CN108452836A - A kind of catalytic cracking catalyst - Google Patents
A kind of catalytic cracking catalyst Download PDFInfo
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- CN108452836A CN108452836A CN201710097152.1A CN201710097152A CN108452836A CN 108452836 A CN108452836 A CN 108452836A CN 201710097152 A CN201710097152 A CN 201710097152A CN 108452836 A CN108452836 A CN 108452836A
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- 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
-
- 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
- B01J29/04—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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- 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
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
A kind of catalytic cracking catalyst, aluminium oxide and clay containing Modified Zeolite Y, containing additive；The rare earth oxide content of the Modified Zeolite Y is 5 weight of weight %~12 %, sodium oxide content is 0.1 weight of weight %~0.7 %, total pore volume is 0.33mL/g~0.39mL/g, the percentage that the pore volume for the second hole that the aperture of the Modified Zeolite Y is 2nm~100nm accounts for total pore volume is 10%~25%, lattice constant is 2.440nm~2.455nm, non-framework aluminum content accounts for the percentage of total aluminium content not higher than 20% in the Modified Zeolite Y, lattice collapse temperature is not less than 1050 DEG C, and B acid amount and the ratio of L acid amounts are not less than 2.50.The catalytic cracking catalyst has higher heavy oil conversion activity and lower coke selectivity, has higher yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield.
Description
Technical field
The present invention relates to a kind of catalyst for heavy oil catalytic cracking and preparation method thereof.
Background technology
Currently, industrially producing Y-type high-Si zeolite mainly uses hydro-thermal method.NaY zeolite is subjected to multiple rare earth ion friendship
It changes and is roasted with multiple high temp, the Y-type high-Si zeolite containing rare earth can be prepared, this is also that prepare Y-type high-Si zeolite the most conventional
Method, but hydro-thermal method prepares rare-earth type high-silicon gamma-zeolite and is disadvantageous in that：Due to excessively harsh hydrothermal conditions
The structure of zeolite can be destroyed, the very high y-type zeolite of silica alumina ratio cannot be obtained；Though the generation of the outer aluminium of skeleton is to the stabilization of raising zeolite
Property and form the outer aluminium of the beneficial but excessive skeleton in new acid site and reduce the selectivity of zeolite；In addition, many de- in zeolite
Aluminium hole cannot be filled by the silicon migrated out on skeleton in time, often result in the lattice defect of zeolite, the crystal retention of zeolite
It is relatively low；Therefore, the heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that hydro-thermal method is prepared are poor, show that its lattice collapses
Temperature of collapsing is low, its crystallinity retention rate and specific surface area retention rate are low after hydrothermal aging.
In United States Patent (USP) US4584287 and US4429053, NaY zeolite is first then subjected to water steaming with rare earth ion exchanged
Gas disposal, the method make the aluminium removing of zeolite during steam treatment compare due to the shielding action and support of rare earth ion
Difficulty, cell parameter of the zeolite before steam treatment increase to 2.465~2.475nm, and after handling for 2.420~
It is higher (593~733 DEG C) to reduce cell parameter required temperature by 2.464nm.
In the method that United States Patent (USP) US5340957 and US5206194 are provided, the SiO of raw material NaY zeolite2/Al2O3Than for
6.0, method is also after NaY is carried out rare earth exchanged, then to carry out hydro-thermal process, equally exist aforesaid U.S. Patent
The shortcomings that US4584287 and US4429053.
Gas chemistry method is the important side of another kind for preparing silica-rich zeolite that Beyer and Mankui were reported first in 1980
Method.Gas chemistry method generally uses the SiCl under nitrogen protection4It is reacted at a certain temperature with anhydrous NaY zeolite.Entirely
Reaction process makes full use of SiCl4The external sources Si provided are once completed dealuminzation by same order elements and mend pasc reaction.The U.S. is special
Sharp US4273753, US4438178, Chinese patent CN1382525A, CN1194941A, CN1683244A, which are disclosed, utilizes SiCl4
The method of gas chemistry dealuminzation ultrastable.But pore structure study shows gas phase that super stable molecular sieve does not have second hole.
Hydro-thermal method or the performance of the super stable molecular sieve catalytic cracking catalyst of vapor phase method preparation are used in the prior art not
The needs of current processing heavy oil and poor oil can be met well.
Invention content
The technical problem to be solved in the present invention is to provide a kind of heat and hydrothermal stability higher, gasoline yield higher, heavy oil
The catalytic cracking catalyst that conversion capability is stronger, coke selectivity is good, the catalyst contain Y type molecular sieve.
A kind of catalytic cracking catalyst of present invention offer contains 10 weight in terms of butt on the basis of the weight of catalyst
Measure the aluminium oxide containing additive of the weight % of the Modified Zeolite Y of the weight of %~50 %, in terms of butt 2 weight~40 and with dry
The clay of the weight % of 10 weight of base meter~80；It is described containing adding in terms of butt on the basis of the alumina weight containing additive
Add the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide of agent, the additive of 0.5 weight %-40 weight % described
Additive is selected from one or more of the compound containing alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements；Described
The rare earth oxide content of modified molecular screen is 5~12 weight %, and sodium oxide content is 0.1~0.7 weight %, and total pore volume is
0.33~0.39mL/g, the Modified Zeolite Y aperture are that the pore volume of the second hole of 2nm~100nm accounts for modification Y type molecules
The percentage for sieving total pore volume is 10%~25%, and lattice constant is 2.440nm~2.455nm, framework si-al ratio (SiO2/
Al2O3Molar ratio) be：7.3~14.0, non-framework aluminum content accounts for the percentage of total aluminium content and is not higher than 20% in molecular sieve, lattice
Collapse temperature is not less than 1050 DEG C, also, the Modified Zeolite Y total acid measured at 200 DEG C with pyridine adsorption infrared method
B acid amount and the ratio of L acid amounts are not less than 2.50 in amount.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, lattice collapse temperature is not less than
1050 DEG C, it is preferred that 1055 DEG C~1080 DEG C, for example, 1057~1075 DEG C of the molecular sieve lattice collapse temperature.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y is existed with pyridine adsorption infrared method
It is, for example, 2.7 that the ratio of B acid amount and L acid amounts, which is preferably 2.6~4.0, in the Modified Zeolite Y total acid content measured at 200 DEG C
~3.3.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, lattice constant be 2.440nm~
2.455nm is, for example, 2.442~2.450nm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y is high-Si Y-type molecular sieve, bone
Frame silica alumina ratio (SiO2/Al2O3Molar ratio) it is 7.3~14.0, for example, 8.5~12.6.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, non-framework aluminum content in molecular sieve
The percentage for accounting for total aluminium content is not higher than 20%, for example, 13~19 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, relative crystallinity be not less than
60%, it is preferred that the relative crystallinity of the Modified Zeolite Y provided by the invention be 60~70%, for example, 60~
66%.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, 800 DEG C, normal pressure, 100 bodies
It is, for example, 38~48% or 39~45% that crystal retention under product % water vapour atmospheres after aging 17 hours, which is 38% or more,.Institute
The normal pressure stated is 1atm.
In catalytic cracking catalyst provided by the invention, a kind of embodiment, the specific surface of the Modified Zeolite Y
Product is 620~670m2/ g is, for example, 630~660m2/g。
In catalytic cracking catalyst provided by the invention, it is preferred that the Modified Zeolite Y total pore volume is 0.35
~0.39mL/g is, for example, 0.36~0.375mL/g.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, aperture (referring to diameter) is 2.0nm
The percentage that the pore volume of the second hole of~100nm accounts for total pore volume is 10%~25%, preferably 15~21%.
A kind of embodiment, in catalytic cracking catalyst provided by the invention, the porous body of the Modified Zeolite Y
Product is that 0.25~0.35mL/g is, for example, 0.26~0.32mL/g.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y contains rare earth element, modification Y
With RE in type molecular sieve2O3The rare earth oxide content of meter is that 5~12 weight % are preferably 5.5~10 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y sodium oxide content is no more than
0.7%, can be, for example, 0.35~0.60 weight % or 0.4~0.55 weight % for 0.3~0.7 weight %.
In catalytic cracking catalyst provided by the invention, the modification Y types containing in terms of butt 10 weight of weight %~50 %
Molecular sieve, it is preferred that the content of the Modified Zeolite Y is that 15~45 weight % are, for example, 20~40 weight % or 25~35
Weight %.
Clay can also be contained in catalytic cracking catalyst provided by the present invention, with the weight of the catalytic cracking catalyst
On the basis of, the content of the clay is no more than 70 weight %, preferably 10 weight %-70 weight %.Catalysis provided by the invention
The content of clay described in Cracking catalyst can be 20~55 weight % or 30~50 weight % in terms of butt.The clay is selected from
One or more of clay as cracking catalyst component, for example, kaolin, halloysite, montmorillonite, diatomite, angstrom
One or more of Lip river stone, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.These clays are this field
Well known to those of ordinary skill.
In catalytic cracking catalyst of the present invention, contain the aluminium oxide containing additive, is catalyzed with the catalytic cracking
On the basis of the weight of agent, the content of the aluminium oxide containing additive is calculated as 2 weight %-40 weight %, preferably 2 weights with butt
Measure %-20 weight %.The aluminium oxide containing additive can be according to patent CN1915486A, CN1915485A, CN1916116A
It is prepared by the method.It is preferred that on the basis of the aluminium oxide dry weight containing additive, the aluminium oxide containing additive
In the aluminium oxide containing 70 weight %-95 weight %, the additive of in terms of butt 5 weight %-30 weight %.Wherein described adds
It is preferably phosphorous and/or magnesium compound to add agent.
The dry weight is that substance roasts 1 hour obtained solid product weight at 800 DEG C.
Preferably, the preparation method of the aluminium oxide containing additive includes the following steps：
(1) boehmite is mixed under stiring with being enough to make the water of its pulp and acid, wherein the dosage of acid make it is described
The weight ratio of acid and aluminium oxide in boehmite is 0.01-0.5；
(2) by the mixed serum of step (1) at a temperature of -90 DEG C of room temperature aging 0-24 hours；
(3) product of step (2) is mixed with additive, optionally drying and optionally roasting.
In the preparation method of the aluminium oxide containing additive, it is preferred that sour dosage makes institute in the wherein described step (1)
The weight ratio for stating acid and aluminium oxide in boehmite is 0.05-0.3.Step (1) described pulp makes boehmite and water
The solid content of the slurries of formation is 10~50 weight %, preferably 15~30 weight %.The acid is in inorganic acid, organic acid
One or more, for example, the inorganic acid can be hydrochloric acid, nitric acid, sulfuric acid, one or more of phosphoric acid, the organic acid
Can be one or more of formic acid, acetic acid, oxalic acid or stubborn rubber acid, hydrochloric acid preferably wherein or nitric acid.
In the preparation method of the aluminium oxide containing additive, it is preferred that the aging temperature in the wherein described step (2) is
Room temperature~80 DEG C, the room temperature are, for example, 15~40 DEG C, and ageing time is 0.5-4 hours.By the production of step (2) in step (3)
The mixture that object is formed with additive, is used directly for preparing catalytic cracking catalyst, i.e., will be formed by mixture and shape
It is mixed at other components of catalytic cracking catalyst, can also dry and be used to prepare catalyst after roasting.The drying example
As dried, being spray-dried.
In the preparation method of the aluminium oxide containing additive, the temperature of a kind of embodiment, step (3) described roasting is
350~800 DEG C such as 400~600 DEG C, roasting time such as 0.5~8 hour.The additive is selected from alkaline including earth metal, group of the lanthanides
One or more of the compound of metal, silicon, gallium, canopy or P elements, it is described containing alkaline-earth metal, copper system metal, silicon, transfer,
The compound of canopy or P elements can be oxide, the hydrous oxide of these elements, such as magnesia, the hydrogen in alkaline-earth metal
Magnesia, the oxidation rare earth in lanthanide series metal, silica, Ludox, one or more of phosphorous oxide:Can also be containing upper
The salt for stating element, such as the nitrate in alkaline-earth metal, the rare earth chloride in lanthanide series metal, silicate, one kind in phosphate or
It is several.When the additive is the oxide and/or water oxycompound of the element, the mixing is to obtain the step 2
The product arrived is directly mixed；When the additive is one or more of the salt containing the element, the mixing
It is preferred that the product that the salt is configured to obtain with the step (2) again after aqueous solution is mixed first.It is mixed described in each step
It closes, existing various methods can be used and realize that the method on excellent side is to be enough to make the material (such as:Boehmite, addition
Agent) it mixes under conditions of pulp, the pulp is known to those skilled in the art, including to make material pulp introduce foot
The introduction volume of the water enough measured, the water makes the solid content of slurries be usually 10-50 weight %, preferably 15-30 weight %.
In catalytic cracking catalyst of the present invention, preferably also contain alumina binder, using the weight of catalyst as base
Standard, in terms of butt, the content of the alumina binder is no more than 32 weight %, the weight % of preferably 5 weight~32.The oxygen
Change in aluminium oxide, hydrated alumina and Aluminum sol of the al binder selected from the commonly used various forms of Cracking catalyst
One or more, for example, selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite
(Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite), bayerite (Bayerite) or aluminium are molten
Containing with dry in one or more of glue, preferably boehmite and/or Aluminum sol, such as the catalytic cracking catalyst
2~15 weight % of base the meter preferably aluminium sol adhesive of 3~10 weight %, in terms of butt 10~30 weight % preferably 15~25 weights
Measure the boehmite binder of %.
It is preferred that on the basis of the weight of catalyst, alumina binder described in catalyst of the present invention and containing addition
The total content of the aluminium oxide of agent is that 10 weight %-40 weight % are, for example, containing for 20~35 weight % and the aluminium oxide containing additive
Amount is 2 weight %-20 weight %.
In catalyst of the present invention, on the basis of the weight of catalyst, preferably comprise：In terms of butt 10 weight %~50
The Modified Zeolite Y of weight % such as 15~45 weight % or 25~40 weight %, in terms of butt 50 weight %-90 weights
Measure the matrix of % such as 55~85 weight % or 60~75 weight %.The matrix includes the aluminium oxide containing additive, viscous
Native and optional binder, the binder are preferably alumina binder.
Catalyst provided by the invention also contains other molecular sieves other than the Modified Zeolite Y, described other
The molecular sieve that molecular sieve uses in catalytic cracking catalyst, such as with MFI structure zeolite, Beta zeolites, the boiling of other Y types
The one or more of stone, non-zeolite molecular sieve.The content of other molecular sieves can be that 0~40 weight % is, for example, 0~30
Weight % or 1~20 weight %.Preferably, the content of other Y type molecular sieves is no more than 40 weight % for example in terms of butt
Can be 1~40 weight % or 0~20 weight %.In described other y-type zeolites such as REY, REHY, DASY, SOY, PSRY
One or more, one or more in described MFI structure zeolite such as HZSM-5, ZRP, the ZSP, described beta zeolite examples
Such as H β, one in non-zeolite molecular sieve such as aluminium phosphate molecular sieve (AlPO molecular sieves), sial phosphorus molecular sieve (SAPO molecular sieve)
Kind is a variety of.It is preferred that on the basis of the weight of catalyst, the content of other molecular sieves is no more than 20 weight %.
Method for preparing catalyst of the present invention be existing method, these preparation methods patent CN1916116A,
There is detailed description in CN1362472A, CN1727442A, CN1132898C, CN1727445A, CN1098130A, here together
As with reference to reference.It generally includes to be formed the slurries including Modified Zeolite Y, binder, clay and water, spray drying, appoint
Choosing washing and dry step.Spray drying, washing, drying are the prior art, and the present invention does not have particular/special requirement.Such as a kind of system
Preparation Method includes by the Modified Zeolite Y, the aluminium oxide containing additive, clay, optional alumina binder and water
The step be mixed with beating, be spray-dried and wash, filter, drying.
Catalytic cracking catalyst preparation method provided by the invention, a kind of embodiment, including prepare modified Y type molecules
Sieve, formed include the Modified Zeolite Y, the aluminium oxide containing additive, clay, water and optional alumina binder slurry
The step of liquid, spray drying, wherein the method for preparing the Modified Zeolite Y includes the following steps:
(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 dilute for containing of reducing the sodium oxide content
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) the Y type molecular sieve sample and SiCl reduced the lattice constant4The item that gas is 200~650 DEG C in temperature
Haptoreaction under part, wherein SiCl4：The weight ratio for the Y type molecular sieve that the lattice constant that the step of in terms of butt (2) obtains reduces
=0.1~0.7：1, in 10 minutes to 5 hours reaction time, then washed, filtering obtains Modified Zeolite Y.Wherein, institute
The water content for stating the Y type molecular sieve sample of lattice constant reduction is preferably more than 1 weight %；If step (2) modification obtains
To Y type molecular sieve sample in (in the Y type molecular sieve that roasting obtains) water content be no more than 1 weight %, be used directly for
Silicon tetrachloride contact carries out the reaction, if water content is more than 1 in the Y type molecular sieve sample that step (2) modification obtains
Weight %, the Y type molecular sieve sample that the lattice constant that step (2) modification obtains reduces, which is dried, makes its water content
Less than 1 weight %.
Catalytic cracking catalyst provided by the invention, be used for heavy oil catalytic cracking, have higher gasoline, light oil yield and
Total liquid yield, heavy oil cracking ability is strong, has excellent coke selectivity.Such as modification Y prepared by the method containing the present invention
The catalytic cracking catalyst SC3 of type molecular sieve SZ3, using heavy oil in 500 DEG C, weight (hourly) space velocity (WHSV) 16h after aging- 1, oil ratio
It is evaluated under (weight ratio) 4, heavy oil conversion rate is 75.63 weight %, and yield of gasoline is 52.64 weight %, yield of light oil
For 69.76 weight %, 87.04 weight % of total liquid yield, coke selectivity 5.80%, and prepared containing existing method super steady
The catalyst DC3 of molecular sieve, using heavy oil in 500 DEG C, weight (hourly) space velocity (WHSV) 16h after aging- 1, under oil ratio (weight ratio) 5 into
Row evaluation, heavy oil conversion rate are 75.14 weight %, and yield of gasoline is 51.29 weight %, and yield of light oil is 67.87 weight %,
Coke selectivity is that 8.45% total liquid yield is 83.88% weight；As it can be seen that catalytic cracking catalyst provided by the invention has
Higher heat and hydrothermal stability have higher heavy oil conversion performance and gasoline and yield of light oil, tool after hydrothermal aging
There is higher liquid to receive, there is more excellent coke selectivity.
Catalyst of the present invention is suitable for hydrocarbon oil catalytic cracking, is particularly suited for heavy oil catalytic cracking.The hydrocarbon ils such as normal pressure
Residual oil, decompression residuum, vacuum gas oil (VGO), AGO (atmospheric gas oil), straight run gas oil, propane is light/heavy deasphalted oil and coker gas oil
One or more of.
Specific implementation mode
Catalytic cracking catalyst provided by the invention contains in terms of butt 10 weight % on the basis of the weight of catalyst
Aluminium oxide described in the Modified Zeolite Y of~50 weight %, in terms of butt 2~40 weight % containing additive, with dry
The clay of the weight % of the alumina binder of the weight % of 0 weight of base meter~40 and in terms of butt 10 weight~80.Preferably, described
Catalytic cracking catalyst contains the Modified Zeolite Y of in terms of butt 25 weight of weight %~40 %, in terms of butt 2~20
The alumina binder of the weight % of the aluminium oxide containing additive of weight %, in terms of butt 5 weight~30 and in terms of butt
The clay of the weight % of 30 weight~50, and the total content of alumina binder and the aluminium oxide containing additive is 20~35 weights
Measure %.
In catalytic cracking catalyst provided by the invention, containing Modified Zeolite Y, a kind of embodiment, described changes
Property Y type molecular sieve, rare earth oxide content be 5~12 weight %, preferably 5.5~10 weight %, sodium oxide content be 0.1~
0.7 weight %, preferably 0.3~0.7 weight %, total pore volume are 0.33~0.39mL/g, and aperture is the two of 2nm~100nm
Grade hole pore volume account for total pore volume percentage be 10%~25%, preferably 15%~21%, lattice constant be 2.440nm~
2.455nm, framework si-al ratio (SiO2/Al2O3Molar ratio) be：7.3~14.0, non-framework aluminum content accounts for total aluminium and contains in molecular sieve
The percentage of amount be not higher than 20%, preferably 13~19, relative crystallinity be not less than 60%, lattice collapse temperature be 1055 DEG C~
1080 DEG C, also, B acid amount and L acid in the Modified Zeolite Y total acid content measured at 200 DEG C with pyridine adsorption infrared method
The ratio of amount is not less than 2.50, preferably 2.6~4.0.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, preparation process includes by Y
Type molecular sieve contacts the step of carrying out dealumination complement silicon reaction with silicon tetrachloride.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(1) NaY molecular sieve and earth solution are subjected to ion-exchange reactions in, to obtain the routine containing rare earth of sodium oxide content reduction
The Y type molecular sieve of unit cell dimension.The NaY molecular sieve, can be commercially available or prepares, a kind of embodiment according to existing method,
The NaY molecular sieve lattice constant is 2.465~2.472nm, framework si-al ratio (SiO2/Al2O3Molar 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 weight %.Described in step (1)
NaY molecular sieve carries out ion-exchange reactions with earth solution, and it is, for example, 65~95 DEG C that exchange temperature, which is preferably 15~95 DEG C, is exchanged
Time is preferably such as 45~90 minutes 30~120 minutes.NaY molecular sieve (in terms of butt):Rare-earth salts is (with RE2O3Meter):H2O
=1:0.01~0.18:5~15 weight ratios.A kind of embodiment, the NaY molecular sieve carry out ion exchange with earth solution
Reaction includes, according to NaY molecular sieve:Rare-earth salts:H2O=1:0.01~0.18:NaY molecular sieve (is also referred to as by 5~15 weight ratio
NaY zeolite), rare-earth salts and water form mixture, 15~95 DEG C of preferred stirrings of such as 65~95 DEG C stirrings 30~120 minutes into
Row rare earth ion is exchanged with sodium ion, the water such as decationized Y sieve water, deionized water or their mixture.By NaY
Molecular sieve, rare-earth salts and water form mixture, can NaY molecular sieve and water be formed slurries, then added in the slurries
Enter the aqueous solution of rare-earth salts and/or rare-earth salts, the earth solution is the solution of rare-earth salts, and the rare-earth salts is preferably chlorine
Change rare earth and/or nitric acid rare earth.It is one or more in the rare earth such as La, Ce, Pr, Nd and mischmetal, preferably
, containing one or more in La, Ce, Pr and Nd in the mischmetal, or also contain in addition to La, Ce, Pr and Nd
At least one of rare earth.Washing described in step (1), it is therefore an objective to the sodium ion being swapped out is washed away, it is, for example, possible to use going
Ionized water or decationized Y sieve water washing.It is preferred that the conventional unit cell dimension containing rare earth that the sodium oxide content that step (1) obtains reduces
Y type molecular sieve content of rare earth with RE2O3It is, for example, 7~14 weight or 5.5~12 weight %, oxygen to be calculated as 5.5~14 weight %
It is, for example, 5.5~8.5 weight % or 5.5~7.5 weight % to change sodium content to be no more than 9 weight %, lattice constant for 2.465nm~
2.472nm。
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(2) by the Y type molecular sieve of the conventional unit cell dimension containing rare earth in 350~480 DEG C of temperature, 30~90 volume % water vapour atmospheres in
Lower roasting is modified processing in 4.5~7 hours, it is preferred that the calcination temperature described in step (2) is 380~460 DEG C, roasts gas
Atmosphere is 40~80 volume % water vapour atmospheres, and roasting time is 5~6 hours.In 30~90 volume % water vapour atmospheres
Containing 30~90 volume % vapor, also contain one or more in other gases, such as air, helium or nitrogen.Step
(2) Y type molecular sieve that the lattice constant described in reduces, lattice constant are 2.450nm~2.462nm.It is preferred that step (2)
In also the obtained molecular sieve of roasting is dried so that the water content in the Y type molecular sieve that the lattice constant reduces is preferred
No more than 1 weight %.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(3) in, SiCl4：The weight ratio of y-type zeolite (in terms of butt) is preferably 0.3~0.6：1, the temperature of the reaction is preferably 350
~500 DEG C, conventional washing methods may be used in the washing methods described in step (3), and such as decationized Y sieve water can be washed with water
Or deionized water washing, it is therefore an objective to remove Na remaining in zeolite+、Cl-And Al3+Equal soluble by-products, such as wash conditions
Can be：The weight ratio of washings and molecular sieve can be 5~20：1, usual molecular sieve：H2Weight ratio=1 O:6~15, pH value
Preferably 2.5~5.0, wash temperature is 30~60 DEG C.Preferably, the washing makes inspection in the cleaning solution after washing not measure
Free Na+、Cl-And Al3+Plasma, usually Na in the sieve sample after washing+, Cl-And Al3+The respective content of ion is not
More than 0.05 weight %.
In catalytic cracking catalyst preparation method provided by the invention, the preparation method of the Modified Zeolite Y is a kind of
Embodiment includes the following steps：
(1) NaY molecular sieve (also referred to as NaY zeolite) is subjected to ion-exchange reactions with earth solution, 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~
480 DEG C, contains and roasted 4.5~7 hours under the atmosphere of 30~90 volume % water vapours, it is dry, water content is obtained less than 1 weight %'s
The Y type molecular sieve that lattice constant reduces；The lattice constant for the Y type molecular sieve that the lattice constant reduces be 2.450nm~
2.462nm；
(3) the Y type molecular sieve sample that the lattice constant by water content less than 1 weight % reduces and heated vaporization
SiCl4Gas contacts, wherein SiCl4：The Y type molecular sieve (in terms of butt) that lattice constant of the water content less than 1 weight % reduces
Weight ratio=0.1~0.7：1, haptoreaction 10 minutes to 5 hours, washed and mistake under conditions of temperature is 200~650 DEG C
Filter, obtains Modified Zeolite Y provided by the invention.
The following examples will be further described the present invention, but not thereby limiting the invention.
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 the chemically pure reagent that nitric acid rare earth is Beijing Chemical Plant's production.It is quasi- thin
Diaspore is that Shandong Aluminum Plant produces industrial products, 61 weight % of solid content；Kaolin is the production of Suzhou China Kaolin Co., Ltd
The special kaolin of Cracking catalyst, 76 weight % of solid content；Aluminum sol is by asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd
It provides, wherein 21 weight % of alumina content.
Analysis method：In each comparative example and embodiment, the constituent content of zeolite is by x-ray fluorescence spectrometry；Boiling
Lattice constant, the relative crystallinity of stone use the standard side RIPP145-90, RIPP146-90 by x-ray powder diffraction (XRD)
Method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) it measures, boiling
The framework si-al ratio of stone is calculated by following formula and is obtained：SiO2/Al2O3=(2.5858-a0)×2/(a0- 2.4191)] wherein, a0For crystalline substance
Born of the same parents' constant, unit nm；Total silica alumina ratio of zeolite is calculated according to Si and the Al constituent content of x-ray fluorescence spectrometry,
The framework si-al ratio measured by XRD methods can calculate the ratio of skeleton Al and total Al with the XRF total silica alumina ratios measured, and then calculate non-
The ratio of 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 measures.Laboratory apparatus：The U.S. Bruker companies IFS113V types FT-IR (fourier-transform infrared) spectrometer.Use pyridine adsorption
It is as follows that infrared method measures sour amount method at 200 DEG C：Experimental method：By sample self-supporting tabletting, it is placed in the original of infrared spectrometer
Position seals in pond.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, it is that 2.67Pa pyridine steams keep adsorption equilibrium 30min to import pressure.200 DEG C are then heated to, is evacuated to 10-3Under Pa
30min is desorbed, is down to room temperature and takes the photograph spectrum, scan wave-number range：1400cm-1~1700cm-1, obtain the pyrrole that sample is desorbed through 200 DEG C
Infrared spectrogram is adsorbed in pyridine.According to 1540cm in Pyridine adsorption IR spectra figure-1And 1450cm-1The intensity of feature adsorption peak, obtains
To total in molecular sieveThe relative quantity in acid site (acid sites B) and the acid sites Lewis (acid sites L).
In each comparative example and embodiment, wherein the assay method of described two 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 methods
Total pore volume is subtracted micro pore volume and obtains two 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 8000 grams of NaY molecular sieves to be added to stirring in 80 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RE (NO of 2400ml are added3)3(earth solution concentration is with RE for solution2O3It is calculated as 319g/L), stirring is warming up to 90~95 DEG C
It is kept for 1 hour, is then filtered, washed, for filter cake in 120 DEG C of dryings, it is 2.471nm, 7.0 weight of sodium oxide content to obtain lattice constant
Measure %, with RE2O3Count the Y type molecular sieve of content of rare earth 8.8 weight %, later in 390 DEG C of temperature, containing 50 volume % water vapours and
It is roasted 6 hours under the atmosphere of 50 volume % air, obtains the Y type molecular sieve that lattice constant is 2.455nm and be dried later
Processing makes its water content be less than 1 weight %, then according to SiCl4：Y type molecular sieve (butt meter)=0.5：1 weight ratio is led to
Enter the SiCl of heated vaporization4Gas reacts 2 hours, under conditions of temperature is 400 DEG C later, with 80 liters of decationized Y sieve water
Washing, then filters, obtains Modified Zeolite Y provided by the invention, be denoted as SZ1, physico-chemical property is listed in Table 1 below, by SZ1
In naked state after 800 DEG C, 1atm, 100% vapor aging 17 hours, with point before and after the method analysis SZ1 agings of XRD
The relative crystallinity of son sieve simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2, wherein：
It is that the boehmite of 61 weight % is added in 7818 grams of decationized Y sieve water to take 1572 grams of alumina contents, is being stirred
It mixes and the pure hydrochloric acid of 195ml chemistry (containing 36 weight %HCl) is added under state, in 70 DEG C of agings 1 hour, 165ml phosphorus is added later
Acid (Beijing Chemical Plant produces, concentration 85%, and analysis is pure) and magnesium chloride hexahydrate (the bicyclic chemical reagent work's production in Beijing, analysis are pure) are water-soluble
390 grams of liquid (wherein 204 grams of magnesium chloride hexahydrate), mashing, obtains the slurries of the aluminium oxide containing additive.
It takes the Aluminum sol that 4998 grams of alumina contents are 21 weight % to be added in 10950 grams of decationized Y sieve water, is then stirring
The lower kaolin that 5853 grams of solid contents are added as 76 weight % is mixed, is beaten 60 minutes, obtains kaolin slurry.2361 grams are aoxidized
Aluminium content is that the boehmite of 61 weight % is added in 9381 grams of decationized Y sieve water, is beaten, then under stiring thereto
231ml chemistry pure hydrochloric acid (containing 36 weight %HCl) is added, prepared kaolin slurry is added in aging after sixty minutes, adds
Then SZ1 molecular sieves 2600 grams (butts) and REY molecular sieves is added in the slurries of the prepared aluminium oxide containing additive, mashing
[asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces, and content of rare earth is (with RE2O3Meter) 18 weight %, silica alumina ratio (SiO2/
Al2O3Molar ratio 4.6)] 400 grams (butts), mashing, then carried out at 650 DEG C of dry gas inlet temperature, 180 DEG C of exhaust temperature
Spray drying, is washed with deionized, and drying obtains catalyst, is denoted as SC1.
Embodiment 2
Taking 8000 grams of NaY molecular sieves to be added to stirring in 100 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RECl of 3200ml is added3Solution is (with RE2O3The solution concentration of meter is：319g/L), it stirs, is warming up to 90~95 DEG C of holdings
It 1 hour, is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 5.5 weights in 120 DEG C of dryings
Measure %, with RE2O3The Y type molecular sieve that content of rare earth is 11.3 weight % is counted, is roasted at 450 DEG C of temperature, 80% water vapour later
It 5.5 hours, obtains the Y type molecular sieve that lattice constant is 2.461nm and processing is dried later, its water content is made to be less than 1 weight
% is measured, then according to SiCl4：Y-type zeolite=0.6：1 weight ratio is passed through the SiCl of heated vaporization4Gas is in temperature
It under conditions of 480 DEG C, reacts 1.5 hours, later, with 80 liters of decationized Y sieve water washings, then filters, obtain modified Y type molecules
Sieve, is denoted as SZ2.Its physico-chemical property is listed in Table 1 below, by SZ2 in naked state through 800 DEG C, 100% vapor aging in 17 hours
Afterwards, the crystallinity of the zeolite before and after analyzing SZ2 agings with the method for XRD simultaneously calculates the opposite crystal retention after aging,
It the results are shown in Table 2.
The boehmite that 1181 grams of alumina contents are 61 weight % is added in 5875 grams of decationized Y sieve water, is being stirred
The pure hydrochloric acid of lower addition 148ml chemistry (containing 36 weight %HCl) is mixed, then in 70 DEG C of agings 1 hour, six water chlorinations are added later
Magnesium (the bicyclic chemical reagent work's production in Beijing, analysis are pure) 864 grams of aqueous solution (wherein 493 grams of magnesium chloride hexahydrate), mashing are obtained containing addition
The slurries of the aluminium oxide of agent.
It takes the Aluminum sol that 3427 grams of alumina contents are 21 weight % to be added in 3002 grams of decationized Y sieve water, is added with stirring
The kaolin that 7009 grams of solid contents are 76 weight % is beaten 60 minutes, obtains kaolin slurry.It is by 3539 grams of alumina contents
The boehmite of 61 weight % is added in 17629 grams of decationized Y sieve water, and 385ml hydrochloric acid (chemistry is added under stirring
It is pure, 36 weight % of concentration), prepared kaolin slurry is added in aging after sixty minutes, and mashing adds prepared containing and adds
Then SZ2 molecular sieves 3836 grams (butts) and (the Sinopec catalysis of ZRP-5 molecular sieves is added in the slurries of the aluminium oxide of agent, mashing
Asphalt in Shenli Refinery of agent Co., Ltd produces, 0.5 weight % of content of rare earth, silica alumina ratio 45) 200 grams (butts), mashing, then sprayed
Mist is dried and carrying out washing treatment (with example 1), and drying obtains catalyst SC2.
Embodiment 3
Taking 8000 grams of NaY molecular sieves (butt) to be added to stirring in 88 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RECl of 2280ml3Solution is (with RE2O3A concentration of 319g/L of earth solution of meter), stirring is warming up to 90~95 DEG C of holdings and stirs
It mixes 1 hour, 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 at 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 processing is dried later, its water content is made to be less than 1
Weight %, then according to SiCl4：Y-type zeolite=0.4：1 weight ratio is passed through the SiCl of heated vaporization4Gas is in temperature
Under conditions of 500 DEG C, reacts 1 hour, later, with 80 liters of decationized Y sieve water washings, then filters, obtain Modified Zeolite Y,
It is denoted as SZ3.Its physico-chemical property is listed in Table 1 below, and by SZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, is used
The crystallinity of zeolite before and after the method analysis SZ3 agings of XRD simultaneously calculates the opposite crystal retention after aging, the results are shown in Table
2。
It is that the boehmite of 61 weight % is added in 6463 grams of decationized Y sieve water to take 1299 grams of alumina contents, is being stirred
The pure hydrochloric acid of lower addition 163ml chemistry (HCl contents are 36 weight %) is mixed, in 70 DEG C of agings 1 hour, 388ml phosphorus is added later
Acid (Beijing Chemical Plant produces, concentration 85%, and analysis is pure), mashing obtains the slurries of the aluminium oxide containing additive.
It takes the Aluminum sol that 3770 grams of alumina contents are 21 weight % to be added in 6027 grams of decationized Y sieve water, is added with stirring
The kaolin that 7710 grams of solid contents are 76 weight % is beaten 60 minutes, obtains kaolin slurry.5192 grams of alumina contents are taken to be
The boehmite of 61 weight % is added in 16803 grams of decationized Y sieve water, and the pure hydrochloric acid of 562ml chemistry is added under stirring
(36 weight % of concentration), aging are added prepared kaolin slurry after sixty minutes, mashing, add and prepared contain additive
Aluminium oxide slurries, mashing, then be added SZ3 molecular sieves 4719 grams (butts), mashing, carry out spray drying and carrying out washing treatment
(with example 1), drying, obtains catalyst, is denoted as SC3.
Comparative example 1
Taking 4000 grams of NaY molecular sieves (butt) to be added to stirring in 40 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 2000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
5 hours progress hydrothermal modification treatments are roasted under 650 DEG C of temperature, 100% water vapour afterwards and are added to 40 liters of decationized Y sieves later
Stirring makes it be uniformly mixed in aqueous solution, and 2000 grams of (NH are added4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, then
It is filtered, washed, is roasted at 650 DEG C of temperature, 100% water vapour 5 hours after filter cake is dry in 120 DEG C and carry out second of hydro-thermal
Modification obtains ion exchange super steady hydro-thermal super-stable Y molecular sieves without rare earth of hydro-thermal twice twice, is denoted as DZ1.Its
Physico-chemical property is listed in Table 1 below, by DZ1 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, with the method for XRD
It analyzes the crystallinity of the zeolite before and after DZ1 agings and calculates the opposite crystal retention after aging, the results are shown in Table 2.
It takes the Aluminum sol that 1429 grams of alumina contents are 21 weight % to be added in 3131 grams of decationized Y sieve water, opens stirring,
The kaolin that 5526 grams of solid contents are 76 weight % is added to disperse 60 minutes.It is the quasi- of 61 weight % to take 4098 grams of alumina contents
Boehmite is added in 16292 grams of decationized Y sieve water, and pure hydrochloric acid (36 weight of concentration of 420ml chemistry is added under stirring
Measure %), scattered kaolin slurry is added in acidification after sixty minutes, and levigate DZ1 molecular sieves 3000 grams (butts) are then added,
After stirring evenly, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as DC1.
Comparative example 2
Taking 4000 grams of NaY molecular sieves (butt) to be added to stirring in 40 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 2000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
After carry out hydrothermal modification treatment, the condition of the hydrothermal modification treatment：It is roasted 5 hours under 650 DEG C of temperature, 100% water vapour, it
Afterwards, being added to stirring in 40 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and the RE (NO of 400ml are added3)3Solution is (with RE2O3
It is a concentration of to count earth solution：319g/L) and 1800 grams of (NH4)2SO4, stirring is warming up to 90~95 DEG C and kept for 1 hour, then mistake
Filter, washing, second hydrothermal modification treatment is carried out after filter cake is dry in 120 DEG C, and (650 DEG C of temperature roasts under 100% water vapour
5 hours), ion exchange super steady hydro-thermal super-stable Y molecular sieves containing rare earth of hydro-thermal twice twice are obtained, DZ2 is denoted as.Its materialization
Property is listed in Table 1 below, and by DZ2 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, is analyzed with the method for XRD
The crystallinity of zeolite before and after DZ2 agings simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.
It takes the Aluminum sol that 1429 grams of alumina contents are 21 weight % to be added in 3131 grams of decationized Y sieve water, opens stirring,
The kaolin that 5526 grams of solid contents are 76 weight % is added to disperse 60 minutes.It is the quasi- of 61 weight % to take 4098 grams of alumina contents
Boehmite is added in 16292 grams of decationized Y sieve water, and pure hydrochloric acid (36 weight of concentration of 420ml chemistry is added under stirring
Measure %), scattered kaolin slurry is added in acidification after sixty minutes, and levigate DZ2 molecular sieves 3000 grams (butts) are then added,
After stirring evenly, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as DC2.
Comparative example 3
Taking 4000 grams of NaY molecular sieves (butt) to be added to stirring in 40 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RE (NO of 1300ml3)3Solution (319g/L), stirring are warming up to 90~95 DEG C and are kept for 1 hour, be then filtered, washed, later
The super steady modification of gas phase is carried out, molecular sieve drying process is first carried out, so that its water content is less than 1 heavy %, 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 the high silicon super-stable Y molecular sieves of gas phase, be denoted as DZ3.Its
Physico-chemical property is listed in Table 1 below, by DZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, with the method for XRD
It analyzes the crystallinity of the zeolite before and after DZ3 agings and calculates the opposite crystal retention after aging, the results are shown in Table 2.
It takes the Aluminum sol that 1429 grams of alumina contents are 21 weight % to be added in 3131 grams of decationized Y sieve water, opens stirring,
The kaolin that 5526 grams of solid contents are 76 weight % is added to disperse 60 minutes.It is the quasi- of 61 weight % to take 4098 grams of alumina contents
Boehmite is added in 16292 grams of decationized Y sieve water, and pure hydrochloric acid (36 weight of concentration of 420ml chemistry is added under stirring
Measure %), scattered kaolin slurry is added in acidification after sixty minutes, and levigate DZ3 molecular sieves 3000 grams (butts) are then added,
After stirring evenly, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as DC3.
Embodiment 4
Catalyst SC4 is prepared according to the method for embodiment 3, prepared catalyst composition is as follows：
In terms of butt, the SZ3 molecular sieves containing 36 weight %, the aluminium oxide containing additive of 2 weight % and in terms of butt
The boehmite binder of the aluminium sol adhesive of the clay of 34 weight % and 4 weight %, 24 weight %.
Comparative example 4
Catalyst DC4 is prepared according to the method for embodiment 3, the difference is that the molecular sieve DZ3 prepared with comparative example 3 replaces it
In molecular sieve SZ3.
Embodiment 5~8
The catalyst respectively prepared by Examples 1 to 4, SC1, SC2, SC3 and SC4 are at 800 DEG C, 4 hours or 17 hours
After 100% vapor aging, the light oil microactivity of catalyst is evaluated, evaluation result is listed in Table 3 below.
Light oil microactivity evaluation method：
Using RIPP92-90 standard method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui is surely equal to be compiled,
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)=(gasoline production+gas yield+coke output for being less than 216 DEG C in product)/charging
Total amount × 100%.
Comparative example 5~8
Catalyst DC1, DC2, DC3 and DC4 prepared by comparative example 1~4 is in 800 DEG C, 4 hours or 17 hours 100% water
After steam aging, its light oil microactivity is evaluated.Evaluation method is shown in embodiment 5~8, and evaluation result is listed in Table 3 below.
Embodiment 9~12
By SC1, SC2, SC3, SC4 catalyst through 800 DEG C, after 100% vapor aging 17 hours, in small-sized fixed fluidisation
Its catalytic cracking reaction performance is evaluated on bed reactor (ACE), cracked gas and product oil are not collected by gas chromatographic analysis.It urges
Agent loading amount is 9g, 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 16h- 1, agent weight of oil ratio be shown in Table 5, ACE experiment feedstock property
4 are shown in Table, evaluation result is shown in Table 5.
Comparative example 9~12
DC1, DC2 and DC3, DC4 catalyst are through 800 DEG C, after 100% vapor aging 17 hours, in small-sized fixed fluidisation
Its catalytic cracking reaction performance is evaluated on bed reactor (ACE), evaluation method is shown in that embodiment 9, the feedstock property of ACE experiments are shown in Table
4, evaluation result is listed in Table 5 below.
Table 1
By table 1 as it can be seen that the Modified Zeolite Y of high stability provided by the invention, is provided simultaneously with following advantages：Sodium oxide molybdena
Content is low, and the non-framework aluminum content when sial of molecular sieve is relatively high is less, second hole 2.0nm~100nm hole bodies in molecular sieve
Product accounts for that total pore volume percentage is relatively high, also, B acid/L acid (the ratio between total B acid acid amounts and L acid acid amounts) is higher, brilliant in molecular sieve
The crystallinity value that the smaller content of rare earth of born of the same parents' constant measures when higher is higher, has high thermal stability.
Table 2
As shown in Table 2, Modified Zeolite Y provided by the invention passes through 800 DEG C under sieve sample naked state,
After harsh conditions aging in 17 hours, sample has higher opposite crystal retention, shows modified Y types provided by the invention point
Sub- sifter device has high hydrothermal stability.
Table 3
Table 4ACE evaluates raw material oil nature
Table 5
By the result listed by table 3 and table 5 it is found that catalytic cracking catalyst provided by the invention has very high hydrothermally stable
Property, there is significantly lower coke selectivity, there is considerably higher liquid to receive, yield of light oil is considerably higher, and yield of gasoline carries
Height, heavy oil conversion activity higher.
Claims (13)
1. a kind of catalytic cracking catalyst, the Modified Zeolite Y containing in terms of butt 10 weight of weight %~50 %, with butt
Count the clay of the aluminium oxide containing additive and the weight % of in terms of butt 10 weight~80 of the weight % of 2 weight~40；Wherein, with dry
Base meter, the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide containing additive, 0.5 weight %-40 weight %
Additive, the one kind of the additive in the compound containing alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements
Or it is several；The rare earth oxide content of the Modified Zeolite Y is the 5 weight % of weight %~12, and sodium oxide content is 0.1 weight
Measure the weight % of %~0.7, total pore volume is 0.33mL/g~0.39mL/g, the aperture of the Modified Zeolite Y be 2nm~
The pore volume of the second hole of 100nm account for total pore volume percentage be 10%~25%, lattice constant be 2.440nm~
2.455nm, non-framework aluminum content accounts for the percentage of total aluminium content and is not higher than 20% in the Modified Zeolite Y, lattice avalanche temperature
Degree is not less than 1050 DEG C, also, B in the total acid content of the Modified Zeolite Y measured at 200 DEG C with pyridine adsorption infrared method
Acid amount and the ratio of L acid amounts are not less than 2.50.
2. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that aperture is in the Modified Zeolite Y
The percentage that the pore volume of the second hole of 2nm~100nm accounts for total pore volume is 15%~21%, and non-framework aluminum content accounts for total aluminium and contains
The percentage of amount is 13~19%, and framework si-al ratio is with SiO2/Al2O3Molar ratio computing is 7.3~14, molecular sieve lattice avalanche temperature
1055 DEG C~1080 DEG C of degree, B acid in the Modified Zeolite Y total acid content measured at 200 DEG C with pyridine adsorption infrared method
The ratio of amount and L acid amounts is 2.6~4.0.
3. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the opposite knot of the Modified Zeolite Y
Brilliant degree is 60~70%, after 800 DEG C, normal pressure, the harsh aging in 17 hours of 100% steam atmosphere, the Modified Zeolite Y
Opposite crystal retention be 38% or more be, for example, 38~48%.
4. according to any catalytic cracking catalyst of Claims 1 to 4, which is characterized in that the Modified Zeolite Y
Rare earth oxide content be 5.5~10 weight %, sodium oxide content be 0.3~0.7 weight %, lattice constant be 2.442~
2.450nm, framework si-al ratio are 8.5~12.6.
5. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the catalyst includes in terms of butt 25
Oxidation containing additive described in the Modified Zeolite Y of the weight of weight %~40 %, in terms of butt 2~20 weight %
The clay of the weight % of the alumina binder of the weight % of aluminium, in terms of aluminium oxide 5 weight~30 and in terms of butt 30 weight~50.
6. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that it is high that the clay is selected from kaolin, more water
Ridge soil, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, one kind in bentonite or
It is a variety of；
The preparation method of the aluminium oxide containing additive includes the following steps：
(1), boehmite is mixed under stiring with being enough to make the water of its pulp and acid, wherein the dosage of acid make the acid with
The weight ratio of aluminium oxide is 0.01-0.5 in boehmite；
(2), by the mixed serum of step (1) at a temperature of room temperature~90 DEG C aging 0~24 hour；
(3), the product of step (2) is mixed with additive, optionally drying and optionally roasting.
7. a kind of preparation method of catalytic cracking catalyst, including Modified Zeolite Y is prepared, formation includes the modified Y types
The step of slurries of molecular sieve, the aluminium oxide containing additive, clay and water, spray drying, wherein with the oxygen containing additive
On the basis of the weight for changing aluminium, the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide containing additive, 0.5 weight
The additive of %-40 weight % is measured, the additive, which is selected from, contains alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements
One or more of compound；The preparation method of the Modified Zeolite Y includes the following steps：
(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) according to SiCl4：Y type molecular sieve=0.1~0.7 that the lattice constant in terms of butt reduces：1 weight ratio is by institute
Y type molecular sieve and the silicon tetrachloride gas haptoreaction of lattice constant reduction are stated, reaction temperature is 200 DEG C~650 DEG C, when reaction
Between be 10 minutes to 5 hours, washing and filtering, obtain Modified Zeolite Y.
8. according to method of claim 7, which is characterized in that sodium oxide content described in step (1) reduce containing rare earth
The Y type molecular sieve of conventional unit cell dimension, lattice constant are 2.465~2.472nm, and sodium oxide content is no more than 9.0 weight %；
The lattice constant for the Y type molecular sieve that the lattice constant obtained in step (2) reduces is 2.450nm~2.462nm, described
Water content in the Y type molecular sieve that lattice constant reduces is no more than 1 weight %.
9. according to the method described in claim 8, it is characterized in that, in step (1), what the sodium oxide content reduced contains rare earth
Conventional unit cell dimension Y type molecular sieve in, content of rare earth is with RE2O35.5~14 weight % are calculated as, sodium oxide content is 4~9
Weight % is, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.
10. the method according to the description of claim 7 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：H2O=1：0.01~0.18：5~15 weight ratio will
NaY molecular sieve, rare-earth salts and water form mixture, stirring.
11. the method according to claim 7 or 10, which is characterized in that step (1) is described molten with rare earth by NaY molecular sieve
Liquid contact carries out ion-exchange reactions, including：NaY molecular sieve is mixed with water, under stirring, rare-earth salts and/or rare-earth salts is added
Solution carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions is：Exchange temperature is 15~95 DEG C, when exchange
Between be 30~120 minutes, the rare-earth salt solution be rare-earth salts aqueous solution；The rare-earth salts is, for example, rare earth chloride
And/or nitric acid rare earth.
12. the method according to the description of claim 7 is characterized in that step (2) described calcination temperature be 380~460 DEG C, institute
It is 40~80 volume % water vapour atmospheres to state calcination atmosphere, and the roasting time is 5~6 hours.
13. the method according to the description of claim 7 is characterized in that the washing methods described in step (3) is to be washed with water, wash
The condition of washing is molecular sieve：H2O=1:6~15, pH value is 2.5~5.0, and wash temperature is 30~60 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN101285001A (en) * | 2007-04-12 | 2008-10-15 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
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2017
- 2017-02-22 CN CN201710097152.1A patent/CN108452836B/en active Active
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|---|---|---|---|---|
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN101285001A (en) * | 2007-04-12 | 2008-10-15 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
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