。
在优选的实施方式中，所述步骤(1)进一步包括：将NaY分子筛与水混合，搅拌下加入稀土盐和/或稀土盐溶液进行稀土离子与钠离子的交换，过滤，洗涤；其中，洗涤的目的是为洗去交换出的钠离子，可以使用去离子水进行洗涤。
在优选的实施方式中，在所述步骤(1)中，按照NaY分子筛∶稀土盐∶H 2O质量比为约1∶(0.01-0.18)∶(5-15)的比例，将NaY分子筛、稀土盐和水形成混合物，在约15-95℃的温度下搅拌约30-120分钟进行稀土离子与钠离子的交换。
在优选的实施方式中，所述步骤(2)的水热超稳改性/水热焙烧处理包括将离子交换后的分子筛在约350-480℃的温度和约30-90体积％水蒸汽气氛下(也称30-90体积％水蒸汽气氛或称30-90％水蒸汽)焙烧约4.5-7小时。优选地，将离子交换后的分子筛在约380-460℃的温度和约40-80体积％水蒸汽气氛下焙烧约5-6小时。例如，所述焙烧处理可以在约390℃、约450℃或约470℃的温度，和约50体积％、约70体积％或约80体积％水蒸汽气氛下进行。
在某些优选的实施方式中，所述步骤(2)的水蒸汽气氛中还可以含有其它气体，例如空气、氦气或氮气中的一种或多种。
在优选的实施方式中，经步骤(2)处理后的分子筛的晶胞常数降低至约2.450-2.462nm，水含量低于约1wt％。
在优选的实施方式中，所述步骤(3)进一步包括将步骤(2)得到的分子筛进行干燥，以使晶胞常数降低的Y型分子筛中的水含量不超过约1wt％，所述干燥可采用气流干燥、烘干、闪蒸干燥等方法。
在优选的实施方式中，所述步骤(3)进一步包括将步骤(2)得到的晶胞常数降低的Y型分子筛与含有磷化合物的溶液接触反应。
在优选的实施方式中，步骤(3)中所用的磷化合物可以是磷酸、磷酸铵、磷酸二氢铵、磷酸氢二铵等中的一种或多种。
在优选的实施方式中，在所述步骤(3)中，溶液中水的质量与分子筛(步骤(2)得到的分子筛)的质量比为约(2-5)∶1，优选为约(3-4)∶1。
在优选的实施方式中，在所述步骤(3)中，磷(以P 2O 5计)与分子筛的质量比为约(0.0005-0.10)∶1，优选(0.001-0.05)∶1。
在优选的实施方式中，在步骤(3)中，所述磷改性处理的温度可以为约15-100℃，优选为约30-95℃，处理时间可以为约10-100分钟。
在优选的实施方式中，所述步骤(3)进一步包括使分子筛与所述溶液在约15-100℃下反应约10-100分钟，然后过滤，洗涤；可用分子筛质量约5-15倍的水，例如去离子水进行洗涤。
在优选的实施方式中，在所述步骤(4)中，所用的四氯化硅与磷改性分子筛(以干基计)的质量比可以为约(0.1-0.7)∶1，优选为约(0.3-0.6)∶1，例如约0.4∶1、0.5∶1、0.6∶1等。
在优选的实施方式中，在所述步骤(4)中，分子筛与四氯化硅的反应温度可以为约200℃-650℃，优选为约350℃-500℃，例如约400℃、480℃、500℃等。
在优选的实施方式中，步骤(4)中分子筛与四氯化硅反应的反应时间为约10分钟至约5小时。任选地，在反应之后进行洗涤和过滤，以除去分子筛中残存的Na +、Cl -及Al 3+等可溶性副产物。
在进一步优选的实施方式中，步骤(4)的洗涤使用去离子水在如下条件下进行：所用水与分子筛的质量比可以为约(5-20)∶1，优选为约(6-15)∶1；洗涤温度为约30-60℃；洗涤液的pH值可以为约2.5-5.0。通常，所述洗涤进行到洗涤后的洗涤液中检测不出游离的Na +，Cl -及Al 3+等离子。
在优选的实施方式中，步骤(5)所用的锌盐可以是硝酸锌或氯化锌。
在优选的实施方式中，所述步骤(5)进一步包括将锌盐配成溶液， 所用的锌盐(以ZnO计)与分子筛的重量比为约(0.5-5.0)∶100，锌盐溶液的浓度可以为约0.020-0.080克/毫升。
在优选的实施方式中，步骤(5)的浸渍温度为约10-60℃。任选地，浸渍后的分子筛可在约130℃的温度下烘干约5小时，然后进行焙烧，焙烧温度可以为约350-600℃，焙烧时间可以为约1-4小时。
在本公开的一种具体实施方式中，制备改性Y型分子筛的方法包括以下步骤：
(1)将NaY分子筛与稀土盐溶液接触进行离子交换反应，过滤，洗涤，得到氧化钠含量降低的含稀土的常规晶胞大小的Y型分子筛；所述离子交换在搅拌、温度为约15-95℃的条件下进行约30-120分钟；
(2)将所述氧化钠含量降低的含稀土的常规晶胞大小的Y型分子筛在约350-480℃温度和含约30-90体积％水蒸汽的气氛下焙烧约4.5-7小时，干燥，得到水含量低于约1wt％的晶胞常数降低的Y型分子筛，其晶胞常数为约2.450-2.462nm；
(3)将所述晶胞常数降低的Y型分子筛加入到含有磷化合物的溶液中，在约15-100℃的条件下反应约10-100分钟，过滤，洗涤；其中，所述溶液中的水与分子筛的质量比为约2-5，优选约3-4，磷(以P 2O 5计)与分子筛的质量比为约0.0005-0.10，干燥，得到水含量低于约1wt％的含磷的晶胞常数降低的Y型分子筛；
(4)将所述水含量低于约1wt％的含磷的晶胞常数降低的Y型分子筛与经加热汽化的SiCl 4气体接触，其中SiCl 4∶水含量低于约1wt％的晶胞常数降低的Y型分子筛(以干基计)的质量比为约(0.1-0.7)∶1，在温度为约200-650℃的条件下接触反应约10分钟至约5小时，然后洗涤和过滤；以及
(5)将步骤(4)得到的改性Y分子筛用锌盐溶液浸渍，浸渍温度为约10-60℃，浸渍后的分子筛先在约130℃烘干约5小时，然后在约350-600℃下焙烧约1-4小时，得到所述改性Y分子筛。
本公开提供的改性Y型分子筛的制备方法，可以制备高结晶度、高热稳定性及高水热稳定性的具有一定二级孔结构的含磷、稀土及锌的高硅Y型分子筛，该分子筛中铝分布均匀，非骨架铝含量少。
包含本公开方法制得的改性Y型分子筛的催化裂化催化剂，用于加氢LCO催化裂化时，具有高的LCO转化效率(即LCO有效转化率 高)、较低的焦炭选择性，以及更高的且富含BTX的汽油收率，并且气体产物中含有较多的乙烯和丙烯。
在第三方面，本公开提供了一种催化裂化催化剂，以所述催化剂的干基重量为基准，所述催化剂包含约10-50wt％的改性Y型分子筛、粘结剂和粘土，其中所述改性Y型分子筛为根据本公开的改性Y型分子筛或者通过本公开的方法制备得到的改性Y型分子筛。
在优选的实施方式中，以干基计，所述催化剂的改性Y型分子筛的含量可以为约10-50wt％，优选为约15-45wt％，进一步优选为约25-40wt％，例如具体可以为约25wt％、30wt％、40wt％等。
在优选的实施方式中，所述粘土可以是适合用作裂化催化剂组分的粘土中的一种或多种，例如选自高岭土、多水高岭土、蒙脱土、硅藻土、埃洛石、皂石、累托土、海泡石、凹凸棒石、水滑石、膨润土等。优选地，以干基计，所述催化剂中粘土的含量为约10-80wt％，优选为约20-55wt％或约30-50wt％。
在优选的实施方式中，所述粘结剂为氧化铝粘结剂。优选地，所述催化剂中氧化铝粘结剂的含量可以为约10-40wt％，优选为约20-35wt％。
在优选的实施方式中，所述氧化铝粘结剂可以是裂化催化剂中常用的各种形态的氧化铝、水合氧化铝以及铝溶胶中的一种或多种，例如，可以选自γ-氧化铝、η-氧化铝、θ-氧化铝、χ-氧化铝、拟薄水铝石(pseudobohemite)、一水铝石(boehmite)、三水铝石(gibbsite)、拜耳石(Bayerite)、铝溶胶等，优选为拟薄水铝石和铝溶胶。
在优选的实施方式中，所述催化剂含有以氧化铝计约2-15wt％、优选约3-10wt％的铝溶胶，和以氧化铝计约10-30wt％、优选约15-25wt％的拟薄水铝石。
在优选的实施方式中，所述催化剂还可以含有所述改性Y型分子筛以外的其它分子筛，以催化剂的质量为基准，以干基计，所述其它分子筛的含量可以为约0-40wt％，优选为约0-30wt％，进一步优选为约1-20wt％。
在进一步优选的实施方式中，所述其它分子筛可以是催化裂化催化剂中常用的分子筛，例如具有MFI结构沸石、Beta沸石、其它Y型沸石、非沸石分子筛中的一种或多种。优选地，以干基计，其它Y型 沸石的质量不超过所述催化剂质量的约40％，可以为约0-40wt％，优选为约1-20wt％。
在优选的实施方式中，所述其它Y型沸石例如可以为REY、REHY，DASY、SOY、PSRY中的一种或多种；MFI结构沸石例如可以为HZSM-5、ZRP、ZSP中的一种或多种；Beta沸石例如Hβ，非沸石分子筛例如可以为磷酸铝分子筛(AlPO分子筛)、硅铝磷分子筛(SAPO分子筛)中的一种或多种。
本公开提供的催化裂化催化剂，含有热和水热稳定性高的改性Y型分子筛，具有较高的水热稳定性。此外，本公开提供的催化裂化催化剂以同时具备强的裂化能力及较弱的氢转移性能的高稳定性的改性分子筛作为活性组元，能够强化裂化反应，控制氢转移反应，用于加氢LCO催化裂化时，与现有含Y型分子筛的常规催化裂化催化剂相比，具有更高的LCO转化效率、较低的焦炭选择性、以及更高的且富含BTX的汽油收率，并且气体产物中含有较多的乙烯和丙烯。
在第四方面，本公开提供了一种制备催化裂化催化剂的方法，包括如下步骤：提供改性Y型分子筛，形成包括所述改性Y型分子筛、粘结剂、粘土和水的浆液，以及喷雾干燥，任选洗涤和任选干燥，得到所述催化裂化催化剂，其中所述提供改性Y型分子筛包括提供根据本公开的改性Y型分子筛，或者按照本公开的方法制备改性Y型分子筛。
除了所述提供改性Y型分子筛的步骤之外，本公开的催化剂制备方法的其它步骤可参考现有方法，例如按照中国专利申请公开CN1098130A和CN1362472A所记载的方法进行。
本公开提供的催化剂的制备方法中，所述喷雾干燥、洗涤和干燥可以采用现有技术，本发明没有特殊要求。
在第五方面，本公开提供了根据本公开的改性Y型分子筛在烃类原料，特别是加氢轻循环油，的催化裂化反应中的应用，包括在催化裂化条件下使所述烃类原料与包含所述改性Y型分子筛的催化裂化催化剂接触。
在第六方面，本公开提供了根据本公开的催化裂化催化剂在烃类原料，特别是加氢轻循环油，的催化裂化反应中的应用，包括在催化裂化条件下使所述烃类原料与所述催化裂化催化剂接触。
在第七方面，本公开提供了一种用于加工加氢轻循环油(加氢LCO)的催化裂化方法，包括在催化裂化条件下，使所述加氢LCO与本公开的催化裂化催化剂或者包含本公开的改性Y型分子筛的催化裂化催化剂接触的步骤。
根据本公开，优选地，所述催化裂化条件可以包括：反应温度为约500-610℃，重时空速为约2-16h -1，剂油重量比为约3-10。
在优选的实施方式中，所述加氢LCO具有以下性质：密度(20℃)为约0.850-0.920g/cm 3，H含量为约10.5-12wt％，S含量＜50μg/g，N含量＜10μg/g，总芳烃含量为约70-85wt％，多环芳烃含量≤15wt％。
在某些优选实施方式中，本公开提供了以下的技术方案：
A1、一种改性Y型分子筛，其中，稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝的质量占总铝质量的百分比不高于约20％，孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约15-30％。
A2、根据项目A1所述的分子筛，其中，所述总孔体积为约0.33-0.39mL/g。
A3、根据项目A1或A2所述的分子筛，其中，所述稀土含量为约4.5-10wt％，所述钠含量为约0.4-0.6wt％，所述磷含量为约0.1-6wt％，晶胞常数为约2.440-2.453nm，骨架硅铝比为约8.5-12.6。
A4、根据项目A3所述的分子筛，其中，所述非骨架铝的质量占所述总铝质量的百分比为约13-19％。
A5、根据项目A3所述的分子筛，其中，所述孔径为2-100nm的二级孔的孔体积占所述总孔体积的百分比为约20-30％。
A6、根据项目A1或A2所述的分子筛，其中，用吡啶吸附红外法在350℃测定，B酸量与L酸量的比值不低于约3.50。
A7、一种改性Y型分子筛的制备方法，包括如下步骤：
(1)将NaY分子筛与稀土盐溶液进行离子交换；
(2)将离子交换后的分子筛进行焙烧；
(3)将焙烧后的分子筛进行磷改性处理；
(4)将磷改性处理后的分子筛与四氯化硅反应；以及
(5)将步骤(4)反应后的分子筛用锌盐溶液浸渍。
A8、根据项目A7所述的方法，其中，所述步骤(1)中，离子交换的交换温度为约15-95℃，交换时间为约30-120分钟，所述NaY分子筛、稀土盐、水的质量比为约1∶(0.01-0.18)∶(5-15)，所述NaY分子筛的质量以干基计，所述稀土盐的质量以氧化稀土计。
A9、根据项目A7述的方法，其中，所述步骤(2)的焙烧在350-480℃、水蒸汽含量为约30-90体积％的气氛下进行，焙烧时间为约4.5-7小时。
A10、根据项目A7所述的方法，其中，所述步骤(3)中，进行磷改性处理的温度为约15-100℃，时间为约10-100分钟。
A11、根据项目A7所述的方法，其中，所述步骤(3)中，用于进行磷改性处理的磷化合物选自磷酸、磷酸铵、磷酸二氢铵、磷酸氢二铵中的一种或多种。
A12、根据项目A7所述的方法，其中，所述步骤(4)中，反应温度为约200℃-650℃，反应时间为约10分钟至约5小时，所述四氯化硅与所述磷改性处理后的分子筛的质量比为约(0.1-0.7)∶1，所述焙烧后的分子筛的质量以干基计。
A13、根据项目A7所述的方法，其中，所述步骤(5)包括将浸渍后的分子筛进行焙烧，浸渍温度为约10-60℃，焙烧温度为约350-600℃，焙烧时间为约1-4小时。
B1、一种用于加工加氢LCO的催化裂化催化剂，包括改性Y型分子筛；在所述改性Y型分子筛中，稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝的质量占总铝质量的百分比不高于约20％，所述改性Y型分子筛的孔径为2-100nm的二级孔的孔体积占所述改性Y型分子筛的总孔体积的百分比为约15-30％。
B2、根据项目B1所述的催化剂，其中，所述改性Y型分子筛的总孔体积为约0.33-0.39mL/g。
B3、根据项目B1所述的催化剂，其中，在所述改性Y型分子筛中，所述稀土含量为约4.5-10wt％，所述钠含量为约0.4-0.6wt％，所述磷含量为约0.1-6wt％，晶胞常数为约2.440-2.453nm，骨架硅铝比为约 8.5-12.6。
B4、根据项目B1所述的催化剂，其中，在所述改性Y型分子筛中，所述非骨架铝的质量占所述总铝质量的百分比为约13-19％。
B5、根据项目B1所述的催化剂，其中，在所述改性Y型分子筛中，所述孔径为2-100nm的二级孔的孔体积占所述总孔体积的百分比为约20-30％。
B6、根据项目B1或B2所述的催化剂，其中，在所述改性Y型分子筛中，用吡啶吸附红外法在350℃测定，B酸量与L酸量的比值不低于约3.50。
B7、根据项目B1所述的催化剂，包括约10-50wt％的所述改性Y型分子筛、粘结剂和粘土。
B8、一种用于加工加氢LCO的催化裂化催化剂的制备方法，包括制备活性组分改性Y型分子筛的步骤，所述制备活性组分改性Y型分子筛的步骤包括：
(1)将NaY分子筛与稀土盐溶液进行离子交换；
(2)将离子交换后的分子筛进行焙烧；
(3)将焙烧后的分子筛进行磷改性处理；
(4)将磷改性处理后的分子筛与四氯化硅反应；以及
(5)将步骤(4)反应后的分子筛用锌盐溶液浸渍。
B9、根据项目B8所述的方法，其中，所述步骤(1)中，离子交换的交换温度为约15-95℃，交换时间为约30-120分钟，所述NaY分子筛、稀土盐、水的质量比为约1∶(0.01-0.18)∶(5-15)，所述NaY分子筛的质量以干基计，所述稀土盐的质量以氧化稀土计。
B10、根据项目B8所述的方法，其中，所述步骤(2)的焙烧在350-480℃、水蒸汽含量为约30-90体积％的气氛下进行，焙烧时间为约4.5-7小时。
B11、根据项目B8所述的方法，其中，所述步骤(3)中，进行磷改性处理的温度为约15-100℃，时间为约10-100分钟。
B12、根据项目B8所述的方法，其中，所述步骤(3)中，用于进行磷改性处理的磷化合物选自磷酸、磷酸铵、磷酸二氢铵、磷酸氢二铵中的一种或多种。
B13、根据项目B8所述的方法，其中，所述步骤(4)中，反应温度 为约200℃-650℃，反应时间为约10分钟至约5小时，所述四氯化硅与所述磷改性处理后的分子筛的质量比为约(0.1-0.7)∶1，所述焙烧后的分子筛的质量以干基计。
B14、根据项目B8所述的方法，其中，所述步骤(5)包括将浸渍后的分子筛进行焙烧，浸渍温度为约10-60℃，焙烧温度为约350-600℃，焙烧时间为约1-4小时。
B15、根据项目B8至B14中任一项所述的方法，包括将约10-50wt％的所述改性Y型分子筛、粘结剂、粘土和水形成浆液，经喷雾干燥，制得所述催化剂。
B16、一种加工加氢LCO的催化裂化方法，包括在催化裂化条件下，将加氢LCO与项目B1至B7中任一项所述的催化剂接触的步骤；其中，所述催化裂化条件包括：反应温度为约500-610℃，重时空速为约2-16h -1，剂油重量比为约3-10，所述剂油比为重量比。
实施例
下面的实施例将对本公开予以进一步的说明，但并不因此而限制本公开。
原料
在下述的实施例和对比例中，所使用的NaY分子筛(也称NaY沸石)为中国石化催化剂有限公司齐鲁分公司提供，其氧化钠含量为13.5wt％，骨架硅铝比(SiO 2/Al 2O 3摩尔比)为4.6，晶胞常数为2.470nm，相对结晶度为90％。
氯化稀土和硝酸稀土为北京化工厂生产的化学纯试剂；硝酸锌和氯化锌为北京化工厂生产的化学纯试剂；拟薄水铝石为山东铝厂生产工业产品，固含量61wt％；高岭土为苏州中国高岭土公司生产的裂化催化剂专用高岭土，固含量76wt％；铝溶胶由中国石化催化剂有限公司齐鲁分公司提供，其中氧化铝含量为21wt％。
对比例和实施例中所用化学试剂未特别注明的，均为市售产品，其规格为化学纯。
分析方法
在各对比例和实施例中，分子筛的元素含量由X射线荧光光谱法测定。
分子筛的晶胞常数、相对结晶度由X射线粉末衍射法(XRD)采用RIPP145-90、RIPP146-90标准方法(见《石油化工分析方法(RIPP试验方法))》，杨翠定等编，科学出版社，1990年出版，第412-415页)测定。
分子筛的骨架硅铝比由下式计算而得：
骨架SiO 2/Al 2O 3摩尔比＝(2.5858-a 0)×2/(a 0-2.4191)，
其中，a 0为晶胞常数，单位为nm。
分子筛的总硅铝比是依据X射线荧光光谱法测定的Si与Al元素含量计算的，由XRD法测定的骨架硅铝比与XRF测定的总硅铝比可计算骨架Al与总Al的比值，进而计算非骨架Al与总Al的比值。
晶格崩塌温度由差热分析法(DTA)测定。
在各对比例和实施例中，分子筛的酸中心类型及其酸量采用吡啶吸附的红外法分析测定。实验仪器：美国Bruker公司IFS113V型FT-IR(傅立叶变换红外)光谱仪。用吡啶吸附红外法在350℃时测定酸量。实验方法：将样品自支撑压片，置于红外光谱仪的原位池中密封；升温至400℃，并抽真空至10 -3Pa，恒温2h，脱除样品吸附的气体分子；降至室温，导入压力为2.67Pa吡啶蒸气保持吸附平衡30min；然后升温至350℃，抽真空至10 -3Pa下脱附30min，降至室温摄谱，扫描波数范围：1400-1700cm -1，获得样品经350℃脱附的吡啶吸附红外光谱图。根据吡啶吸附红外光谱图中1540cm -1和1450cm -1特征吸附峰的强度，得到分子筛中强的BrOnsted酸中心(B酸中心)与Lewis酸中心(L酸中心)的相对量。
在各对比例和实施例中，二级孔体积的测定方法如下：按照RIPP 151-90标准方法(参见《石油化工分析方法(RIPP试验方法))》，杨翠定等编，科学出版社，1990年出版，第424-426页)根据吸附等温线测定出分子筛的总孔体积，然后从吸附等温线按照T作图法测定出分子筛的微孔体积，将总孔体积减去微孔体积得到二级孔体积。
以下的实施例1-3为根据本发明的改性Y型分子筛和催化裂化催化剂的制备实施例。
实施例1
取2000克NaY分子筛(以干基计)加入到20升去离子水中搅拌 使其混合均匀，加入600ml的RE(NO 3) 3溶液(稀土盐溶液浓度以RE 2O 3计为319g/L，RE是La和Ce的混合稀土，以稀土氧化物质量计La 2O 3∶Ce 2O 3＝3∶2)，搅拌，升温至90-95℃保持1小时，然后过滤、洗涤，滤饼于120℃干燥，得到晶胞常数为2.471nm、氧化钠含量7.0wt％、以RE 2O 3计稀土含量8.8wt％的Y型分子筛。
之后，将该分子筛在温度390℃、含50体积％水蒸汽和50体积％空气的气氛下焙烧6小时，得到晶胞常数为2.455nm的Y型分子筛。
冷却之后，将晶胞常数为2.455nm的Y型分子筛加入到溶有35克磷酸的6升水溶液中，升温至90℃，进行30分钟的磷改性处理，之后，将分子筛过滤洗涤，并将滤饼进行干燥处理，使其水含量低于1wt％。
然后，按照SiCl 4∶Y型分子筛(干基计)＝0.5∶1的质量比，向磷改性处理后的分子筛通入经加热汽化的SiCl 4气体，在温度为400℃的条件下，反应2小时，之后，用20升去离子水洗涤，然后过滤。
在所得滤饼中缓慢加入2300毫升浓度为0.020克/毫升的Zn(NO 3) 2溶液浸渍4小时，浸渍后的分子筛先在130℃烘干5小时，然后进行焙烧，焙烧条件400℃下焙烧3小时，得到改性Y型分子筛，记为SZ1，其物化性质列于表1中。
将SZ1在裸露状态经800℃、常压、100％水蒸气老化17小时后，用XRD分析SZ1老化前后的分子筛的相对结晶度并计算老化后的相对结晶度保留率，结果见表2，其中：
Figure PCTCN2019101513-appb-000001
取714.5克氧化铝含量为21wt％的铝溶胶加入1565.5克去离子水中，开启搅拌，加入2763克固含量为76wt％的高岭土分散60分钟。取2049克氧化铝含量为61wt％的拟薄水铝石加入8146克去离子水中，在搅拌状态下加入210ml质量浓度为36％盐酸，酸化60分钟后加入分散好的高岭土浆液，然后加入磨细的SZ1分子筛1500克(干基)，搅拌均匀后，进行喷雾干燥和洗涤处理，烘干得到催化剂，记为SC1。
其中，所得到的SC1催化剂中含有SZ1分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
实施例2
取2000克NaY分子筛(以干基计)加入到25升去离子水中搅拌使其混合均匀，加入800ml的RECl 3溶液(以RE 2O 3计的溶液浓度为：319g/L，RE是La和Ce的混合稀土，以稀土氧化物质量计La 2O 3∶Ce 2O 3＝3∶2)，搅拌，升温至90-95℃保持1小时，然后过滤、洗涤，滤饼于120℃干燥，得到晶胞常数为2.471nm、氧化钠含量为5.5wt％、以RE 2O 3计稀土含量为11.3wt％的Y型分子筛。
之后，将该分子筛于温度450℃、80％水蒸汽下焙烧5.5小时，得到晶胞常数为2.461nm的Y型分子筛。
冷却之后，将晶胞常数为2.461nm的Y型分子筛加入到溶有268克磷酸铵的6升水溶液中，升温至60℃，进行50分钟的磷改性处理，之后，将分子筛过滤洗涤，并将滤饼进行干燥处理，使其水含量低于1wt％。
然后，按照SiCl 4∶Y型分子筛＝0.6∶1的质量比，向磷改性处理后的分子筛通入经加热汽化的SiCl 4气体，在温度为480℃的条件下，反应1.5小时，之后，用20升去离子水洗涤，然后过滤。
在所得滤饼中缓慢加入2300毫升浓度为0.030克/毫升的ZnCl 2溶液浸渍4小时，浸渍后的分子筛先在130℃烘干5小时，然后进行焙烧，焙烧条件380℃下焙烧3.5小时，得到改性Y型分子筛，记为SZ2，其物化性质列于表1中。
将SZ2在裸露状态经800℃、17小时100％水蒸气老化后，用XRD分析了SZ2老化前后的分子筛的相对结晶度并计算了老化后的相对结晶度保留率，结果见表2。
取714.5克氧化铝含量为21wt％的铝溶胶加入1565.5克去离子水中，开启搅拌，加入2763克固含量为76wt％的高岭土分散60分钟。取2049克氧化铝含量为61wt％的拟薄水铝石加入8146克去离子水中，在搅拌状态下加入210ml化学纯的盐酸，酸化60分钟后加入分散好的高岭土浆液，然后加入磨细的SZ2分子筛1500克(干基)，搅拌均匀后，进行喷雾干燥和洗涤处理，烘干得到催化剂，记为SC2。
其中，所得到的SC2催化剂中含有SZ2分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
实施例3
取2000克NaY分子筛(干基)加入到22升去离子水中搅拌使其混合均匀，加入570ml的RECl 3溶液(以RE 2O 3计的稀土盐溶液浓度为319g/L，RE是La和Ce的混合稀土，以稀土氧化物质量计La 2O 3∶Ce 2O 3＝3∶2)，搅拌，升温至90-95℃保持搅拌1小时，然后过滤、洗涤，滤饼于120℃干燥，得到晶胞常数为2.471nm、氧化钠含量为7.5wt％、以RE 2O 3计稀土含量为8.5wt％的Y型分子筛。
之后，将该分子筛于温度470℃、70体积％水蒸汽下焙烧5小时，得到晶胞常数为2.458nm的Y型分子筛。
冷却之后，将晶胞常数为2.458nm的Y型分子筛加入到溶有95克磷酸氢二铵的6升水溶液中，升温至40℃，进行80分钟的磷改性处理，之后，将分子筛过滤洗涤，并将滤饼进行干燥处理，使其水含量低于1wt％。
然后，按照SiCl 4∶Y型分子筛＝0.4∶1的质量比，向磷改性处理后的分子筛通入经加热汽化的SiCl 4气体，在温度为500℃的条件下反应1小时，之后，用20升去离子水洗涤，然后过滤。
在所得滤饼中缓慢加入2500毫升浓度为0.070克/毫升的Zn(NO 3) 2溶液浸渍4小时浸渍后的分子筛先在130℃烘干5小时，然后进行焙烧，焙烧条件500℃下焙烧2小时，得到改性Y型分子筛，记为SZ3，其物化性质列于表1中。
将SZ3在裸露状态经800℃、17小时100％水蒸气老化后，用XRD分析SZ3老化前后的分子筛的相对结晶度并计算了老化后的相对结晶度保留率，结果见表2。
取714.5克氧化铝含量为21wt％的铝溶胶加入1565.5克去离子水中，开启搅拌，加入2763克固含量为76wt％的高岭土分散60分钟。取2049克氧化铝含量为61wt％的拟薄水铝石加入8146克去离子水中，在搅拌状态下加入210ml化学纯的盐酸，酸化60分钟后加入分散好的高岭土浆液，然后加入磨细的SZ3分子筛1500克(干基)，搅拌均匀后，进行喷雾干燥和洗涤处理，烘干得到催化剂，记为SC3。
其中，所得到的SC3催化剂中含有SZ3分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
以下的对比例1-3为非本发明的改性Y型分子筛和催化裂化催化剂的制备实施例。
对比例1
取2000克NaY分子筛(干基)加入到20升去离子水中搅拌使其混合均匀，加入1000克(NH 4) 2SO 4，搅拌，升温至90-95℃保持1小时，然后过滤、洗涤。
滤饼于120℃干燥之后于温度650℃、100％水蒸汽下焙烧5小时进行水热改性处理，之后，加入到20升去离子水中搅拌使其混合均匀，加入1000克(NH 4) 2SO 4，搅拌，升温至90-95℃保持1小时，然后过滤、洗涤。
滤饼于120℃干燥之后在温度650℃、100％水蒸汽下焙烧5小时进行第二次水热改性处理，得到两次离子交换两次水热超稳的不含稀土的水热超稳Y型分子筛，记为DZ1，其物化性质列于表1中。
将DZ1在裸露状态经800℃、17小时100％水蒸气老化后，用XRD分析了DZ1老化前后的分子筛的相对结晶度并计算了老化后的相对结晶度保留率，结果见表2。
将DZ1分子筛、高岭土、水、拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC1(参考实施例1的制备方法)。
其中，所得到的DC1催化剂中含有DZ1分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
对比例2
取2000克NaY分子筛(干基)加入到20升去离子水中搅拌使其混合均匀，加入1000克(NH 4) 2SO 4，搅拌，升温至90-95℃保持1小时，然后过滤、洗涤。
滤饼于120℃干燥之后进行水热改性处理，所述水热改性处理的温度650℃、100％水蒸汽下焙烧5小时，之后，加入到20升去离子水中搅拌使其混合均匀，加入200ml的RE(NO 3) 3溶液(以RE 2O 3计稀土盐溶液浓度为：319g/L，RE是La和Ce的混合稀土，以稀土氧化物质量计La 2O 3∶Ce 2O 3＝3∶2)及900克(NH 4) 2SO 4，搅拌，升温至90-95℃保持 1小时，然后过滤、洗涤。
滤饼于120℃干燥之后进行第二次水热改性处理(温度650℃，100％水蒸汽下焙烧5小时)，得到两次离子交换两次水热超稳的含稀土的水热超稳Y型分子筛，记为DZ2，其物化性质列于表1中。
将DZ2在裸露状态经800℃、17小时100％水蒸气老化后，用XRD分析了DZ2老化前后的分子筛的相对结晶度并计算了老化后的相对结晶度保留率，结果见表2。
将DZ2分子筛、高岭土、水、拟薄水铝石粘合剂以及铝溶胶按常规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC2(参考实施例1的制备方法)。
其中，所得到的DC2催化剂中含有DZ2分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
对比例3
取2000克NaY分子筛(干基)加入到22升去离子水中搅拌使其混合均匀，加入570ml的RECl 3溶液(以RE 2O 3计的稀土盐溶液浓度为319g/L，RE是La和Ce的混合稀土，以稀土氧化物质量计La 2O 3∶Ce 2O 3＝3∶2)，搅拌，升温至90-95℃保持搅拌1小时，然后过滤、洗涤。
滤饼于120℃干燥，得到晶胞常数为2.471nm、氧化钠含量为7.5wt％、以RE 2O 3计稀土含量为8.5wt％的Y型分子筛，然后，将分子筛加入到溶有95克磷酸氢二铵的6升水溶液中，升温至40℃，进行80分钟的磷改性处理，之后，将分子筛过滤洗涤，并将滤饼进行干燥处理，使其水含量低于1wt％。
然后，按照SiCl 4∶Y型分子筛＝0.4∶1的质量比，通入经加热汽化的SiCl 4气体，在温度为580℃的条件下，反应1.5小时，之后，用20升去离子水洗涤，然后过滤，得到改性Y型分子筛，记为DZ3，其物化性质列于表1中。
将DZ3在裸露状态经800℃、17小时100％水蒸气老化后，用XRD分析SZ3老化前后的分子筛的相对结晶度并计算了老化后的相对结晶度保留率，结果见表2。
将DZ3分子筛、高岭土、水、拟薄水铝石粘合剂以及铝溶胶按常 规的催化裂化催化剂的制备方法形成浆液、喷雾干燥制备成微球催化剂，所制备的催化裂化催化剂记为DC3(参考实施例1的制备方法)。
其中，所得到的DC3催化剂中含有DZ3分子筛30wt％，高岭土42wt％，拟薄水铝石25wt％，铝溶胶3wt％。
测试实施例
分别将实施例1-3制备的催化剂SC1、SC2以及SC3经800℃，100％水蒸气气氛下老化4小时或17小时后，评价其轻油微反活性，评价结果列于表3中，催化剂SC1、SC2、SC3对应的测试实施例编号分别为测试实施例1、测试实施例2、测试实施例3。
轻油微反活性评价方法：
采用RIPP 92-90的标准方法(见《石油化工分析方法(RIPP试验方法))》，杨翠定等编，科学出版社，1990年出版，第263-268页)评价各催化剂的轻油微反活性，催化剂装量为5.0g，反应温度为460℃，原料油为馏程235-337℃大港轻柴油，产物组成由气相色谱分析，根据产物组成计算出轻油微反活性。
轻油微反活性(MA)＝(产物中低于216℃的汽油产量+气体产量+焦炭产量)/进料总量×100％。
测试对比例
分别将对比例1-3制备的催化剂DC1、DC2以及DC3经800℃、100％水蒸气气氛下老化4小时或17小时后，评价其轻油微反活性。评价方法见测试实施例部分，评价结果列于表3中，催化剂DC1、DC2及DC3对应的测试对比例编号分别为测试对比例1、测试对比例2、测试对比例3。
应用实施例
将SC1、SC2、SC3催化剂经800℃、100％水蒸气气氛下老化12小时后，在小型固定流化床反应器(ACE)上评价其用于加工加氢LCO的催化裂化反应性能，裂化气和产品油分别收集由气相色谱分析。催化剂装量为9g，反应温度500℃，重时空速为16h -1，剂油质量比见表5，ACE实验的原料性质见表4，评价结果见表5。SC1、SC2、SC3催 化剂对应的应用实施例编号分别为应用实施例1、应用实施例2、应用实施例3。
其中，LCO有效转化率/％＝100-柴油产率-干气产率-焦炭产率-重油产率。
应用对比例
将DC1、DC2、DC3催化剂及中国专利申请公开CN 104560187A的实施例中所使用的HAC催化剂经800℃、100％水蒸气气氛下老化12小时后，在小型固定流化床反应器(ACE)上评价其用于加工加氢LCO的催化裂化反应性能，评价方法见应用实施例部分，ACE实验的原料性质见表4，评价结果列于表5中。DC1、DC2、DC3催化剂及HAC催化剂对应的应用对比例编号分别为应用对比例1、应用对比例2、应用对比例3、应用对比例4。
其中，LCO有效转化率/％＝100-柴油产率-干气产率-焦炭产率-重油产率。
表1实施例1-3和对比例1-3所得分子筛的性质
Figure PCTCN2019101513-appb-000002
Figure PCTCN2019101513-appb-000003
由表1可见，本公开提供的含磷、稀土及锌的改性Y型分子筛，同时具备以下优点：氧化钠含量低，硅铝比较高时的非骨架铝含量较少，孔径为2.0-100nm的二级孔的孔体积占总孔体积百分比较高，并且，B酸/L酸(强的B酸酸量与L酸酸量之比)较高，在分子筛晶胞常数较小稀土含量较高时测定的结晶度值较高，具有高的热稳定性。
表2实施例1-3和对比例1-3所得分子筛的老化测试结果
Figure PCTCN2019101513-appb-000004
由表2可知，本公开提供的含磷、稀土及锌的改性Y型分子筛，在裸露状态下经过800℃、17小时的苛刻条件老化后，分子筛样品具有较高的相对结晶度保留率，表明本公开提供的改性Y型分子筛具有高的水热稳定性。
表3测试实施例1-3和测试对比例1-3的测试结果
Figure PCTCN2019101513-appb-000005
表4应用实施例中所用加氢LCO的性质
项目 数值
碳含量，％ 88.91
氢含量，％ 11.01
20℃密度，kg/m 3 910.7
质谱烃质量组成，％  
链烷烃 10.1
总环烷烃 16.9
总单环芳烃 60.3
总双环芳烃 11.5
三环芳烃 1.2
总芳烃 73
胶质 0
总重量 100
氮含量，mg/L 0.9
硫含量，mg/L 49
表5应用实施例1-3和应用对比例1-4的实验结果
Figure PCTCN2019101513-appb-000006
由表3及表5可知，与对比例的催化剂相比，本公开提供的催化剂具有很高的水热稳定性、明显更低的焦炭选择性、明显更高的汽油收率，汽油中BTX(苯+甲苯+二甲苯)的产率显著提高，并且气体产物中乙烯和丙烯的总收率有明显提高。
以上详细描述了本公开的优选实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
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，本公开对各种可能的组合方式不再另行说明。此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (15)

  1. 一种改性Y型分子筛，以所述改性Y型分子筛的干基重量为基准，所述改性Y型分子筛的稀土含量以氧化稀土计为约4-11wt％，钠含量以氧化钠计为不超过约0.7wt％，锌含量以氧化锌计为约0.5-5wt％，磷含量以五氧化二磷计为约0.05-10wt％，骨架硅铝比以SiO 2/Al 2O 3摩尔比计为约7-14，非骨架铝含量占总铝含量的百分比不高于约20％，孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约15-30％。
  2. 根据权利要求1所述的改性Y型分子筛，其中所述改性Y型分子筛具有以下特性中的一项或多项：
    所述改性Y型分子筛的总孔体积为约0.33-0.39mL/g；
    所述改性Y型分子筛的晶胞常数为约2.440-2.455nm；
    所述改性Y型分子筛的非骨架铝含量占所述总铝含量的百分比为约13-19％；
    所述改性Y型分子筛的孔径为2-100nm的二级孔的孔体积占总孔体积的百分比为约20-30％；
    用吡啶吸附红外法在350℃测得的所述改性Y型分子筛的强酸量中B酸量与L酸量的比值不低于约3.50；
    所述改性Y型分子筛的晶格崩塌温度不低于约1050℃；
    所述改性Y型分子筛的相对结晶度不低于约60％；和/或
    所述改性Y型分子筛在800℃、常压、100体积％水蒸汽气氛下老化17小时后的相对结晶度保留率为约35％以上。
  3. 根据权利要求1或2所述的改性Y型分子筛，其中，以所述改性Y型分子筛的干基重量为基准，所述改性Y型分子筛的稀土含量为约4.5-10wt％，钠含量为约0.4-0.6wt％，磷含量为约0.1-6wt％，晶胞常数为约2.440-2.453nm，骨架硅铝比为约8.5-12.6。
  4. 一种改性Y型分子筛的制备方法，包括以下步骤：
    (1)使NaY分子筛与稀土盐溶液接触进行离子交换反应，得到离子交换后的分子筛；
    (2)对所述离子交换后的分子筛进行水热超稳改性处理，得到水热超稳改性的分子筛；
    (3)使所述水热超稳改性的分子筛与磷化合物接触进行磷改性处理，得到磷改性分子筛；
    (4)使所述磷改性分子筛与气态SiCl 4接触反应进行气相超稳改性，得到气相超稳改性的分子筛；以及
    (5)将所述气相超稳改性的分子筛用锌盐溶液浸渍，得到所述改性Y型分子筛。
  5. 根据权利要求4所述的方法，其中，所述步骤(1)进一步包括使NaY分子筛与稀土盐在水溶液中接触进行离子交换反应，其中所述离子交换反应的条件包括：
    交换温度为约15-95℃，交换时间为约30-120分钟，所述NaY分子筛、稀土盐、水的质量比为约1∶(0.01-0.18)∶(5-15)，所述NaY分子筛的质量以干基计，所述稀土盐的质量以氧化稀土计。
  6. 根据权利要求4或5所述的方法，其中，所述步骤(2)的水热超稳改性处理通过在约350-480℃的温度和约30-90体积％水蒸汽气氛下焙烧约4.5-7h来进行。
  7. 根据权利要求4-6中任一项所述的方法，其中，所述步骤(3)中，进行磷改性处理的温度为约15-100℃，时间为约10-100分钟；
    优选地，用于进行磷改性处理的所述磷化合物选自磷酸、磷酸铵、磷酸二氢铵、磷酸氢二铵中的一种或多种
  8. 根据权利要求4-7中任一项所述的方法，其中，所述步骤(4)中，反应温度为约200-650℃，反应时间为约10分钟至约5小时，SiCl 4与所述磷改性分子筛的质量比为约(0.1-0.7)∶1，所述磷改性分子筛的质量以干基计。
  9. 根据权利要求4-8中任一项所述的方法，其中，所述步骤(5)进一步包括对浸渍后的分子筛进行焙烧，其中浸渍温度为约10-60℃，焙烧温度为约350-600℃，焙烧时间为约1-4小时。
  10. 一种催化裂化催化剂，以所述催化剂的干基重量为基准，所述催化剂包含约10-50wt％的改性Y型分子筛、粘结剂和粘土；其中所述改性Y型分子筛为根据权利要求1-3中任一项所述的改性Y型分子筛或者通过权利要求4-9中任一项所述的方法制备得到的改性Y型分子筛。
  11. 根据权利要求10所述的催化裂化催化剂，其中，以干基计并 以所述催化剂的重量为基准，所述催化剂包含约10-50wt％的所述改性Y型分子筛、约10-40wt％的粘结剂和约10-80wt％的粘土。
  12. 根据权利要求10或11所述的催化裂化催化剂，所述粘土选自高岭土、多水高岭土、蒙脱土、硅藻土、埃洛石、皂石、累托土、海泡石、凹凸棒石、水滑石、膨润土，和它们的任意组合。
  13. 根据权利要求10-12中任一项所述的催化裂化催化剂，其中所述粘结剂为选自氧化铝、水合氧化铝、铝溶胶，和它们的任意组合的氧化铝粘结剂，并且所述粘结剂的含量以氧化铝计。
  14. 权利要求1-3中任一项所述的改性Y型分子筛在烃类原料的催化裂化反应中的应用，包括在催化裂化条件下使所述烃类原料与包含所述改性Y型分子筛的催化裂化催化剂接触。
  15. 根据权利要求14所述的应用，其中所述烃类原料为加氢轻循环油，并且所述催化裂化条件包括：反应温度为约500-610℃，重时空速为约2-16h -1，剂油重量比为约3-10。
PCT/CN2019/101513 2018-08-20 2019-08-20 改性y型分子筛、包含它的催化裂化催化剂、及其制备和应用 WO2020038347A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/268,371 US11130917B2 (en) 2018-08-20 2019-08-20 Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
SG11202012300PA SG11202012300PA (en) 2018-08-20 2019-08-20 Modified y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
AU2019326622A AU2019326622A1 (en) 2018-08-20 2019-08-20 Modified Y type molecular sieve, catalytic cracking catalyst having same, preparation methods therefor and applications thereof
JP2021509150A JP7394116B2 (ja) 2018-08-20 2019-08-20 改質ｙ型分子篩、それを含む接触分解触媒、及びそれらの作製と応用

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201810948782.X 2018-08-20
CN201810949445.2 2018-08-20
CN201810948782.XA CN110841691B (zh) 2018-08-20 2018-08-20 一种用于加工加氢lco的催化裂化催化剂及其制备方法
CN201810949445.2A CN110841695B (zh) 2018-08-20 2018-08-20 一种改性y型分子筛及其制备方法

Publications (1)

Publication Number Publication Date
WO2020038347A1 true WO2020038347A1 (zh) 2020-02-27

Family

ID=69570428

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/101513 WO2020038347A1 (zh) 2018-08-20 2019-08-20 改性y型分子筛、包含它的催化裂化催化剂、及其制备和应用

Country Status (7)

Country Link
US (1) US11130917B2 (zh)
JP (1) JP7394116B2 (zh)
AU (1) AU2019326622A1 (zh)
FR (1) FR3085005B1 (zh)
SG (1) SG11202012300PA (zh)
TW (1) TWI812772B (zh)
WO (1) WO2020038347A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116062765B (zh) * 2021-10-29 2024-07-02 中国石油化工股份有限公司 一种纳米y型分子筛的制备方法
CN116062764B (zh) * 2021-10-29 2024-05-10 中国石油化工股份有限公司 具有核壳结构的y-y复合型分子筛及其制备方法和应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597850A (zh) * 2003-09-15 2005-03-23 中国石油天然气股份有限公司 一种降低汽油硫含量的催化裂化催化剂及其制备方法
CN101745418A (zh) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 一种催化裂化催化剂及其制备和应用
CN102744092A (zh) * 2011-04-22 2012-10-24 中国石油天然气股份有限公司 一种磷和稀土改性的分子筛
US8524630B2 (en) * 2010-10-08 2013-09-03 Exxonmobil Research And Engineering Company Mesoporous aluminas stabilized with rare earth and phosphorous
CN107971011A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
CN107971017A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
CN108452832A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种富含二级孔的含磷和稀土改性y型分子筛及其制备方法
CN108452828A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种含磷和稀土的超稳y型分子筛及其制备方法
CN108452829A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种催化裂化催化剂
CN108452825A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种镁改性高硅超稳y型分子筛及其制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034718C (zh) 1993-07-29 1997-04-30 中国石油化工总公司 一种裂化催化剂及其制备方法
US6797155B1 (en) * 1999-12-21 2004-09-28 Exxonmobil Research & Engineering Co. Catalytic cracking process using a modified mesoporous aluminophosphate material
CN1160436C (zh) 2001-01-04 2004-08-04 中国石油化工股份有限公司 一种催化裂化催化剂的制备方法
US6635168B2 (en) * 2001-04-13 2003-10-21 W. R. Grace & Co.-Conn Gasoline sulfur reduction catalyst for fluid catalytic cracking process
CN1261216C (zh) * 2003-05-30 2006-06-28 中国石油化工股份有限公司 一种含分子筛的烃类裂化催化剂及其制备方法
CN1257769C (zh) * 2003-10-31 2006-05-31 中国石油化工股份有限公司 一种含磷和金属组分的mfi结构分子筛及其应用
TWI428180B (zh) * 2005-02-25 2014-03-01 Grace W R & Co 適用於流體化觸媒裂解程序之汽油硫減量觸媒
EP2877281B1 (en) * 2012-07-24 2021-08-18 Indian Oil Corporation Ltd Catalyst composition for fluid catalytic cracking, process for preparing the same and use thereof
CN103923698B (zh) 2013-01-11 2016-01-20 中国石油化工股份有限公司 一种生产芳香族化合物的催化转化方法
CN104560187B (zh) 2013-10-28 2016-05-25 中国石油化工股份有限公司 一种生产富含芳烃汽油的催化转化方法
CN104560185B (zh) 2013-10-28 2016-05-25 中国石油化工股份有限公司 一种生产富含芳香族化合物汽油的催化转化方法
WO2015098733A1 (ja) * 2013-12-25 2015-07-02 出光興産株式会社 酒類用金属担持ゼオライト及び酒類の製造方法
US10287511B2 (en) * 2015-06-09 2019-05-14 Hindustan Petroleum Corporation Ltd. Catalyst composition for fluid catalytic cracking, and use thereof
JP6803703B2 (ja) * 2016-08-29 2020-12-23 国立大学法人北海道大学 マンニトールの脱水用固体触媒、およびこの触媒を使用する２，５−ソルビタン及び／又はイソマンニドの製造方法
CN107973314B (zh) * 2016-10-21 2019-11-15 中国石油化工股份有限公司 一种含磷和稀土的y分子筛及其制备方法
US10899770B2 (en) * 2017-02-20 2021-01-26 Hangzhou Solipharma Co., Ltd. Crystal form of ACP-196 salt and preparation method, pharmaceutical composition, and use thereof
JP7037573B2 (ja) * 2017-02-21 2022-03-16 中国石油化工股▲ふん▼有限公司 改質ｙ型分子篩、その生成方法、およびそれを含む触媒
MY195283A (en) * 2017-02-21 2023-01-12 Sinopec Res Inst Petroleum Magnesium Modified Y-Type Molecular Sieve, Preparation Thereof and Catalyst Comprising the same
MY191917A (en) * 2017-02-22 2022-07-18 China Petroleum & Chem Corp Catalytic cracking catalyst and preparation thereof
SG11202013050QA (en) * 2018-08-20 2021-01-28 China Petroleum & Chem Corp Modified y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
US10894248B2 (en) * 2018-09-13 2021-01-19 Indian Oil Corporation Limited Catalyst composition for enhancing yield of olefins in fluid catalytic cracking process (FCC)
US10899685B1 (en) * 2019-10-07 2021-01-26 Saudi Arabian Oil Company Catalytic hydrodearylation of heavy aromatic stream containing dissolved hydrogen
US10899972B1 (en) * 2019-12-18 2021-01-26 Saudi Arabian Oil Company Fluid catalytic cracking of petroleum oil with reduced emissions

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1597850A (zh) * 2003-09-15 2005-03-23 中国石油天然气股份有限公司 一种降低汽油硫含量的催化裂化催化剂及其制备方法
CN101745418A (zh) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 一种催化裂化催化剂及其制备和应用
US8524630B2 (en) * 2010-10-08 2013-09-03 Exxonmobil Research And Engineering Company Mesoporous aluminas stabilized with rare earth and phosphorous
CN102744092A (zh) * 2011-04-22 2012-10-24 中国石油天然气股份有限公司 一种磷和稀土改性的分子筛
CN107971011A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
CN107971017A (zh) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 一种催化裂解催化剂及其制备方法
CN108452832A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种富含二级孔的含磷和稀土改性y型分子筛及其制备方法
CN108452828A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种含磷和稀土的超稳y型分子筛及其制备方法
CN108452829A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种催化裂化催化剂
CN108452825A (zh) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 一种镁改性高硅超稳y型分子筛及其制备方法

Also Published As

Publication number Publication date
US20210163828A1 (en) 2021-06-03
TWI812772B (zh) 2023-08-21
SG11202012300PA (en) 2021-01-28
FR3085005B1 (fr) 2022-05-13
FR3085005A1 (fr) 2020-02-21
JP7394116B2 (ja) 2023-12-07
JP2021534067A (ja) 2021-12-09
TW202009217A (zh) 2020-03-01
US11130917B2 (en) 2021-09-28
AU2019326622A1 (en) 2021-01-28

Similar Documents

Publication Publication Date Title
TW201833028A (zh) 改性y型分子篩、其製備方法及包含它的催化劑
US11517887B2 (en) Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
TWI812772B (zh) 改性y型分子篩、包含它的催化裂解催化劑、及其製備和用途
US11691132B2 (en) Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
US11504702B2 (en) Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, its preparation and application thereof
CN110833850B (zh) 催化裂化催化剂及其制备方法和应用
CN110833855B (zh) 催化裂化催化剂及其制备方法和应用
US11541377B2 (en) Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof
CN110841696B (zh) 一种用于加工加氢lco的催化裂化催化剂及其制备方法
CN110833852B (zh) 催化裂化催化剂及其制备方法和应用
CN110833851B (zh) 催化裂化催化剂及其制备方法和应用
CN110833863B (zh) 催化裂化催化剂及其制备方法和应用
CN110833860B (zh) 催化裂化催化剂及其制备方法和应用
CN110841691B (zh) 一种用于加工加氢lco的催化裂化催化剂及其制备方法
AU2019296817A1 (en) Modified Y-type molecular sieve, catalytic cracking catalyst including same, and preparation and use thereof
RU2798995C2 (ru) Модифицированное молекулярное сито типа y, содержащий его катализатор каталитического крекинга, их получение и применение
CN110841694B (zh) 一种用于加工加氢lco的催化裂化催化剂及其制备方法
CN110841692B (zh) 一种用于加工加氢lco的催化裂化催化剂及其制备方法
RU2802819C2 (ru) Модифицированные молекулярные сита типа y, катализатор каталитического крекинга, содержащий их, его получение и их применение
CN110841690B (zh) 一种改性y型分子筛及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19852788

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019326622

Country of ref document: AU

Date of ref document: 20190820

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2021509150

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19852788

Country of ref document: EP

Kind code of ref document: A1