CN110193376A

CN110193376A - A kind of catalytic cracking petroleum hydrocarbons catalyst

Info

Publication number: CN110193376A
Application number: CN201810159587.9A
Authority: CN
Inventors: 王鹏; 周灵萍; 姜秋桥; 宋海涛; 孙言; 严加松; 田辉平; 张久顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-02-26
Filing date: 2018-02-26
Publication date: 2019-09-03
Anticipated expiration: 2038-02-26
Also published as: CN110193376B

Abstract

A kind of catalytic cracking petroleum hydrocarbons catalyst, the molecular sieve for being 0.59-0.73 nanometers containing carrier, Y type molecular sieve, the mesopore molecular sieve with M41S structure and channel openings diameter；Described Y type molecular sieve includes phosphorous and rare earth super-stable Y molecular sieves, its total pore volume is 0.33~0.39mL/g, the pore volume of the second hole of 2~100nm accounts for the 10~25% of total pore volume, lattice constant is 2.440~2.455nm, the total aluminium content ratio of non-framework aluminum content Zhan is not higher than 20%, lattice collapse temperature is not less than 1050 DEG C, and the ratio of the B acid amount and L acid amount that are measured with pyridine adsorption infrared method at 200 DEG C is not less than 2.50.The catalyst heavy oil conversion activity is high, and coke selectivity is good, and yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield are high.

Description

A kind of catalytic cracking petroleum hydrocarbons catalyst

Technical field

The present invention relates to a kind of catalytic cracking petroleum hydrocarbons catalyst.

Background technique

Catalytic cracking is the important means of hydrocarbon ils processing, and catalytically cracked material slag-mixing amount increases in recent years, since residual oil is big Ratio shared by molecule is big, and arene content is high, is easy to coking in reaction process, proposes to the heavy oil cracking activity of Cracking catalyst Requirements at the higher level.In order to improve the processing performance of residual oil, in the prior art to catalytic cracking is carried out after residual hydrogenation again, with production The fuel such as gasoline, diesel oil.

The Cracking catalyst of heavy oil conversion depth is improved at present in the catalyst using super steady Y type molecular sieve.For example, CN1060976、CN1060977、CN1128673、CN1005405、CN1119206、CN1065844、US5340957、 The hydro-thermal of super-stable Y molecular sieves is provided in US5206194, US4273753, US4438178, US4584287 and US4429053 Preparation method, but the above method is easy that the crystal structure of molecular sieve is made to generate defect, obtained super-stable Y molecular sieves, and heavy oil is split Change activity is not high, and coke selectivity is bad.

CN1382525A, CN1194941A, CN1683244A, which are disclosed, utilizes SiCl₄Gas chemistry dealuminzation prepares super steady Y The method of type molecular sieve.But existing gas phase super stable molecular sieve still has the not high problem of activity, Bu Nengman for residual oil cracking The processing of sufficient mink cell focus and poor oil needs, and affects the product distribution and economic benefit of catalytic cracking unit.

CN1330981A, CN1353086A, CN1506161A, CN1317547A and CN1436727A draw in y-type zeolite Enter phosphorus and rare earth.But the Cracking catalyst that the prior art uses these zeolites to prepare, is used for hydrogenated residue cracking, and residual oil cracking is living Property and selectivity it is bad.

CN106268932A provides a kind of catalytic cracking catalyst and the preparation method and application thereof.The catalyst contains base The IM-5 molecular sieve of matter, the USY molecular sieve of super stabilizing and super stabilizing, on the basis of the weight of the catalyst, the super stabilizing USY molecular sieve and the total weight content of IM-5 molecular sieve of super stabilizing be 50wt%~90wt%, and the IM-5 of super stabilizing point The weight ratio of the USY molecular sieve of son sieve and super stabilizing is (0.01~0.25): 1.The catalyst is suitable for plus the conversion of hydrogen wax oil, uses It is converted in hydrogenated residue, cracking activity and yield of gasoline be not high, and coke selectivity is bad.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of catalytic cracking petroleum hydrocarbons catalyst, and the catalyst is for weight Oily cracking has higher heavy oil cracking activity and better coke selectivity.The invention solves second technical problem be A kind of preparation method and application method of catalyst is provided.

The present invention provides a kind of catalytic cracking of petroleum hydrocarbon catalyst, and with dry basis, the catalytic cracking of petroleum hydrocarbon is urged Agent contains the carrier of 40-80 weight % such as 50~70 weight %, the Y type point of 10~50 weight % such as 20-50 weight % Son sieve, the mesopore molecular sieve with M41S structure of 5-15 weight %, the channel openings diameter of 5-15 weight % are 0.59-0.73 The molecular sieve of nanometer, the Y type molecular sieve includes phosphorous and the super-stable Y molecular sieves of rare earth (the referred to as modified Y type point of the present invention Son sieve), the rare earth oxide content of phosphorous and rare earth the super-stable Y molecular sieves is 4~11 weight %, and phosphorus content is with P₂O₅Meter contains Amount is 0.05~10 weight %, and sodium oxide content is 0.1~0.7 weight %, and total pore volume is 0.33~0.39mL/g, this is phosphorous The pore volume for the second hole that super-stable Y molecular sieves aperture with rare earth is 2nm~100nm accounts for the phosphorous and rare earth superstable gamma-type The percentage of molecular sieve total pore volume is 10%~25%, and lattice constant is 2.440nm~2.455nm, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) it can be 7.3~14.0:1, the percentage of the total aluminium content of non-framework aluminum content Zhan is not high in molecular sieve In 20%, lattice collapse temperature is not less than 1050 DEG C, also, measured with pyridine adsorption infrared method at 200 DEG C this it is phosphorous and The ratio of B acid amount and L acid amount is not less than 2.50 in the super-stable Y molecular sieves total acid content of rare earth.

The superstable gamma-type of the phosphorous and rare earth used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention point Son sieve, lattice collapse temperature are not less than 1050 DEG C, it is preferred that 1055 DEG C~1080 DEG C of the molecular sieve lattice collapse temperature, such as It is 1057~1075 DEG C.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, B acid amount and L in phosphorous and rare earth the super-stable Y molecular sieves total acid content measured with pyridine adsorption infrared method at 200 DEG C It is, for example, 2.7~3.3 that the ratio of acid amount, which is preferably 2.6~4.0,.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, lattice constant are that 2.440nm~2.455nm is, for example, 2.442~2.450nm.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve is high-Si Y-type molecular sieve, framework si-al ratio (SiO₂/Al₂O₃Molar ratio) it is 7.3~14.0, for example, 8.5~12.6.

The super-stable Y molecular sieves of the phosphorous and rare earth used in catalyst provided by the invention, it is non-in molecular sieve The percentage of the total aluminium content of framework aluminum content Zhan is not higher than 20 weight %, for example, 13~19 weight %.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, the crystal retention under 800 DEG C, normal pressure, 100 volume % water vapour atmospheres after aging 17 hours are, for example, for 38% or more 38~48% or 39~45%.The normal pressure is 1atm.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, relative crystallinity are not less than 60%, it is preferred that described phosphorous and rare earth super-stable Y molecular sieves provided by the invention Relative crystallinity is 60~70%, for example, 60~66%.The measurement of described relative crystallinity (abbreviation crystallinity) in the present invention Method is referring in " petrochemical egineering analysis method (RIPP test methods) " (Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) RIPP 146-90 standard method.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, a kind of embodiment, specific surface area are 620~670m²/ g is, for example, 630~660m²/g。

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, it is preferred that total pore volume is that 0.35~0.39mL/g is, for example, 0.36~0.375mL/g.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, the percentage that the pore volume for the second hole that aperture (referring to diameter) is 2.0nm~100nm accounts for total pore volume is 10%~25%, Preferably 15~21%.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, containing rare earth element, with RE in phosphorous and rare earth the super-stable Y molecular sieves₂O₃The rare earth oxide content of meter is 4~11 weights Measuring % is preferably 4.5~10 weight %.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, described phosphorous and rare earth super-stable Y molecular sieves contain P Modification element, P in super-stable Y molecular sieves of the phosphorous and rare earth₂O₅(i.e. with P₂O₅The phosphorus content of meter) it is 0.05~10 weight Measure %, for example, 0.1~6 weight %, preferably 0.1~5 weight %.

Described phosphorous and rare earth superstable gamma-type molecule used in catalytic cracking of petroleum hydrocarbon catalyst provided by the invention Sieve, sodium oxide content be no more than 0.7%, can for 0.3~0.7 weight % be, for example, 0.35~0.60 weight % or 0.4~ 0.55 weight %.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, used described phosphorous and rare earth superstable gamma-type point Son sieve preparation method the following steps are included:

(1) NaY molecular sieve is contacted with earth solution and carries out ion-exchange reactions, be filtered, washed, obtain sodium oxide content The Y type molecular sieve of the conventional unit cell dimension containing rare earth reduced；Wherein earth solution is also referred to as rare-earth salt solution；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content reduces is modified processing, Optionally drying, obtains the Y type molecular sieve of lattice constant reduction, and the modification is to reduce the sodium oxide content containing dilute The Y type molecular sieve of the conventional unit cell dimension of soil is in 350~480 DEG C of temperature, the atmosphere (also referred to as 30 containing 30~90 volume % water vapours ~90 volume % water vapour atmospheres or 30~90% water vapours) under roast 4.5~7 hours；

(3) Y type molecular sieve that obtained lattice constant reduces is subjected to P Modification processing with phosphorus compound, it is dry, it obtains The Y type molecular sieve that phosphorous lattice constant reduces；Wherein, the water content for the Y type molecular sieve that the phosphorous lattice constant reduces Preferably more than 1 weight %；

(4) Y type molecular sieve and SiCl that the phosphorous lattice constant for obtaining step (3) reduces₄Gas is in temperature Haptoreaction under conditions of being 200~650 DEG C, wherein SiCl₄: the phosphorous lattice constant that (3) obtain the step of in terms of butt Weight ratio=0.1 of reduced Y type molecular sieve~0.7:1, the reaction time 10 minutes to 5 hours, then washed, filtering obtained To described phosphorous and rare earth super-stable Y molecular sieves.

Catalytic cracking of petroleum hydrocarbon catalyst provided by the present invention, containing carrier, wherein described carrier can be it is existing Conventional carrier, the present invention used in catalytic cracking catalyst are not particularly limited it, such as can be clay, oxidation One of alumina supporter, silica support, silicaalumina carrier are a variety of.The clay such as kaolin, more Hydrokaolinite, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, one in bentonite Kind is several.The alumina support can be one of aluminium oxide, hydrated alumina and Aluminum sol of various forms Or it is several；For example, one in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, hydrated alumina or Aluminum sol Kind or several, the hydrated alumina such as boehmite (Pseudoboemite), a diaspore (Boehmite), three One of diaspore (Gibbsite), bayerite (Bayerite) are a variety of.The alumina support preferably intends thin water aluminium Stone and Aluminum sol.A kind of embodiment, on the basis of the weight of catalyst, containing with oxidation in the catalytic cracking catalyst 2~15 weight % of aluminium the meter preferably Aluminum sol of 3~10 weight %, the weight of the 5-40 in terms of aluminium oxide % or 10~30 weight % are preferred The boehmite of 15~25 weight %.The silica support can be Silica hydrogel, waterglass and/or silica solution, preferably , the silica support includes silica solution, on the basis of the weight of catalyst, with SiO₂The content of silica solution is counted as 1-30 weight Measuring % or 0.5~25 weight % is, for example, 0.5-20 weight % or 1-15 weight %, and it is molten that the silica solution can be neutral silicon Glue, acidic silicasol or alkaline silica sol.Silicaalumina carrier such as silicon-aluminum sol, silica-alumina gel, amorphous One of silicon-aluminium oxide is a variety of.

Contain the mesopore molecular sieve with M41S structure in catalytic cracking petroleum hydrocarbons catalyst provided by the present invention, with On the basis of catalytic cracking petroleum hydrocarbons catalyst weight, the mesopore molecular sieve content with M41S structure is calculated as 5- with butt 15 weight %.One of described mesopore molecular sieve such as MCM-41, MCM-48 and MCM-50 with M41S structure is a variety of. In general, the M41S structure molecular screen sial atomic molar ratio be 10~400:1 such as 50~350:1 or 100-300:1 or 10-200:1 or 10-100:1 or 20~80:1 or 15~50:1.The M41S structure molecular screen sodium oxide content is no more than 0.1 weight %, the M41S structure molecular screen can be Hydrogen M41S structure molecular screen, for example, HMCM-41, H-Al- One of MCM-48 and HMCM-50 or a variety of.Hydrogen M41S molecular sieve can be passed through by the sodium form M41S molecular sieve synthesized Peracid and/or ammonium exchange, roasting obtain, this is known to the skilled person.

On the basis of catalytic cracking petroleum hydrocarbons catalyst weight, catalytic cracking petroleum hydrocarbons catalyst provided by the invention In the channel openings diameter containing 5-15 weight % be 0.59-0.73 nanometers of molecular sieve.The channel openings diameter is 0.59- 0.73 nanometer of molecular sieve, which is selected from, has AFR structure molecular screen, the molecular sieve of AFS structure, the molecular sieve of AFI structure, BEA structure Molecular sieve, the molecular sieve of BOG structure, the molecular sieve of CON structure, the molecular sieve of GME structure, the molecular sieve of LTL structure, MEI At least one of the molecular sieve of structure, the molecular sieve of MOR structure and molecular sieve of OFF structure.It is preferred that are as follows: Beta molecular sieve, SAPO-5 molecular sieve, SAPO-40 molecular sieve, SSZ-24 molecular sieve, CIT-1 molecular sieve, ZSM-18 molecular sieve, modenite, sodium At least one of chabasie and offretite.Preferably, the molecular sieve that described channel openings diameter is 0.59-0.73 nanometers Including one of ZSM-18 molecular sieve, SAPO-5 molecular sieve, Beta molecular sieve or a variety of.Channel openings diameter is 0.59- 0.73 nanometer of molecular sieve is preferably the molecular sieve that Hydrogen channel openings diameter is 0.59-0.73 nanometers, and sodium oxide content is not It is, for example, 0.01-1.5wt% or 0.1~1 weight % or 0.2~0.5 weight %, sial atomic molar ratio more than 1.5 weight % It is, for example, 0.1-300:1 or 0.5-200:1 or 1~100:1 for 0.1-500.For example, it is preferable to channel openings diameter be 0.59- 0.73 nanometer of molecular sieve is Si-Al zeolite, for example, Beta molecular sieve, SAPO-40 molecular sieve, SSZ-24 molecular sieve, CIT-1 One of molecular sieve, ZSM-18 molecular sieve, modenite, sodium chabazite and offretite are a variety of, sial atomic molar Than being respectively 0.1-100 or 1-100:1 or 5~80:1 or 10~50:1 or 20~40:1.

In catalytic cracking petroleum hydrocarbons catalyst provided by the invention, the Y type molecular sieve includes described phosphorous and rare earth Super-stable Y molecular sieves, on the basis of catalytic cracking petroleum hydrocarbons catalyst weight, the superstable gamma-type point of the phosphorous and rare earth The content of son sieve is 10~50 weight %, preferably 20-40 weight %.The Y type molecular sieve can also include other types Y type molecular sieve, such as the Y type molecular sieve that existing method obtains, other types of Y type molecular sieve content be preferably more than 30 weights Measure %, for example, 0-20 weight % or 0-10 weight %.Preferably, the Y type molecular sieve is of the present invention phosphorous and rare earth Super-stable Y molecular sieves.

The present invention also provides a kind of catalytic cracking of petroleum hydrocarbon method for preparing catalyst, comprising: by carrier, Y type molecular sieve, tool There is the mesopore molecular sieve of M41S structure, the molecular sieve that channel openings diameter is 0.59-0.73 nanometer and water formation slurries, drying Step；Wherein the Y type molecular sieve preferably include or for the phosphorous and rare earth super-stable Y molecular sieves, this it is phosphorous with The super-stable Y molecular sieves preparation method of rare earth the following steps are included:

(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains The Y type molecular sieve of the conventional unit cell dimension containing rare earth reduced to sodium oxide content；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content temperature 350~ 480 DEG C, roast 4.5~7 hours under 30~90 volume % water vapour atmospheres, optionally drying obtains the Y type point of lattice constant reduction Son sieve；

(3) Y type molecular sieve that the lattice constant that step (2) obtains reduces is subjected to P Modification processing with phosphorus compound, done It is dry, obtain the Y type molecular sieve that phosphorous lattice constant reduces；

(4) Y type molecular sieve and silicon tetrachloride gas haptoreaction reduced the phosphorous lattice constant, washing and mistake Filter, it is preferred that according to SiCl₄: Y type molecular sieve=0.1~0.7:1 that the phosphorous lattice constant in terms of butt reduces The Y type molecular sieve and silicon tetrachloride gas haptoreaction that weight ratio reduces the phosphorous lattice constant, reaction temperature 200 DEG C~650 DEG C, the reaction time is 10 minutes to 5 hours, and washing and filtering obtain described phosphorous and rare earth superstable gamma-type molecule Sieve.Wherein, the water content for the Y type molecular sieve that the phosphorous lattice constant reduces is preferably more than 1 weight %.

Catalytic cracking of petroleum hydrocarbon method for preparing catalyst provided by the invention, optional further includes that will dry for example spraying do Dry obtained catalyst microspheres washing and dry step.The formation slurries, spray drying, washing and drying are existing skill Art, the present invention do not have particular/special requirement.

It can be with or without rare earth element, with petroleum in the carrier of catalytic cracking of petroleum hydrocarbon catalyst provided by the present invention On the basis of the weight of hydrocarbon catalytic cracking catalyst, the catalyst carrier can the rare earth containing 0-5 weight % (with RE₂O₃Meter), In described rare earth element be, for example, mixed rare-earth elements based on lanthanum and/or cerium, wherein the content of lanthanum and/or cerium is total dilute The 50 weight % or more of soil amount, such as 60 weight % or more.Rare earth element is added in the carrier can improve the stabilization of catalyst Property.When containing rare earth element in carrier, during forming catalyst slurry, rare earth compound, Ke Yixian is added Rare earth compound is mixed with carrier, then carrier and molecular sieve first can also be mixed to form slurry with molecular sieve mixture again Then liquid adds rare earth compound, or rare earth compound and Component Vectors is mixed to form mixture and are then added to part In the slurries that carrier and molecular sieve are formed.

Catalytic cracking of petroleum hydrocarbon catalyst of the present invention is converted suitable for hydrocarbon oil catalytic cracking, is particularly suitable for heavy oil and is urged Change cracking.For this purpose, the present invention provides a kind of Heavy oil conversion method, including urging heavy oil and the catalytic cracking of petroleum hydrocarbon Agent is under catalytic cracking condition the step of haptoreaction, and wherein reaction temperature is 400-600 DEG C, weight (hourly) space velocity (WHSV) 5-30 hours^-1, Oil ratio 1-10 (weight ratio)；Preferable reaction temperature is 450-550 DEG C or 480-530 DEG C, and weight (hourly) space velocity (WHSV) is preferably 8-25 small When^-1, the preferred 2-7 of oil ratio.The heavy oil such as reduced crude, decompression residuum, wax tailings, deasphalted oil or this above-mentioned hydrocarbon One of hydrotreating oil that oil obtains after hydrotreating is a variety of.Heavy oil conversion method provided by the invention is especially Suitable for hydrogenated residue catalyzed conversion.A kind of embodiment, the heavy oil are hydrogenated residue, the arene content of the hydrogenated residue For 40~75 weight % such as 45~65 weight % or 50~70 weight %, paraffinicity is that 1~25 weight % is, for example, 5- 20 weight % or 8-15 weight %, naphthene content be 15~45 weight % such as 20~45 weight % or 25~35 weight %, Specific gravity is 0.92~0.95g/cm³, such as 0.925~0.945g/cm³Or 0.93~0.942g/cm³, oil ratio refer to catalyst with The weight ratio of feedstock oil.

Super-stable Y molecular sieves containing the phosphorous and rare earth in catalyst provided by the invention and described have There is the molecular sieve that the mesopore molecular sieve and channel openings diameter of M41S structure are 0.59-0.73 nanometers superior heavy oil to divide greatly Sub- cracking capability and good product selectivity, heavy oil conversion rate and yield of light oil are high, and coke selectivity is good, can be more existing The catalytic cracking catalyst that method obtains has higher heavy oil conversion activity and lower coke selectivity, is used for arene content Higher hydrogenated residue conversion, can have higher yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield.

Catalytic cracking catalyst preparation method provided by the invention will including preparing phosphorous and rare earth stabilization Y-type molecular sieve Phosphorous and rare earth the super-stable Y molecular sieves are with carrier, the mesopore molecular sieve with M41S structure, channel openings diameter 0.59-0.73 nanometers of molecular sieve and water forms the step of slurries, drying, can prepare petroleum hydrocarbon catalysis provided by the invention Cracking catalyst.

Heavy oil conversion method provided by the invention, heavy oil conversion rate is high, and coke yield is low, and yield of light oil is high, more existing Heavy oil conversion method has higher yield of gasoline, yield of liquefied gas and total liquid yield.

Specific embodiment

Catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, using catalytic cracking of petroleum hydrocarbon catalyst dry weight as base Standard, the catalytic cracking of petroleum hydrocarbon catalyst contain the carrier by dry basis 40-80 weight %, by dry basis 10~ The Y type molecular sieve of 50 weight %, the mesopore molecular sieve by dry basis 5-15 weight % with M41S structure and press butt The molecular sieve that the channel openings diameter of poidometer 5-15 weight % is 0.59-0.73 nanometers, it is preferred that press dry basis, institute State catalytic cracking of petroleum hydrocarbon catalyst to contain: carrier 50-75 weight % is preferably 50-70 or 55-75 weight %, Y type molecular sieve 15-50 weight % is preferably 20~40 weight % or 25-45 weight %, the mesopore molecular sieve 5-15 weight % with M41S structure Preferably 5-10 weight %, molecular sieve (present invention is also referred to as shape-selective molecular sieve) 5- that channel openings diameter is 0.59-0.73 nanometers 15 weight % are preferably 5-10 weight %.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, the oxygen of described phosphorous and rare earth super-stable Y molecular sieves Change content of rare earth is 4~11 weight %, preferably 4.5~10 weight %；P in phosphorous and rare earth the super-stable Y molecular sieves₂O₅ (i.e. with P₂O₅The phosphorus content of meter) it is 0.05~10 weight %, for example, 0.1~6 weight %, preferably 0.1~5 weight %；Oxygen Change sodium content is 0.1~0.7 weight %, and preferably 0.3~0.7 weight %, total pore volume is 0.33~0.39mL/g, and aperture is The percentage that the pore volume of the second hole of 2nm~100nm accounts for total pore volume is 10%~25%, preferably 15%~21%, structure cell Constant is 2.440nm~2.455nm, framework si-al ratio (SiO2/Al2O3 molar ratio) are as follows: 7.3~14.0, non-bone in molecular sieve The percentage of the total aluminium content of frame aluminium content Zhan is not higher than 20%, preferably 13~19, and relative crystallinity is not less than 60%, and lattice collapses Temperature of collapsing is 1055 DEG C~1080 DEG C, also, measured with pyridine adsorption infrared method at 200 DEG C this is phosphorous and rare earth super steady The ratio of B acid amount and L acid amount is not less than 2.50, preferably 2.6~4.0 in Y type molecular sieve total acid content.

In catalytic cracking of petroleum hydrocarbon catalyst provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth, for containing The gas phase of phosphorus and rare earth super steady Modified Zeolite Y includes that Y type molecular sieve is contacted to progress with silicon tetrachloride in preparation process The step of dealumination complement silicon reacts.The molecular sieve has high-crystallinity, has second level pore structure, and heat and hydrothermal stability are high.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth In preparation method, NaY molecular sieve and earth solution are subjected to ion-exchange reactions in step (1), to obtain sodium oxide content drop The Y type molecular sieve of the low conventional unit cell dimension containing rare earth.The NaY molecular sieve, can be commercially available or according to existing method system Standby, a kind of embodiment, the NaY molecular sieve lattice constant is 2.465~2.472nm, framework si-al ratio (SiO₂/Al₂O₃It rubs That ratio) it is 4.5~5.2, it is, for example, 85~95% that relative crystallinity, which is 85% or more, and sodium oxide content is 13.0~13.8 weights Measure %.NaY molecular sieve described in step (1) and earth solution carry out ion-exchange reactions, and exchange temperature is preferably 15~95 DEG C For example, 65~95 DEG C, swap time is preferably such as 45~90 minutes 30~120 minutes.NaY molecular sieve (in terms of butt): dilute Earth salt is (with RE₂O₃Meter): H₂The weight ratio of O=1:0.01~0.18:5~15.A kind of embodiment, the NaY molecular sieve with it is dilute Native solution carries out ion-exchange reactions, according to NaY molecular sieve: rare-earth salts: H₂The weight of O=1:0.01~0.18:5~15 It is excellent in 15~95 DEG C of such as 65~95 DEG C stirrings than NaY molecular sieve (also referred to as NaY zeolite), rare-earth salts and water are formed mixture Choosing stirring carries out exchanging for rare earth ion and sodium ion for 30~120 minutes, the water such as decationized Y sieve water, deionized water or Its mixture.NaY molecular sieve, rare-earth salts and water are formed into mixture, NaY molecular sieve and water slurries can be formed into, then existed The aqueous solution of rare-earth salts and/or rare-earth salts is added in the slurries, the earth solution is the solution of rare-earth salts, described Rare-earth salts is preferably rare earth chloride and/or nitric acid rare earth.One in the rare earth such as La, Ce, Pr, Nd and mischmetal Kind or it is a variety of, it is preferred that containing one of La, Ce, Pr and Nd or a variety of in the mischmetal, or also containing except La, At least one of rare earth other than Ce, Pr and Nd.A kind of embodiment, the rare earth are mischmetal.Step (1) is described Washing, it is therefore an objective to wash away the sodium ion being swapped out, it is, for example, possible to use deionized water or decationized Y sieve water washings.It is preferred that step Suddenly the content of rare earth of the Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content that (1) obtains reduces is with RE₂O₃Meter It is, for example, 7~14 weight or 5.5~12 weight % for 5.5~14 weight %, sodium oxide content is no more than 9 weight % and is, for example, 5.5~8.5 weight % or 5.5~7.5 weight %, lattice constant are 2.465nm~2.472nm.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth Preparation method, by the Y type molecular sieve of the conventional unit cell dimension containing rare earth at 350~480 DEG C of temperature in step (2), 30~90 bodies It roasts 4.5~7 hours and is handled under product % water vapour atmosphere, it is preferred that maturing temperature described in step (2) is 380~460 DEG C, calcination atmosphere is 40~80 volume % water vapour atmospheres, and calcining time is 5~6 hours.Contain in the water vapour atmosphere 30~90 volume % vapor also contain one of other gases, such as air, helium or nitrogen or a variety of.In step (2) The Y type molecular sieve that the lattice constant reduces, lattice constant are 2.450nm~2.462nm.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth Preparation method, step (3) carry out the Y type molecular sieve that the lattice constant that step (2) obtains reduces at P Modification with phosphorus compound Reason, to introduce phosphorus in molecular sieve, the P Modification processing generally includes the Y type point that step (2) is obtained to lattice constant reduction Son sieve is contacted with exchange liquid, and the exchange liquid contains phosphorus compound, and the contact is usually at 15~100 DEG C preferably 30~95 DEG C Contact 10-100 minutes, is then filtered, and is washed.Wherein, exchange liquid in water and molecular sieve weight ratio be 2~5, preferably 3~ 4, phosphorus is (with P₂O₅Meter) with the weight ratio of molecular sieve are as follows: 0.0005~0.10, preferably 0.001~0.05.Described phosphorus compound can Selected from one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or a variety of.The washing is for example with molecular sieve 5 ~15 times of water such as decationized Y sieve or deionized water are washed.Also the molecular sieve that roasting obtains is done in step (3) It is dry, so that the water content in the Y type molecular sieve that the phosphorous lattice constant reduces is preferably more than 1 weight %.The drying, Existing method can be used, for example, by using pneumatic conveying drying, drying, expansion drying method.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth A kind of embodiment of preparation method, the P Modification treatment conditions are as follows: the Y type molecular sieve powder for reducing the lattice constant Last sample is added in the exchange liquid containing phosphorus compound, the exchange reaction 10~100 minutes under conditions of 15~100 DEG C, filtering, Washing；Wherein, the weight ratio for exchanging water and molecular sieve in liquid is 2~5, preferably 3~4, and phosphorus is (with P₂O₅Meter) with the weight of molecular sieve Measure ratio are as follows: 0.0005~0.10, preferably 0.001~0.05.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth In preparation method, in step (4), SiCl₄: the weight ratio of Y type molecular sieve (in terms of butt) is preferably 0.3~0.6:1, described anti- The temperature answered is preferably 350~500 DEG C, and washing methods described in step (4) can be washed with water using conventional washing methods Wash such as decationized Y sieve water or deionized water washing, it is therefore an objective to remove Na remaining in zeolite⁺, Cl^-And Al³⁺Deng soluble by-product Object, such as wash conditions can be with are as follows: the weight ratio of washing water and molecular sieve can be 5~20:1, usual molecular sieve: H₂O weight Than=1:6~15, pH value is preferably 2.5~5.0, and wash temperature is 30~60 DEG C.Preferably, the washing, after making washing Detected in cleaning solution do not go on a tour from Na⁺, Cl^-And Al³⁺Plasma, usually Na in the sieve sample after washing⁺, Cl^-And Al³⁺ The respective content of ion is no more than 0.05 weight %.

In catalytic cracking catalyst preparation method provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth Preparation method, a kind of embodiment the following steps are included:

(1) NaY molecular sieve (also referred to as NaY zeolite) and earth solution are subjected to ion-exchange reactions, filtered, washing obtains The Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium oxide content reduces；The ion exchange usually stirring, temperature be It is exchanged 30~120 minutes under conditions of 15~95 DEG C preferably 65~95 DEG C；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing the sodium oxide content temperature 350~ It 480 DEG C, roasts 4.5~7 hours under the atmosphere containing 30~90 volume % water vapours, it is dry, obtain the Y type point of lattice constant reduction Son sieve；The lattice constant for the Y type molecular sieve that the lattice constant reduces is 2.450nm~2.462nm；

(3) Y type molecular sieve for reducing the lattice constant is added in the exchange liquid containing phosphorus compound, 15~100 Exchange reaction 10~100 minutes under conditions of DEG C are filtered, washing；Wherein, the weight ratio for exchanging water and molecular sieve in liquid is 2 ~5, preferably 3~4, phosphorus is (with P₂O₅Meter) it with the weight ratio of molecular sieve is 0.0005~0.10 preferably 0.001~0.05, it is dry, Obtain the Y type molecular sieve that phosphorous lattice constant of the water content lower than 1 weight % reduces；

(4) Y type molecular sieve and heated vaporization that the phosphorous lattice constant by the water content lower than 1 weight % reduces SiCl₄Gas contacts, wherein SiCl₄: Y type molecular sieve that phosphorous lattice constant of the water content lower than 1 weight % reduces (with Butt meter) weight ratio=0.1~0.7:1, temperature be 200~650 DEG C under conditions of haptoreaction 10 minutes to 5 hours, Washed and filtering obtains of the present invention phosphorous and rare earth super-stable Y molecular sieves.

It is described to prepare phosphorous and rare earth stabilization Y-type molecular sieve method, available high-crystallinity, high thermal stability and Gao Shui The high-Si Y-type molecular sieve with certain second level pore structure of thermal stability, aluminium is evenly distributed in the molecular sieve, non-framework aluminum content It is few.

In fluidized cracking catalysts preparation method provided by the invention, the carrier can be clay, alumina support, oxygen One of SiClx carrier, silicaalumina carrier are a variety of.The alumina support such as gama-alumina, η-oxidation Aluminium, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite), one or more of bayerite (Bayerite) or Aluminum sol；The silica support such as silica gel, silicon One of gel, silica solution, waterglass are a variety of；The silicaalumina carrier, for example, it is silica-alumina gel, amorphous One of silica-alumina, silicon-aluminum sol are a variety of, and the clay such as kaolin, halloysite, illiteracy is de- One or more of soil, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite, preferably One or more of kaolin, halloysite, montmorillonite, diatomite, tired de- soil, more preferable kaolin.Preferably, described Carrier includes the substance of commonly referred to as binder, such as al binder and/or silicon bonding, and the al binder can be selected from being hydrated Aluminium oxide and/or Aluminum sol, the hydrated alumina such as boehmite (Pseudoboemite), a diaspore (Boehmite), one or more of gibbsite (Gibbsite), bayerite (Bayerite), the hydrated alumina Acidification (acidizing product is also referred to as acidified hydrated alumina) is generally gone through as binder, wherein the acidification includes that will be hydrated oxygen Change the step of aluminium is contacted with acid, wherein the acid-aluminum ratio (36 weight % hydrochloric acid and the aqua oxidation in terms of aluminium oxide that are preferably acidified The weight ratio of aluminium) it is 0.15~0.25:1, preferably 0.18~0.22:1；In the silicon bonding such as silica solution, waterglass One or more, preferably silica solution, the silica solution is, for example, that acidic silicasol (usual pH value is 2~4), neutral silicon are molten One or more of glue (usual pH value is 6~8), alkaline silica sol (usual pH value is 9~10.5).

In fluidized cracking catalysts preparation method provided by the invention, in terms of oxide, silicon bonding accounts for carrier, Y type molecule Point that sieve, the mesopore molecular sieve (abbreviation mesopore molecular sieve) with M41S structure and channel openings diameter are 0.59-0.73 nanometers The ratio of the total dry weight (dry weight that the present invention is known as catalyst slurry) of son sieve (abbreviation shape-selective molecular sieve) is no more than 30 Weight % is, for example, that 0-15 weight % or 1-15 weight % is preferably 5-15 weight %；In terms of oxide, al binder account for carrier, The total butt of molecular sieve that Y type molecular sieve, the mesopore molecular sieve with M41S structure and channel openings diameter are 0.59-0.73 nanometers It is, for example, 0~40 weight % or 12~35 weight % that the ratio of weight, which is no more than 40 weight %,.A kind of embodiment, described is viscous Knot agent is one of boehmite, Aluminum sol and silica solution or a variety of, and binder accounts for carrier, Y type molecule in terms of oxide The total dry weight of molecular sieve that sieve, the mesopore molecular sieve with M41S structure and channel openings diameter are 0.59-0.73 nanometers Ratio is 12~35 weight % preferably 15~30 weight % or 18-28 weight % or 20-25 weight %.In general, other than binder The carrier present invention be known as inorganic oxide matrix, account for the dry weight of catalyst slurry ratio be 0-80 weight %, such as For 10-70 weight % or 20-50 weight % or 25-45 weight %, it is common which is selected from Cracking catalyst One or more of inorganic oxide matrix, preferred inorganic oxide matrix are that clay such as kaolin group's clay is preferably high Ridge soil, it is preferred that clay account for the dry weight of catalyst slurry ratio be 10-60 weight % be, for example, 20~50 weight % or 30~45 weight %.

Catalytic cracking of petroleum hydrocarbon method for preparing catalyst provided by the invention: will include the super steady Y of described phosphorous and rare earth Y type molecular sieve, mesopore molecular sieve, shape-selective molecular sieve, inorganic oxide matrix, the binder of type molecular sieve are mixed with deionized water Mashing forms catalyst slurry, dry, obtains catalytic cracking catalyst.The solid content for being beaten the catalyst slurry formed is generally 10-50 weight %, preferably 15-30 weight %.Drying condition after mashing is to commonly use in catalytic cracking catalyst preparation process Drying condition.In general, drying temperature is 100-350 DEG C, preferably 200-300 DEG C.The drying can use drying, drum Air-dry dry or spray drying method, the method for preferably spray drying.

The following examples illustrate the present invention further, but these embodiments should not be understood as to limit of the invention It is fixed.

In embodiment and in comparative example, NaY molecular sieve (also referred to as NaY zeolite) is Sinopec catalyst Co., Ltd Shandong Branch company provides, and sodium oxide content is 13.5 weight %, framework si-al ratio (SiO₂/Al₂O₃Molar ratio)=4.6, lattice constant is 2.470nm, relative crystallinity 90%；Rare earth chloride and nitric acid rare earth are the chemically pure reagent of Beijing Chemical Plant's production.

Analysis method: in each comparative example and embodiment, the constituent content of zeolite is by x-ray fluorescence spectrometry；Boiling The lattice constant of stone, relative crystallinity (crystallinity) use RIPP145-90, RIPP146- by x-ray powder diffraction (XRD) 90 standard methods (are compiled, Science Press, nineteen ninety goes out see " petrochemical analysis method " (RIPP test method) Yang Cui is surely equal Version) it measures, the framework si-al ratio of zeolite is calculated by following formula and is obtained: SiO₂/Al₂O₃=(2.5858-a₀)×2/(a₀-2.4191)] Wherein, a₀For lattice constant, unit nm；Si and Al element of the total silica alumina ratio of zeolite according to x-ray fluorescence spectrometry What content calculated, total silica alumina ratio of framework si-al ratio and the XRF measurement measured by XRD method can calculate the ratio of skeleton Al and total Al Value, and then calculate the ratio of non-skeleton Al and total Al.Crystal structure collapse temperature is measured by differential thermal analysis (DTA).

In each comparative example and embodiment, the acid site type and its acid amount of molecular sieve are divided using the infrared method of pyridine adsorption Analysis measurement.Laboratory apparatus: the U.S. Bruker company IFS113V type FT-IR (fourier-transform infrared) spectrometer.Use pyridine adsorption Infrared method measures acid amount experimental method at 200 DEG C: by sample self-supporting tabletting, being placed in the Chi Zhongmi in situ of infrared spectrometer Envelope.400 DEG C are warming up to, and is evacuated to 10^-3Pa, constant temperature 2h, the gas molecule of removing sample absorption.It is down to room temperature, imports pressure Power is that 2.67Pa pyridine steam keeps adsorption equilibrium 30min.200 DEG C are then heated to, is evacuated to 10^-330min is desorbed under Pa, It is down to room temperature and takes the photograph spectrum, scan wave-number range: 1400cm^-1~1700cm^-1, it is infrared to obtain the pyridine adsorption that sample is desorbed through 200 DEG C Spectrogram.According to 1540cm in Pyridine adsorption IR spectra figure^-1And 1450cm^-1The intensity of feature adsorption peak, obtains in molecular sieve TotalThe relative quantity in acid site (acid site B) and the acid site Lewis (acid site L).

In each comparative example and embodiment, wherein the measuring method of described second level pore volume is as follows: according to RIPP151-90 Standard method " petrochemical egineering analysis method (RIPP test methods) " (Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) root The total pore volume of molecular sieve is determined according to adsorption isotherm, then determines molecular sieve from adsorption isotherm according to T graphing method Total pore volume is subtracted micro pore volume and obtains second level pore volume by micro pore volume,

Chemical reagent used is not specifically specified in comparative example and embodiment, and specification is that chemistry is pure.

Embodiment 1

Taking 2000 grams of NaY molecular sieves (in terms of butt) to be added to stirring in 20 liters of decationized Y sieve water is uniformly mixed it, adds Enter the RE (NO of 600ml₃)₃(earth solution concentration is with RE for solution₂O₃It is calculated as 319g/L), stirring is warming up to 90~95 DEG C and keeps 1 Hour, be then filtered, washed, filter cake in 120 DEG C of dryings, obtain lattice constant be 2.471nm, 7.0 weight % of sodium oxide content, With RE₂O₃The Y type molecular sieve for counting 8.8 weight % of content of rare earth contains 50 volume % water vapours and 50 bodies later at 390 DEG C of temperature It is roasted 6 hours under the atmosphere of product % air, the Y type molecular sieve that lattice constant is 2.455nm is obtained, after cooling, by molecular sieve It is added in 6 aqueous solutions dissolved with 35 grams of phosphoric acid, is warming up to 90 DEG C, P Modification processing in 30 minutes is carried out, later, by molecule It is sieved through filter washing, and filter cake is dried, makes its water content lower than 1 weight %, then according to SiCl₄: Y type molecular sieve is (dry Base meter)=0.5:1 weight ratio, be passed through the SiCl of heated vaporization₄Gas, under conditions of temperature is 400 DEG C, reaction 2 is small When, it later, with 20 liters of decationized Y sieve water washings, then filters, obtains provided by the invention phosphorous and rare earth superstable gamma-type molecule Sieve, is denoted as SZ1, physico-chemical property is listed in Table 1 below, by SZ1 in naked state through 800 DEG C, 1atm, 100% vapor aging 17 After hour, the relative crystallinity of the molecular sieve before and after SZ1 aging is analyzed with the method for XRD and the opposite crystallization calculated after aging is protected Office Copy the results are shown in Table 2, in which:

Embodiment 2

Taking 2000 grams of NaY molecular sieves (in terms of butt) to be added to stirring in 25 liters of decationized Y sieve water is uniformly mixed it, adds Enter the RECl of 800ml₃Solution is (with RE₂O₃The solution concentration of meter are as follows: 319g/L), stirring is warming up to 90~95 DEG C and is kept for 1 hour, Then be filtered, washed, filter cake in 120 DEG C of dryings, obtain lattice constant be 2.471nm, sodium oxide content be 5.5 weight %, with RE₂O₃The Y type molecular sieve that content of rare earth is 11.3 weight % is counted, roasting 5.5 is small under 450 DEG C of temperature, 80% water vapour later When, it obtains the Y type molecular sieve that lattice constant is 2.461nm and molecular sieve is added to 6 dissolved with 268 grams of ammonium phosphate after cooling In aqueous solution, be warming up to 60 DEG C, carry out P Modification processing in 50 minutes, later, molecular sieve filtration is washed, and by filter cake into Row is dried, and makes its water content lower than 1 weight %, then according to SiCl₄: y-type zeolite=0.6:1 weight ratio, be passed through through Heat the SiCl of vaporization₄Gas is reacted 1.5 hours, later, is washed with 20 liters of decationized Y sieves under conditions of temperature is 480 DEG C It washs, then filters, obtain phosphorous and rare earth super-stable Y molecular sieves, be denoted as SZ2.Its physico-chemical property is listed in Table 1 below, and SZ2 is existed Naked state is through 800 DEG C, after 100% vapor aging in 17 hours, zeolite before and after analyzing SZ2 aging with the method for XRD Crystallinity simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.

Embodiment 3

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve water is uniformly mixed it, is added The RECl of 570ml₃Solution is (with RE₂O₃The earth solution concentration of meter is 319g/L), stirring is warming up to 90~95 DEG C and is kept stirring 1 Hour, it is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 7.5 weights in 120 DEG C of dryings Measure %, with RE₂O₃The Y type molecular sieve that content of rare earth is 8.5 weight % is counted, later under 470 DEG C of temperature, 70 volume % water vapours Roasting 5 hours obtains the Y type molecular sieve that lattice constant is 2.458nm and molecular sieve is added to dissolved with 95 grams of phosphorus after cooling In 6 aqueous solutions of sour hydrogen diammonium, 40 DEG C are warming up to, P Modification processing in 80 minutes is carried out, later, molecular sieve filtration is washed It washs, and filter cake is dried, make its water content lower than 1 weight %, then according to SiCl₄: y-type zeolite=0.4:1 Weight ratio is passed through the SiCl of heated vaporization₄Gas reacts 1 hour, under conditions of temperature is 500 DEG C later, with 20 liters Decationized Y sieve water washing, is then filtered, and is obtained phosphorous and rare earth super-stable Y molecular sieves, is denoted as SZ3.Its physico-chemical property is listed in In table 1, by SZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, before analyzing SZ3 aging with the method for XRD The crystallinity of zeolite afterwards simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.

Comparative example 1

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve water is uniformly mixed it, is added 1000 grams of (NH₄)₂SO₄, stir, be warming up to 90~95 DEG C and kept for 1 hour, is then filtered, washed, filter cake is after 120 DEG C dry Hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) are carried out, later, are added to 20 liters of decationized Y sieve water Stirring is uniformly mixed it in solution, and 1000 grams of (NH are added₄)₂SO₄, stir, be warming up to 90~95 DEG C of holdings 1 hour, then mistake Filter, washing carry out second of hydrothermal modification treatment after filter cake is dry in 120 DEG C, hydrothermal conditions are 650 DEG C of temperature, It is roasted 5 hours under 100% water vapour, obtaining ion exchange twice, the super steady hydro-thermal superstable gamma-type without rare earth of hydro-thermal divides twice Son sieve, is denoted as DZ1.Its physico-chemical property is listed in Table 1 below, by DZ1 in naked state through 800 DEG C, 100% vapor aging in 17 hours Afterwards, the crystallinity of the zeolite before and after analyzing DZ1 aging with the method for XRD simultaneously calculates the opposite crystal retention after aging, It the results are shown in Table 2.

Comparative example 2

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve water is uniformly mixed it, is added 1000 grams of (NH₄)₂SO₄, stir, be warming up to 90~95 DEG C and kept for 1 hour, is then filtered, washed, filter cake is after 120 DEG C dry Hydrothermal modification treatment is carried out, hydrothermal modification treatment roasts 5 hours under 650 DEG C of temperature, 100% water vapour, later, is added to 20 Rising stirring in decationized Y sieve aqueous solution is uniformly mixed it, and the RE (NO of 200ml is added₃)₃Solution is (with RE₂O₃It is dense to count earth solution Degree are as follows: 319g/L) and 900 grams of (NH₄)₂SO₄, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in Second of hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) are carried out after 120 DEG C of dryings, obtain two Secondary ion exchanges the super steady hydro-thermal super-stable Y molecular sieves containing rare earth of hydro-thermal twice, is denoted as DZ2.Its physico-chemical property is listed in table 1 In, by DZ2 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, before analyzing DZ2 aging with the method for XRD The crystallinity of zeolite afterwards simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.

Comparative example 3

Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve water is uniformly mixed it, is added The RECl of 570ml₃Solution is (with RE₂O₃The earth solution concentration of meter is 319g/L), stirring is warming up to 90~95 DEG C and is kept stirring 1 Hour, it is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 7.5 weights in 120 DEG C of dryings Measure %, with RE₂O₃Then molecular sieve is added to dissolved with 95 grams of phosphoric acid hydrogen by the Y type molecular sieve that meter content of rare earth is 8.5 weight % In 6 aqueous solutions of diammonium, 40 DEG C are warming up to, P Modification processing in 80 minutes is carried out, later, molecular sieve filtration is washed, and Filter cake is dried, and filter cake is dried, makes its water content lower than 1 weight %, then according to SiCl₄: Y Type zeolite=0.4:1 weight ratio, is passed through the SiCl of heated vaporization₄Gas, under conditions of temperature is 580 DEG C, reaction 1.5 Hour, it later, with 20 liters of decationized Y sieve water washings, then filters, obtains phosphorous and rare earth super-stable Y molecular sieves, be denoted as DZ3.Its physico-chemical property is listed in Table 1 below, and DZ3 after 100% vapor aging in 17 hours, is used XRD through 800 DEG C in naked state Method analysis SZ3 aging before and after zeolite crystallinity and calculate the opposite crystal retention after aging, the results are shown in Table 2.

Embodiment 4~7

Embodiment 4~7 illustrates method for preparing catalyst provided by the invention and its stability.

Phosphorous and super-stable Y molecular sieves SZ1, SZ2, SZ3 of rare earth by Examples 1 to 3 preparation are prepared into catalysis respectively Agent, catalyst are numbered successively are as follows: A1, A2, A3 and A4.

Kaolin is China Kaolin Co., Ltd's industrial products in embodiment 4-7, and solid content is 84 weight %；It is used intend it is thin Diaspore is Chinese Aluminium Co., Ltd Shandong branch company product, and alumina content is 35 weight %；During Aluminum sol is Asphalt in Shenli Refinery, Effect of Catalysis In Petrochemistry agent Co., Ltd, state produces, and alumina content is 21 weight %, MCM-41 molecular sieves and MCM- 48 molecular sieves are Nanjing Ji Cang nanosecond science and technology Co., Ltd product, and MCM-41 molecular sieve silica alumina ratio is 300 (sial atomic molars Than), crystallinity 90%, 0.1 weight % of sodium oxide content, Hydrogen；100 (sial atomic molar of Al-MCM-48 molecular sieve silica alumina ratio Than), crystallinity 91%, 0.08 weight t% of sodium oxide content, Hydrogen；Beta zeolite, modenite are that Sinopec catalyst has Asphalt in Shenli Refinery, limit company commercial product, Beta (β) molecular sieve: asphalt in Shenli Refinery, Sinopec catalyst Co., Ltd product, Sial atomic molar ratio is 20,0.02 weight % of sodium oxide content；H-mordenite: the limited public affairs of Shanghai Shen environmental friendly material covered with clouds Department's production, sial atomic molar ratio are 10；0.05 weight % of sodium oxide content, Hydrogen.

Acidic silicasol is produced by Beijing Chemical Plant, and silica content is 25 weight %.

Method for preparing catalyst:

(1) it weighs quantitative boehmite (abbreviation aluminium stone) and quantitative water is uniformly mixed, be added under stiring quantitative Concentration be 36 weight % concentrated hydrochloric acid (chemistry pure, Beijing Chemical Plant produce), acid-aluminum ratio is 0.18 (36 weight % hydrochloric acid and aluminium The weight ratio of stone (in terms of aluminium oxide)), gained mixture is warming up to 70 DEG C of agings 1.5 hours, obtain aging intends thin water aluminium Stone, the alumina content of the boehmite of the aging are 12 weight %.

(2) by super-stable Y molecular sieves SZ1, SZ2, SZ3 of quantitative phosphorous and rare earth, quantitative Aluminum sol and/or silicon are molten (i.e. channel openings diameter is for glue, the quantitative mesopore molecular sieve mesopore molecular sieve of M41S structure (i.e. with) and shape-selective molecular sieve 0.59-0.73 nanometers of molecular sieve), the boehmite of quantitative kaolin and above-mentioned aging add deionized water to be uniformly mixed, The slurries of 30 weight % of solid content are obtained, are spray-dried.

Table 3 gives type, the dosage of y-type zeolite used in (2) step, Aluminum sol, silica solution and kaolinic dosage. Table 4 gives the composition of catalyst A1~A4.Y-type zeolite, binder, mesopore molecular sieve, shape-selective molecule in catalyst composition Sieve, kaolinic content are calculated by inventory and are obtained, and the content of rare earth oxide uses x-ray fluorescence spectrometry.

By catalyst after 800 DEG C, 4 hours or 17 hours 100% vapor agings, the light oil micro-reactor for evaluating catalyst is living Property, evaluation result is listed in Table 5 below.

Table 1

Seen from table 1, the super-stable Y molecular sieves of the phosphorous and rare earth of high stability provided by the invention, can be provided simultaneously with Following advantages: sodium oxide content is low, and the non-framework aluminum content when sial of molecular sieve is relatively high is less, and aperture is in molecular sieve The pore volume of 2.0nm~100nm second hole accounts for that total pore volume percentage is relatively high, also, B acid/L acid (total B acid acid amount and L acid The ratio between acid amount) it is higher, the crystallinity value measured when the smaller content of rare earth of molecular sieve lattice constant is higher is higher, has high heat Stability.

Table 2

As shown in Table 2, provided by the invention phosphorous and rare earth super-stable Y molecular sieves, in sieve sample naked state Lower to pass through 800 DEG C, after harsh conditions aging in 17 hours, sample opposite crystal retention with higher shows that the present invention mentions The super-stable Y molecular sieves of the phosphorous and rare earth supplied have high hydrothermal stability.

Table 3

Table 4

The catalyst percentage composition of table 4 is weight percentage composition

Light oil microactivity evaluation method:

Using RIPP92-90 standard method (compiled see " petrochemical analysis method " (RIPP test method) Yang Cui is surely equal, Science Press, nineteen ninety publish) evaluation sample light oil microactivity, catalyst loading 5.0g, reaction temperature 460 DEG C, feedstock oil is 235~337 DEG C of huge port light diesel fuels of boiling range, and product composition is calculated by gas chromatographic analysis according to product composition Light oil microactivity.

Light oil microactivity (MA)=(product mid-boiling point is lower than 216 DEG C of gasoline production+gas yield+coke output)/ Total feed × 100%.

Comparative example 4~6

Comparative example 4~6 illustrates the cracking petroleum hydrocarbons being prepared using the super-stable Y molecular sieves that comparative example 1~3 provides The activity and its stability of catalyst.

Super-stable Y molecular sieves DZ1, the DZ2 for respectively preparing comparative example 1~3 according to the method for preparing catalyst of embodiment 4 And DZ3 (respectively instead of SZ1 molecular sieve) and boehmite, kaolin, mesopore molecular sieve, shape-selective molecular sieve, water and Aluminum sol Mixing, spray drying are prepared into microspherical catalyst, and catalyst is numbered successively are as follows: B1, B2 and B3, Y type molecular sieve in each catalyst The content of (also referred to as y-type zeolite) is 30 weight %, and the composition of remaining component is the same as embodiment 4.By catalyst through 800 DEG C, 4 hours Or after 100% vapor aging in 17 hours, evaluate its light oil microactivity.Evaluation method is shown in embodiment 4~7, evaluation result column In table 5.

Table 5

Embodiment 8~11

Embodiment 8~11 illustrates the cracking reaction performance of catalyst provided by the invention.

By A1, A2, A3 and A4 catalyst through 800 DEG C, after 100% vapor aging in 17 hours, in small fixed flowing bed Its catalytic cracking reaction performance is evaluated on reactor (ACE), cracked gas and product oil Shou Ji not be by gas chromatographic analysis.Catalysis Agent loading amount be 9g, 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 16h^-1, oil ratio (weight ratio) be shown in Table 7, ACE experiment raw material oiliness Matter is shown in Table 6, and evaluation result is shown in Table 7.

Comparative example 7~9

Comparative example 7~9 illustrates B1, B2 and B3 catalyst through 800 DEG C, after 100% vapor aging in 17 hours, small-sized solid Its catalytic cracking reaction performance is evaluated on constant current fluidized bed reactor (ACE), evaluation method is shown in embodiment 7, and ACE is tested feed stock Matter is shown in Table 6, and evaluation result is shown in Table 7.

Table 6

Table 7

By table 5 and table 7 as it can be seen that catalytic cracking catalyst provided by the invention has very high hydrothermal stability, for weight Oil converts the hydrogenated residue conversion of for example high arene content, has significantly lower coke selectivity, with considerably higher total Liquid is received, and yield of light oil is considerably higher, and yield of gasoline significantly improves, and heavy oil conversion activity is higher.

Claims

1. a kind of catalytic cracking of petroleum hydrocarbon catalyst, with dry basis, the catalytic cracking of petroleum hydrocarbon catalyst contains 40-80 The carrier of weight %, the Y type molecular sieve of 10-50 weight %, the mesopore molecular sieve and 5- with M41S structure of 5-15 weight % The molecular sieve that the channel openings diameter of 15 weight % is 0.59-0.73 nanometers；Described Y type molecular sieve includes phosphorous and rare earth Super-stable Y molecular sieves, the content of rare earth of phosphorous and rare earth the super-stable Y molecular sieves is with RE₂O₃4~11 weight % are calculated as, phosphorus contains Amount is with P₂O₅It is calculated as 0.05~10 weight %, Na₂O content is 0.1~0.7 weight %, and total pore volume is 0.33~0.39mL/g, Aperture is that the pore volume of the second hole of 2~100nm accounts for the 10~25% of total pore volume, and lattice constant is 2.440~2.455nm, The total aluminium content ratio of non-framework aluminum content Zhan is not higher than 20%, and lattice collapse temperature is infrared with pyridine adsorption not less than 1050 DEG C The ratio of B acid amount and L acid amount that method is measured at 200 DEG C is not less than 2.50.

2. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that described phosphorous and rare earth super steady The percentage that the pore volume for the second hole that aperture is 2nm~100nm in Y type molecular sieve accounts for total pore volume is 15%~21%.

3. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that described phosphorous and rare earth super steady The percentage of the total aluminium content of non-framework aluminum content Zhan is 13%~19% in Y type molecular sieve, and framework si-al ratio is with SiO₂/Al₂O₃It rubs You are calculated as 7.3~14 by ratio.

4. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that described phosphorous and rare earth super steady 1055 DEG C~1080 DEG C of Y type molecular sieve lattice collapse temperature.

5. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that existed with pyridine adsorption infrared method In described phosphorous and rare earth the super-stable Y molecular sieves total acid content measured at 200 DEG C the ratio of B acid amount and L acid amount be 2.6~ 4.0。

6. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that in 800 DEG C, normal pressure, 100% water After vapor atmosphere aging in 17 hours, the opposite crystal retention of described phosphorous and rare earth super-stable Y molecular sieves is 38% or more For example, 38%~48%；Preferably, the relative crystallinity of phosphorous and rare earth the super-stable Y molecular sieves is 60%~70%.

7. according to any catalytic cracking of petroleum hydrocarbon catalyst of claim 1~7, which is characterized in that described phosphorous and dilute The rare earth oxide content of the super-stable Y molecular sieves of soil is 5.5~10 weight %, and sodium oxide content is 0.3~0.7 weight %, phosphorus Content is with P₂O₅It is calculated as 0.1~6 weight %, lattice constant is 2.442~2.450nm, and framework si-al ratio is 8.5~12.6.

8. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that mesoporous point of the M41S structure Son sieve is at least one of MCM-41, MCM-48 and MCM-50, and preferred its sodium oxide content of M41S structure molecular screen does not surpass Cross 0.1 weight %, it is preferred that its sial atomic molar ratio is 10~400:1 such as 10~100:1；The channel openings diameter For 0.59-0.73 nanometers of molecular sieve, being selected from has AFR, AFS, AFI, BEA, BOG, CON, GME, LTL, MEI, MOR and OFF At least one of molecular sieve of structure, preferably Beta, SAPO-5, SAPO-40, SSZ-24, CIT-1, ZSM-18, mercerising boiling At least one of stone, sodium chabazite and offretite, in general, point that the channel openings diameter is 0.59-0.73 nanometers The sodium oxide content of son sieve is 0.01~1.5 weight %, it is preferred that the channel openings diameter is 0.59-0.73 nanometers The sial atomic molar ratio of molecular sieve is 0.1~100；Described carrier is clay, alumina support, silica support, oxidation One of silicon-alumina support is a variety of.

9. catalytic cracking of petroleum hydrocarbon catalyst described in accordance with the claim 1, which is characterized in that the catalytic cracking of petroleum hydrocarbon is urged Agent contains the carrier of the weight of the 50-70 in terms of butt %, the Y type molecular sieve of the weight of the 20-40 in terms of butt %, the 5-15 in terms of butt The mesopore molecular sieve with M41S structure of weight %, the channel openings diameter of the weight of the 5-15 in terms of butt % is 0.59-0.73 The molecular sieve of nanometer.

10. a kind of preparation method of catalytic cracking catalyst, including by carrier, Y type molecular sieve, mesoporous point with M41S structure Son sieve, the molecular sieve that channel openings diameter is 0.59-0.73 nanometers and water form the step of slurries, drying, wherein the Y type Molecular sieve includes phosphorous and rare earth super-stable Y molecular sieves, the phosphorous and rare earth super-stable Y molecular sieves preparation method include with Lower step:

(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains oxygen Change the Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium content reduces；

(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content 350~480 DEG C of temperature, It is roasted 4.5~7 hours under 30~90 volume % water vapour atmospheres, optionally drying, obtains the Y type molecular sieve of lattice constant reduction；

(3) Y type molecular sieve that the lattice constant that step (2) obtains reduces is subjected to P Modification processing with phosphorus compound, it is dry, it obtains The Y type molecular sieve reduced to phosphorous lattice constant；

(4) Y type molecular sieve and silicon tetrachloride gas haptoreaction reduced the phosphorous lattice constant, washing and filtering, Preferably, according to SiCl₄: Y type molecular sieve=0.1~0.7:1 weight that the phosphorous lattice constant in terms of butt reduces The Y type molecular sieve and silicon tetrachloride gas haptoreaction than reducing the phosphorous lattice constant are measured, reaction temperature is 200 DEG C ~650 DEG C, the reaction time is 10 minutes to 5 hours, and washing and filtering obtain described phosphorous and rare earth super-stable Y molecular sieves.

11. according to method described in any one of claim 10, which is characterized in that sodium oxide content described in step (1) reduced contains rare earth Conventional unit cell dimension Y type molecular sieve, lattice constant be 2.465~2.472nm, sodium oxide content be no more than 9.0 weights Measure %.

12. according to the method for claim 10, which is characterized in that in step (1), what the sodium oxide content reduced contains dilute In the Y type molecular sieve of the conventional unit cell dimension of soil, content of rare earth is with RE₂O₃It is calculated as 4.5~13 weight %, sodium oxide content is 4~ 9 weight % are, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.

13. according to the method for claim 10, which is characterized in that step (1) is described by NaY molecular sieve and rare-earth salt solution Contact carries out ion-exchange reactions, according to NaY molecular sieve: rare-earth salts: H₂The weight ratio of O=1:0.01~0.18:5~15 will NaY molecular sieve, rare-earth salts and water form mixture, stirring.

14. according to method described in claim 10 or 13, which is characterized in that step (1) is described molten with rare earth by NaY molecular sieve Liquid contact carries out ion-exchange reactions, comprising: mixes NaY molecular sieve with water, is added with stirring rare-earth salts and/or rare-earth salts is molten Liquid carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions are as follows: exchange temperature is 15~95 DEG C, swap time It is 30~120 minutes, the rare-earth salt solution is the aqueous solution of rare-earth salts.

15. according to the method for claim 10, which is characterized in that the rare-earth salts is that rare earth chloride or nitric acid are dilute Soil, the phosphorus compound are selected from one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or a variety of.

16. according to the method for claim 10, which is characterized in that step (2) maturing temperature is 380~460 DEG C, institute Stating calcination atmosphere is 40~80% water vapour atmospheres, and the calcining time is 5~6 hours.

17. according to the method for claim 10, which is characterized in that the Y that the lattice constant reduces obtained in step (2) The lattice constant of type molecular sieve is 2.450nm~2.462nm.

18. according to the method for claim 10, which is characterized in that P Modification treatment conditions described in step (3) are as follows: by institute The Y type molecular sieve sample for stating lattice constant reduction is contacted with the exchange liquid containing phosphorus compound, is handed under conditions of 15~100 DEG C It changes reaction 10~100 minutes, filters, washing；Wherein, the weight ratio for exchanging water and molecular sieve in liquid is 2~5 preferably 3~4, With P₂O₅The phosphorus of meter and the weight ratio of molecular sieve are as follows: 0.0005~0.10 preferably 0.001~0.05.

19. according to the method for claim 10, which is characterized in that the Y type that step (3) the phosphorous lattice constant reduces Water content in molecular sieve is no more than 1 weight %.

20. according to the method for claim 10, which is characterized in that washing methods described in step (4) is to be washed with water, and is washed Wash condition are as follows:

Molecular sieve: H₂O weight ratio=1:6~15, pH value are 2.5~5.0, and wash temperature is 30~60 DEG C.

21. according to the method for claim 10, which is characterized in that described carrier is clay, alumina support, silica One of carrier and silicaalumina carrier are a variety of；Preferably, described silica support is silica solution, the silicon SiO in colloidal sol₂Content is 1-30 weight %, and the silica solution can be molten for neutral silica solution, acidic silicasol or alkaline silicon Glue；Preferably, the alumina support is gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, Aluminum sol, hydration One of aluminium oxide is a variety of, the hydrated alumina such as boehmite, a diaspore, gibbsite, bayerite One or more of；Silicaalumina carrier belonging to preferred is silicon-aluminum sol, silica-alumina gel and amorphous silicon oxide- One or more of aluminium oxide.

22. according to the method for claim 10, which is characterized in that the channel openings diameter is 0.59-0.73 nanometers Molecular sieve, in the molecular sieve with AFR, AFS, AFI, BEA, BOG, CON, GME, LTL, MEI, MOR and OFF structure extremely Few one kind；Preferably Beta, SAPO-5, SAPO-40, SSZ-24, CIT-1, ZSM-18, modenite, sodium chabazite and water chestnut potassium At least one of aluminium ore；The molecular sieve sial atomic molar that preferred described channel openings diameter is 0.59-0.73 nanometers Than for 0.1~100:1.

23. a kind of Heavy oil conversion method, including by heavy oil and catalyst according to any one of claims 1 to 9 in catalytic cracking Under the conditions of haptoreaction the step of, reaction temperature be 400-600 DEG C, weight (hourly) space velocity (WHSV) 5-30 hours^-1, oil ratio 1-10 weight ratio； Preferable reaction temperature is 450-550 DEG C or 480-530 DEG C, and weight (hourly) space velocity (WHSV) is preferably 8-25 hours^-1, oil ratio 2-7.

24. according to the method for claim 23, which is characterized in that the heavy oil is hydrogenated residue, the hydrogenated residue Arene content is 40~75 weight %, and paraffinicity is 1-25 weight %, and naphthene content is 15~45 weight %, and specific gravity is 0.92~0.95g/cm³。