CN108452827A - A kind of catalytic cracking catalyst - Google Patents
A kind of catalytic cracking catalyst Download PDFInfo
- Publication number
- CN108452827A CN108452827A CN201710093670.6A CN201710093670A CN108452827A CN 108452827 A CN108452827 A CN 108452827A CN 201710093670 A CN201710093670 A CN 201710093670A CN 108452827 A CN108452827 A CN 108452827A
- Authority
- CN
- China
- Prior art keywords
- weight
- molecular sieve
- rare earth
- phosphorous
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J2029/081—Increasing the silica/alumina ratio; Desalumination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of catalytic cracking catalyst, contain phosphorous and Modified Zeolite Y, alumina binder and clay of rare earth, described phosphorous and rare earth Modified Zeolite Y is containing 4~11 weight % rare earths, 0.05~10 weight % phosphorus, 0.1~0.7 weight % sodium oxide molybdenas, pore volume is 0.33~0.39mL/g, the volume in the holes 2~100nm accounts for the 15~30% of total pore volume, 2.440~2.455nm of lattice constant, non-framework aluminum accounts for 20% or less total aluminium, lattice collapse temperature is more than 1050 DEG C, and the ratio between B acid amount and L acid amounts are not less than 2.50.The catalytic cracking catalyst heavy oil cracking activity is high, and coke selectivity is good, and gasoline yield is high, and liquefied gas yield and total liquid yield are high.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalysts and preparation method thereof.
Background technology
With the increasing weight of catalytic cracking feedstock oils and environmental regulation it is increasingly stringent, it is desirable that catalytic cracking catalyst
Heavy oil conversion performance is improved, while again can voluminous gasoline.The key for obtaining high yield gasoline is catalyst activity component i.e. rare earth
Y-type high-Si zeolite can keep crystal structure intact, have very high heat and hydrothermal stability, have strong acidity and low acid
Density.
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, the 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.But gas
Phase super stable molecular sieve does not have second hole.United States Patent (USP) US4273753, US4438178, Chinese patent CN1382525A,
CN1194941A, CN1683244A, which are disclosed, utilizes SiCl4The method of gas chemistry dealuminzation ultrastable.But existing gas
Phase super stable molecular sieve still has the not high problem of activity for residual oil cracking, cannot meet the processing need of mink cell focus and poor oil
It wants, it directly affects the product distribution and economic benefit of catalytic cracking unit.
In order to make molecular sieve meet the needs of current processing heavy oil and poor oil, the prior art carries out Y type molecular sieve
Rare earth and phosphorus plasma exchange modified and surface and are modified.
CN1330981A discloses a kind of P-contained Y-zeolite and preparation method thereof.Described P-contained Y-zeolite contains phosphorus, also
Containing a kind of silicon component and rare earth component, the silicon component is got on the method load of silicon compound solution dipping zeolite,
With SiO2The content of meter, the silicon component is 1-15 weight %, with P2O5The content of meter, the phosphorus component is 0.1-15 weight %, with dilute
The content of native oxide meter, the rare earth component is 0.2-15 weights %.The molecular sieve be will contain the y-type zeolite of rare earth with it is siliceous,
The solution total immersion of phosphorus, obtains after drying in 550-850 DEG C of hydrothermal calcine.The P-contained Y-zeolite crystallizes after hydro-thermal process
Degree is higher, there is preferable catalytic performance, and the Cracking catalyst of the content y-type zeolite has stronger heavy oil conversion performance and preferably
Product distribution.
CN1353086A discloses the preparation method of a kind of phosphorous and rare earth Y type molecular sieve, and gained Y type molecular sieve can be shown
Writing reduces the olefin(e) centent of FCC gasoline, while can keep good coke selectivity.The method includes NaY molecular sieve is first
With ammonium ion and rare earth ion hybrid switching and hydrothermal calcine, then itself and 0.2~10 weight % in phosphorus compound reaction bonded
(with P2O5Meter) phosphorus, then carry out hydrothermal calcine.The super-stable Y molecular sieves of phosphorous and rare earth prepared by this application method, structure cell are normal
Number is larger, and super steady degree is low, and the crystal retention of molecular sieve is not high.
CN1506161 discloses a kind of hyperastable Y-type RE molecular sieve active component, and this modified molecular screen contains rare earth oxide 8
~25 heavy %, 0.1~3.0 weight of phosphorus；0.3~2.5 heavy % of sodium oxide molybdena, crystallinity 30~55%, lattice constant 2.455~2.472
Nanometer.System with molecular sieve for preparing is standby using NaY zeolite as raw material, by rare earth exchanged and roasting for the first time, obtains " one hands over a roasting " rare earth
NaY, then reacted with rare earth, phosphorus containg substances and ammonium salt, carry out second of calcination process, acquisition phosphorus and rare earth modified modification Y
Zeolite.This modified molecular screen coke yield is moderate.Molecular sieve content of rare earth obtained is higher by this method, lattice constant
Larger, molecular sieve coke selectivity is affected.
CN1317547A discloses a kind of phosphorus and the composite modified Y zeolites of rare earth and preparation method thereof, which has NaY boilings
Stone reacts after rare earth and ammonium salt hybrid switching are handled using hydrothermal calcine with phosphorus compound, then carries out second and roasts
Processing, wherein RE2O3The weight ratio of/Y zeolites is 0.02~0.18, and the weight ratio of ammonium salt/Y zeolites is 0.1~1.0, P/Y zeolites
Weight ratio be 0.003~0.05,250~750 DEG C of calcination temperature, water vapor condition 5~100%, 0.2~3.5 hour time.It should
The super-stable Y molecular sieves of phosphorous and rare earth prepared by method, lattice constant is larger, and super steady degree is low, and the crystallization of molecular sieve retains
Degree is not high.
CN02103910.0 provides a kind of preparation method of " one hands over a roasting " modcfied faujasite, and modcfied faujasite is
An exchange reaction is carried out by faujasite and phosphorus compound and ammonium compounds, then introduces earth solution in exchanging slurries
Further reaction, through being filtered, washed, steam calcination process obtains.It is catalyst cracking made of active component the zeolite
Activity is not high, and heavy oil conversion rate is low.
The Cracking catalyst of existing phosphorous and rare earth super-stable Y molecular sieves, heavy oil cracking activity is not high, coke selection
Type is poor.
Invention content
One of the technical problem to be solved in the present invention is to provide a kind of catalysis suitable for mink cell focus catalyzed cracking processing and splits
Change catalyst, catalyst heat and hydrothermal stability are high, gasoline yield is high, heavy oil conversion performance is strong, and coke selectivity is low.This hair
Bright to be solved second technical problem is to provide a kind of preparation method of the catalytic cracking catalyst.
The present invention provides a kind of catalytic cracking catalyst, contains the phosphorous and dilute of in terms of butt 10 weight of weight %~50 %
The alumina binder of the weight % of native Modified Zeolite Y, in terms of aluminium oxide 10 weight~40 and 10 weight~80 in terms of butt
The clay of weight %, wherein the super steady Modified Zeolite Y (Y type molecular sieve is also referred to as y-type zeolite) of the phosphorous and rare earth
Rare earth oxide content is 4~11 weight %, and phosphorus content is with P2O5Meter content be 0.05~10 weight %, sodium oxide content be 0.1~
0.7 weight %, total pore volume are 0.33~0.39mL/g, which is the second hole of 2nm~100nm
Pore volume account for the Modified Zeolite Y total pore volume percentage be 15%~30%, lattice constant be 2.440nm~
2.455nm, preferred framework si-al ratio (SiO2/Al2O3Molar ratio) be：7~14, non-framework aluminum content accounts for total aluminium in molecular sieve
The percentage of content is not higher than 20%, and lattice collapse temperature is not less than 1050 DEG C, also, with pyridine adsorption infrared method at 200 DEG C
When the Modified Zeolite Y total acid content that measures in B acid amount and the ratio of L acid amounts be not less than 2.50.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth, lattice avalanche
Temperature is not less than 1050 DEG C, it is preferred that 1055 DEG C of molecular sieve lattice collapse temperature~1080 DEG C, for example, 1057~1075
℃。
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth is inhaled with pyridine
In the total acid content that attached infrared method is measured at 200 DEG C the ratio of B acid amount and L acid amounts be preferably 2.6~4.0 be, for example, 2.7~
3.3。
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth, lattice constant
It is, for example, 2.440~2.453nm for 2.440nm~2.455nm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth is high silicon Y
Type molecular sieve, framework si-al ratio (SiO2/Al2O3Molar ratio) it is 7.3~14, for example,：8.5~12.6.
In catalytic cracking catalyst provided by the invention, non-skeleton in the Modified Zeolite Y of the phosphorous and rare earth
The percentage that aluminium content accounts 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 of the phosphorous and rare earth, 800 DEG C,
Crystal retention under normal pressure, 100 volume % water vapour atmospheres after aging 17 hours be 35% or more be, for example, 38~48% or
35~45%.The normal pressure is 1atm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth is opposite to crystallize
Degree is not less than 60%, it is preferred that the relative crystallinity of the Modified Zeolite Y is 60~70%, for example, 60~66%.
A kind of embodiment, in catalytic cracking catalyst provided by the invention, the modification Y types point of the phosphorous and rare earth
Son sieve, specific surface area are 600~670m2/ g is, for example, 610~660m2/g。
Preferably, in catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth is total
Pore volume is that 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 of the phosphorous and rare earth, aperture (refers to
Diameter) be 2.0nm~100nm the pore volume of second hole to account for the percentage of total pore volume be 15%~30%, preferably 20~
30%.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth contains rare earth
Element, with RE2O3The rare earth oxide content of meter is that 4~11 weight % are preferably 4.5~10 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth changes containing phosphorus
Property element, P in the Modified Zeolite Y2O5(i.e. with P2O5The phosphorus content of meter) be 0.05~10 weight %, for example, 0.1~6
Weight %, preferably 0.1~5 weight %.
In catalytic cracking catalyst provided by the invention, sodium oxide molybdena in the Modified Zeolite Y of the phosphorous and rare earth
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 %.
Catalytic cracking catalyst provided by the invention also contains other molecular sieves other than the Modified Zeolite Y,
On the basis of the weight of the catalytic cracking catalyst, the content of its described molecular sieve is, for example, 0~40 weight in terms of butt
It is, for example, 0~30 weight % or 1~20 weight % to measure %.Point that other molecular sieves use in catalytic cracking catalyst
Son sieve, such as the one or more with MFI structure zeolite, Beta zeolites, other y-type zeolites, non-zeolite molecular sieve.It is preferred that
, it can be 1~40 weight % or be 0 that the content of other Y type molecular sieves, which is no more than 40 weight % for example, in terms of butt~
20 weight %.Described other y-type zeolites such as REY, REHY, one or more, the MFI structure zeolite in DASY, SOY, PSRY
Such as one or more in HZSM-5, ZRP, ZSP, beta zeolites such as H β, non-zeolite molecular sieve such as aluminium phosphate molecular sieve
It is one or more in (AlPO molecular sieves), sial phosphorus molecular sieve (SAPO molecular sieve).
In catalytic cracking catalyst provided by the invention, described phosphorous and rare earth the Modified Zeolite Y in terms of butt
It is, for example, 25~40 weight % that content, which is preferably 15~45 weight % for 10~50 weight %,.
In catalytic cracking catalyst provided by the invention, the clay is in the clay as cracking catalyst component
One or more, such as kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, bumps
One or more of stick stone, hydrotalcite, bentonite.These clays are known to those of ordinary skill in the art.Preferably, with
The content of clay described in butt meter catalytic cracking catalyst provided by the invention is 20~55 weight % or 30~50 weight %.
In catalytic cracking catalyst provided by the invention, the content of the alumina binder be 10~40 weight % for example
For 20~35 weight %.Alumina binder of the present invention is selected from the oxygen of the commonly used various forms of Cracking catalyst
Change one or more of aluminium, hydrated alumina and Aluminum sol.For example, selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide,
χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite), Bayer
One or more of stone (Bayerite) or Aluminum sol, preferably boehmite and Aluminum sol, such as the catalytic cracking are urged
Contain in terms of aluminium oxide 2~15 weight the % preferably Aluminum sol of 3~10 weight %, in terms of aluminium oxide 10~30 weight % in agent
It is preferred that the boehmite of 15~25 weight %.
The present invention provides a kind of preparation method of catalytic cracking catalyst, including prepares the modification of the phosphorous and rare earth
Y type molecular sieve, by the raw material of Modified Zeolite Y, alumina binder and clay including the phosphorous and rare earth and
Water forms slurries, the step of spray drying, wherein prepares the phosphorous method with the Modified Zeolite Y of rare earth include with
Lower step:
(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, obtain lattice constant reduction Y types
Molecular sieve；
(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 for the Y type molecular sieve sample that the phosphorous lattice constant reduces
Content is preferably more than 1 weight %；
(4) the Y type molecular sieve sample and SiCl for reducing the phosphorous lattice constant that step (3) obtains4Gas exists
Temperature is haptoreaction under conditions of 200~650 DEG C, wherein preferably, SiCl4：The structure cell that the step of in terms of butt (2) obtains
Weight ratio=0.1~0.7 for the Y type molecular sieve that constant reduces：1,10 minutes to 5 hours reaction time, then washed, mistake
Filter, obtains Modified Zeolite Y.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth, crystallinity
Height has two level pore structure, and heat and hydrothermal stability are high, have higher heavy oil conversion activity and lower coke selectivity,
With higher yield of gasoline, yield of light oil and total liquid yield.Catalyst of the present invention is used for heavy oil catalytic cracking, has higher
Gasoline yield, higher yield of light oil, heavy oil cracking ability is strong, and coke selectivity is high, and hydrothermal stability is high.
In catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y of the phosphorous and rare earth
Preparation method can prepare the phosphorous with certain two level pore structure of high-crystallinity, high thermal stability and high hydrothermal stability
With the high-Si Y-type molecular sieve of rare earth, aluminium is evenly distributed in the molecular sieve, and non-framework aluminum content is few, which is used for
Heavy oil conversion, coke selectivity is good, and heavy oil cracking activity is high, can improve yield of gasoline of the molecular sieve for heavy oil conversion when,
Yield of liquefied gas and total liquid yield.
Catalytic cracking catalyst provided by the invention can be used for heavy oil or poor oil conversion.
Specific implementation mode
Catalytic cracking catalyst provided by the invention contains 10 weight in terms of butt on the basis of the weight of the catalyst
Measure the oxygen of the weight % of described phosphorous and rare earth the Modified Zeolite Y of the weight of %~50 %, in terms of aluminium oxide 10 weight~40
Change the clay of the weight % of al binder and in terms of butt 10 weight~80.Preferably, the catalytic cracking catalyst contains with dry
The weight % of the Modified Zeolite Y of the phosphorous and rare earth of 25 weight of weight %~40 % of base meter, in terms of aluminium oxide 20 weight~35
Alumina binder and the weight % of in terms of butt 30 weight~50 clay.
Catalytic cracking catalyst provided by the invention, a kind of embodiment, the modification Y type molecules of the phosphorous and rare earth
Sieve, rare earth oxide content are 4~11 weight %, preferably 4.5~10 weight %；P in the Modified Zeolite Y2O5Content
(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 15%~30%, preferably 20%~30%, structure cell
Constant is 2.440nm~2.455nm, framework si-al ratio (SiO2/Al2O3Molar ratio) it is 7~14, it is non-in the Modified Zeolite Y
The percentage that framework aluminum content accounts for total aluminium content is not higher than 20%, preferably 13~19%, and relative crystallinity is not less than 60%, crystalline substance
Lattice collapse temperature is 1055 DEG C~1080 DEG C, also, the modification Y type molecules measured at 200 DEG C with pyridine adsorption infrared method
It sieves B acid amount and the ratio of L acid amounts in total acid content and is not less than 2.50, preferably 2.6~4.0.
In catalytic cracking catalyst provided by the invention, the super-stable Y molecular sieves of the phosphorous and rare earth be it is phosphorous and
The super steady Modified Zeolite Y of gas phase of rare earth, preparation process include contacting Y type molecular sieve with silicon tetrachloride to carry out dealuminzation
The step of mending pasc reaction.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y system 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 reduction
The conventional unit cell dimension containing rare earth Y type molecular sieve.The NaY molecular sieve, can be commercially available or prepares according to existing method,
A kind of embodiment, the NaY molecular sieve lattice constant are 2.465~2.472nm, framework si-al ratio (SiO2/Al2O3Mole
Than) 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) carries out ion-exchange reactions with earth solution, 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):It is dilute
Earth salt is (with RE2O3Meter):H2O=1:0.01~0.18:5~15 weight ratios.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:H2O=1:0.01~0.18:5~15 weight
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
30~120 minutes progress rare earth ions of choosing stirring are exchanged with sodium ion.NaY molecular sieve, rare-earth salts and water are formed into mixture,
NaY molecular sieve and water can be formed slurries, the aqueous solution of rare-earth salts and/or rare-earth salts is then added in the slurries,
The earth solution is the solution of rare-earth salts, and the rare-earth salts is preferably rare earth chloride and/or nitric acid rare earth.Described is dilute
It is one or more in soil such as La, Ce, Pr, Nd and mischmetal, it is preferred that in the mischmetal containing La, Ce,
It is one or more in Pr and Nd, or also contain at least one of the rare earth in addition to La, Ce, Pr and Nd.Step (1) is described
Washing, it is therefore an objective to the sodium ion being swapped out is washed away, it is, for example, possible to use deionized water or decationized Y sieve water washing.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, 5.5~13 weight or 5.5~12 weight % or 4.5~11.5 weight % for 4.5~13 weight %, sodium oxide content is not
It is, for example, 5.5~9.5 weight % or 5.5~8.5 weight % more than 9.5 weight %, lattice constant is 2.465nm~2.472nm.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y system of the phosphorous and rare earth
In Preparation Method, by the Y type molecular sieve of the conventional unit cell dimension containing rare earth in 350~480 DEG C of temperature, 30~90 bodies in step (2)
It roasts 4.5~7 hours and is handled under product % water vapour atmospheres, it is preferred that the calcination temperature described in step (2) is 380~460
DEG C, calcination atmosphere is 40~80 volume % water vapour atmospheres, and roasting time is 5~6 hours.Contain in the water vapour atmosphere
30~90 volume % vapor also contain one or more in other gases, such as air, helium or nitrogen.In step (2)
The Y type molecular sieve that the lattice constant reduces, lattice constant are 2.450nm~2.462nm.
Catalytic cracking catalyst preparation method provided by the invention, in the method for the phosphorous and rare earth, step (3) will
The Y type molecular sieve that the lattice constant that step (2) obtains reduces carries out P Modification processing with phosphorus compound, to be introduced in molecular sieve
Phosphorus, the Y type molecular sieve that the P Modification processing generally includes to obtain step (2) lattice constant reduction are contacted with liquid is exchanged, institute
It states and exchanges liquid and contain phosphorus compound, the contact contacts 10-100 minutes usually at 15~100 DEG C preferably 30~95 DEG C, then
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) and molecule
The weight ratio of sieve is：0.0005~0.10, preferably 0.001~0.05.Described phosphorus compound can be selected from phosphoric acid, ammonium phosphate, phosphorus
It is one or more in acid dihydride ammonium, diammonium hydrogen phosphate.The washing is for example with the water such as exhaustion of yang of 5~15 times of molecular sieve
Ion or deionized water are washed.
Catalytic cracking catalyst preparation method provided by the invention, a kind of embodiment, the P Modification treatment conditions
For：The Y type molecular sieve powder sample that the lattice constant is reduced 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) with the weight ratio of molecular sieve be：0.0005~0.10, preferably 0.001~0.05.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y system of the phosphorous and rare earth
Also the molecular sieve that roasting obtains is dried in standby step (3), so that the water in the Y type molecular sieve that the lattice constant reduces
Content is preferably more than 1 weight %.The drying, can be used existing method, for example, by using pneumatic conveying drying, drying, expansion drying
Method.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y system of the phosphorous and rare earth
In Preparation Method, in step (4), the SiCl4：The weight ratio of Y type molecular sieve (in terms of butt) is preferably 0.3~0.6：1, it is described
The temperature of reaction is preferably 350~500 DEG C, and conventional washing methods may be used in the washing methods described in step (3), can use water
Washing 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 secondary
Product, such as wash conditions can be：The weight ratio of washings and molecular sieve can be 5~20：1, usual molecular sieve：H2O weights
Measure ratio=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
Cleaning solution in detect 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 %.
Catalytic cracking catalyst preparation method provided by the invention, a kind of embodiment, the phosphorous and rare earth change
The preparation method of property Y type molecular sieve 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) 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) with the weight ratio of molecular sieve it 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 less than 1 weight % reduces；
(4) Y type molecular sieve and heated vaporization that the phosphorous lattice constant by the water content less than 1 weight % reduces
SiCl4Gas contacts, wherein SiCl4：The Y type molecular sieve that lattice constant of the water content less than 1 weight % reduces (in terms of butt)
Weight ratio=0.1~0.7：1, the haptoreaction 10 minutes to 5 hours under conditions of temperature is 200~650 DEG C, it is washed and
Filtering, obtains Modified Zeolite Y provided by the invention.
Method for preparing catalyst of the present invention can refer to existing method, for example, according to patent CN1098130A,
It is prepared by the method disclosed in CN1362472A.It generally includes to form the slurry for including Modified Zeolite Y, binder, clay and water
The step of liquid, spray drying optionally further includes washing and dry step.The spray drying, washing, drying are existing skill
Art, the present invention do not have particular/special requirement.
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
Infrared method surveys acidotic experimental method at 200 DEG C：By sample self-supporting tabletting, it is placed in close in the pond 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 steams keep 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 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 2000 grams of NaY molecular sieves to be added to stirring in 20 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RE (NO of 600ml 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, after cooling, will divided
Son sieve is added in 6 aqueous solutions dissolved with 35 grams of phosphoric acid, is warming up to 90 DEG C, carries out P Modification processing in 30 minutes, later, will
Molecular sieve filtration washs, and processing is dried in filter cake, so that its water content is less than 1 weight %, then according to SiCl4：Y types point
Son sieve (butt meter)=0.5：1 weight ratio is passed through the SiCl of heated vaporization4Gas, under conditions of temperature is 400 DEG C,
Reaction 2 hours, later, with 20 liters of decationized Y sieve water washings, then filters, obtains Modified Zeolite Y provided by the invention, remembers
For SZ1, physico-chemical property is listed in Table 1 below, by SZ1 naked state through 800 DEG C, 1atm, 100% vapor aging 17 hours
Afterwards, the relative crystallinity of the molecular sieve before and after SZ1 agings is analyzed with the method for XRD and the opposite crystallization calculated after aging retains
Degree, the results are shown in Table 2, wherein：
The Aluminum sol that 714.5 grams of alumina contents are 21 weight % is taken to be added in 1565.5 grams of decationized Y sieve water, unlatching is stirred
It mixes, the kaolin that 2763 grams of solid contents are 76 weight % is added and disperses 60 minutes.It is 61 weight % to take 2049 grams of alumina contents
Boehmite be added 8146 grams of decationized Y sieve water in, under stirring be added 210ml mass concentrations be 36% hydrochloric acid, acid
Scattered kaolin slurry is added in change after sixty minutes, and levigate SZ1 molecular sieves 1500 grams (butts) are then added, stir evenly
Afterwards, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as SC1.Wherein, contain in obtained SC1 catalyst
30 weight % of SZ1 molecular sieves, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Embodiment 2
Taking 2000 grams of NaY molecular sieves to be added to stirring in 25 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RECl of 800ml is added3Solution is (with RE2O3The solution concentration of meter is：319g/L), it stirs, is warming up to 90~95 DEG C and keeps 1
Hour, it 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 molecular sieve is added to dissolved with 268 grams of phosphoric acid after cooling
In 6 aqueous solutions of ammonium, 60 DEG C are warming up to, P Modification processing in 50 minutes is carried out, later, molecular sieve filtration is washed, and will
Processing is dried in filter cake, so that its water content is less than 1 weight %, then according to SiCl4：Y-type zeolite=0.6：1 weight ratio,
It is passed through the SiCl of heated vaporization4Gas, temperature be 480 DEG C under conditions of, react 1.5 hours, later, with 20 liters of exhaustion of yangs from
Sub- water washing, is then filtered, and obtains Modified Zeolite Y, is denoted as SZ2.Its physico-chemical property is listed in Table 1 below, by SZ2 in exposed shape
State is through 800 DEG C, after 100% vapor aging in 17 hours, the crystallinity of the zeolite before and after analyzing SZ2 agings with the method for XRD
And the opposite crystal retention after aging is calculated, it the results are shown in Table 2.
The Aluminum sol that 714.5 grams of alumina contents are 21 weight % is taken to be added in 1565.5 grams of decationized Y sieve water, unlatching is stirred
It mixes, the kaolin that 2763 grams of solid contents are 76 weight % is added and disperses 60 minutes.It is 61 weight % to take 2049 grams of alumina contents
Boehmite be added in 8146 grams of decationized Y sieve water, the pure hydrochloric acid of 210ml chemistry is added under stirring, is acidified 60 points
Scattered kaolin slurry is added after clock, levigate SZ2 molecular sieves 1500 grams (butts) are then added, after stirring evenly, into
Row spray drying and carrying out washing treatment, drying obtain catalyst, are denoted as SC2.Wherein, SZ2 points are contained in obtained SC2 catalyst
Son sieve 30 weight %, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Embodiment 3
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RECl of 570ml3Solution 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 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 processing is dried in filter cake, so that its water content is less 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 obtains Modified Zeolite Y, is denoted as SZ3.Its physico-chemical property is listed in Table 1 below, and SZ3 is existed
Naked state is through 800 DEG C, after 100% vapor aging in 17 hours, with the knot of the zeolite before and after the method analysis SZ3 agings of XRD
Brilliant degree simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.
The Aluminum sol that 714.5 grams of alumina contents are 21 weight % is taken to be added in 1565.5 grams of decationized Y sieve water, unlatching is stirred
It mixes, the kaolin that 2763 grams of solid contents are 76 weight % is added and disperses 60 minutes.It is 61 weight % to take 2049 grams of alumina contents
Boehmite be added in 8146 grams of decationized Y sieve water, the pure hydrochloric acid of 210ml chemistry is added under stirring, is acidified 60 points
Scattered kaolin slurry is added after clock, levigate SZ3 molecular sieves 1500 grams (butts) are then added, after stirring evenly, into
Row spray drying and carrying out washing treatment, drying obtain catalyst, are denoted as SC3.Wherein, SZ3 points are contained in obtained SC3 catalyst
Son sieve 30 weight %, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 1
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 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 20 liters of decationized Y sieves later
Stirring makes it be uniformly mixed in aqueous solution, and 1000 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.
By the catalytic cracking catalysis of DZ1 molecular sieves, kaolin, water, boehmite adhesive and Aluminum sol routinely
The preparation method of agent forms slurries, spray drying is prepared into microspherical catalyst, and prepared catalytic cracking catalyst is denoted as DC1
(preparation method of reference implementation example 1).Wherein, 30 weight % of DZ1 molecular sieves, kaolin are contained in obtained DC1 catalyst
42 weight %, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 2
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 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, 650 DEG C of the temperature of the hydrothermal modification treatment roasts 5 hours under 100% water vapour, later, adds
Entering into 20 liters of decationized Y sieve aqueous solutions stirring makes it be uniformly mixed, and the RE (NO of 200ml are added3)3Solution is (with RE2O3Count rare earth
Solution concentration is：319g/L) and 900 grams of (NH4)2SO4, it stirs, is warming up to 90~95 DEG C and is kept for 1 hour, is then filtered, washed,
Second hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) is carried out after filter cake is dry in 120 DEG C,
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 physico-chemical property arranges
In table 1, after 100% vapor aging in 17 hours, it is old to be analyzed into DZ2 through 800 DEG C in naked state with the method for XRD by DZ2
Change the crystallinity of front and back zeolite and calculate the opposite crystal retention after aging, the results are shown in Table 2.
By the catalytic cracking catalysis of DZ2 molecular sieves, kaolin, water, boehmite adhesive and Aluminum sol routinely
The preparation method of agent forms slurries, spray drying is prepared into microspherical catalyst, and prepared catalytic cracking catalyst is denoted as DC2
(preparation method of reference implementation example 1).Wherein, 30 weight % of DZ2 molecular sieves, kaolin are contained in obtained DC2 catalyst
42 weight %, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 3
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RECl of 570ml3Solution 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 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
Processing is dried in filter cake, and processing is dried in filter cake, so that its water content is less 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, later, with 20 liters of decationized Y sieve water washings, then filters, obtain Modified Zeolite Y, be denoted as DZ3.Its physico-chemical property
It is listed in Table 1 below, it is old with the method analysis SZ3 of XRD after 100% vapor aging in 17 hours by DZ3 in naked state through 800 DEG C
Change the crystallinity of front and back zeolite and calculate the opposite crystal retention after aging, the results are shown in Table 2.
By the catalytic cracking catalysis of DZ3 molecular sieves, kaolin, water, boehmite adhesive and Aluminum sol routinely
The preparation method of agent forms slurries, spray drying is prepared into microspherical catalyst, and prepared catalytic cracking catalyst is denoted as DC3
(preparation method of reference implementation example 1).Wherein, 30 weight % of DZ3 molecular sieves, kaolin are contained in obtained DC3 catalyst
42 weight %, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Embodiment 4~6
Catalytic cracking catalyst SC1, SC2 and the SC3 respectively prepared by Examples 1 to 3 is through 800 DEG C, 4 hours or 17 small
When 100% vapor aging after, evaluate the light oil microactivity of catalyst, 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 4~6
By DC1, DC2 and DC3 catalyst through 800 DEG C, 4 hours or 17 hours 100% vapor agings (17 hours 100%
Vapor aging refers to aging 17 hours under 100% steam atmosphere) after, evaluate its light oil microactivity.Evaluation method is shown in
Embodiment 6, evaluation result is listed in Table 3 below.
Embodiment 7~9
By SC1, SC2, SC3 catalyst through 800 DEG C, under 100% steam atmosphere after aging 17 hours, in small-sized fixed stream
Its catalytic cracking reaction performance is evaluated on fluidized bed reactor (ACE), cracked gas and product oil are not collected by gas chromatographic analysis.
Catalyst loading 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 it is feed stock
Matter is shown in Table 4, and evaluation result is shown in Table 5.
Comparative example 7~9
Catalytic cracking prepared by the ultrastable that 7~9 explanation of comparative example is prepared with the method that comparative example 1~3 provides is urged
The catalytic cracking reaction performance of agent.
DC1, DC2 and DC3 catalyst are through 800 DEG C, (the 100% vapor aging in 17 hours of 100% vapor aging in 17 hours
Refer to aging 17 hours under 100% steam atmosphere) after, evaluate its catalysis on small fixed flowing bed reactor (ACE)
Cracking reaction performance, evaluation method are shown in that embodiment 7, the feedstock property of ACE experiments are shown in Table 4, and evaluation result is listed in Table 5 below.
Table 1
By table 1 as it can be seen that provided by the invention phosphorous and rare earth Modified Zeolite Y, is provided simultaneously with following advantages：Oxidation
Sodium content is low, and the non-framework aluminum content when sial of the Modified Zeolite Y is relatively high is less, second hole 2.0nm in molecular sieve
~100nm pore volumes account for that total pore volume percentage is relatively high, also, B acid/L acid the ratio between (total B acid acid amounts with L acid acid measure) is higher,
The crystallinity value measured when the smaller content of rare earth of molecular sieve lattice constant is higher is higher, has high thermal stability.
Table 2
As shown in Table 2, provided by the invention phosphorous and rare earth Modified Zeolite Y, in sieve sample naked state
Lower to pass through 800 DEG C, after harsh conditions aging in 17 hours, sample has higher opposite crystal retention, shows that the present invention carries
The Modified Zeolite Y of confession has high hydrothermal stability.
Table 3
Table 4ACE evaluates raw material oil nature
Table 5
| Example number | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Sample number into spectrum | SC1 | SC2 | SC3 | DC1 | DC2 | DC3 |
| Molecular sieve used | SZ1 | SZ2 | SZ3 | DZ1 | DZ2 | DZ3 |
| Oil ratio | 5 | 5 | 5 | 9 | 8 | 5 |
| Product distribution/weight % | ||||||
| Dry gas | 1.31 | 1.39 | 1.34 | 1.55 | 1.48 | 1.45 |
| Liquefied gas | 16.98 | 16.75 | 17.31 | 16.86 | 15.33 | 16.25 |
| Coke | 4.35 | 4.51 | 4.25 | 8.33 | 7.61 | 6.16 |
| Gasoline | 53.36 | 54.19 | 52.31 | 38.55 | 43.91 | 51.12 |
| Diesel oil | 16.82 | 16.72 | 17.22 | 20.17 | 19.25 | 16.81 |
| Heavy oil | 7.18 | 6.44 | 7.57 | 14.54 | 12.42 | 8.21 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio/weight % | 76 | 76.84 | 75.21 | 65.29 | 68.33 | 74.98 |
| Coke selectivity/weight % | 5.72 | 5.87 | 5.65 | 12.76 | 11.14 | 8.22 |
| Yield of light oil/weight % | 70.18 | 70.91 | 69.53 | 58.72 | 63.16 | 67.93 |
| Total liquid yield/weight % | 87.16 | 87.66 | 86.84 | 75.58 | 78.49 | 84.18 |
By table 3 and table 5 as it can be seen that catalyst provided by the invention has higher hydrothermal stability, have significantly lower
There is coke selectivity considerably higher liquid to receive, and yield of light oil is considerably higher, and yield of gasoline improves, and heavy oil conversion activity is more
It is high.
Claims (19)
1. a kind of catalytic cracking catalyst, the modification Y types of the phosphorous and rare earth containing in terms of butt 10 weight of weight %~50 %
The weight %'s of the aluminium oxide bonding agent of the weight % of molecular sieve, in terms of aluminium oxide 10 weight~40 and in terms of butt 10 weight~80 is viscous
Soil, wherein described phosphorous and rare earth Modified Zeolite Y is with RE2O3The rare earth oxide content of meter is 4 weights of weight %~11
% is measured, with P2O5The phosphorus content of meter is 0.05~10 weight %, and sodium oxide content is 0.1 weight of weight %~0.7 %, total hole body
Product is 0.33mL/g~0.39mL/g, and the aperture of phosphorous and rare earth the Modified Zeolite Y is the second hole of 2nm~100nm
Pore volume account for total pore volume percentage be 15%~30%, lattice constant be 2.440nm~2.455nm, this is phosphorous and dilute
Soil Modified Zeolite Y in non-framework aluminum content account for total aluminium content percentage be not higher than 20%, lattice collapse temperature is not low
In 1050 DEG C, also, phosphorous and rare earth the Modified Zeolite Y measured at 200 DEG C with pyridine adsorption infrared method is total
B acid amount and the ratio of L acid amounts are not less than 2.50 in acid amount.
2. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the modification Y types of the phosphorous and rare earth
The percentage that the pore volume for the second hole that molecular sieve bore diameter is 2nm~100nm accounts for total pore volume is 20%~30%.
3. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the modification Y types of the phosphorous and rare earth
The percentage that non-framework aluminum content accounts for total aluminium content in molecular sieve is 13~19%, and framework si-al ratio is with SiO2/Al2O3Molar ratio
It is calculated as 7~14.
4. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the modification Y types of the phosphorous and rare earth
1055 DEG C~1080 DEG C of molecular sieve lattice collapse temperature.
5. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that with pyridine adsorption infrared method at 200 DEG C
The ratio of B acid amount and L acid amounts is 2.6~4.0 in the Modified Zeolite Y total acid content measured.
6. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that 800 DEG C, normal pressure, 100% water vapour gas
After atmosphere aging in 17 hours, the opposite crystal retention of the Modified Zeolite Y of the phosphorous and rare earth is 35% or more for example
It is 35~45%.
7. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the modification Y types of the phosphorous and rare earth
The relative crystallinity of molecular sieve is 60~70%.
8. according to any catalytic cracking catalyst of claim 1~7, which is characterized in that the phosphorous and rare earth
The rare earth oxide content of Modified Zeolite Y is 4.5~10 weight %, and sodium oxide content is 0.3~0.7 weight %, phosphorus content
With P2O5It is calculated as 0.1~6 weight %, lattice constant is 2.440~2.453nm, and framework si-al ratio is 8.5~12.6.
9. a kind of preparation method of catalytic cracking catalyst, including prepare the Modified Zeolite Y of the phosphorous and rare earth, shape
At the slurries of Modified Zeolite Y, alumina binder and clay including the phosphorous and rare earth, the step of spray drying
Suddenly；Wherein
The preparation method of the Modified Zeolite Y of the phosphorous and rare earth 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, 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, SiCl4：Weight ratio=0.1~0.7 for the Y type molecular sieve that the phosphorous lattice constant in terms of butt reduces：1、
Reaction temperature is 200 DEG C~650 DEG C, the reaction time is 10 minutes to 5 hours.
10. according to the method described in claim 9, it is characterized in that, the reduction of sodium oxide content described in step (1) 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 9.5 weights
Measure %.
11. according to the method described in claim 9, it 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 5.5
~9.5 weight % are, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.
12. according to the method described in claim 9, it 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
NaY molecular sieve, rare-earth salts and water are formed into mixture, stirring.
13. the method according to claim 9 or 12, 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 decationized Y sieve water, under stirring, be added rare-earth salts and/
Or rare-earth salt solution carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions is：Exchange temperature is 15~95
DEG C, swap time is 30~120 minutes, and the rare-earth salt solution is the aqueous solution of rare-earth salts.
14. according to the method described in claim 9, it is characterized in that, the rare-earth salts be rare earth chloride or nitric acid rare earth,
The phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
15. according to the method described in claim 9, it is characterized in that, step (2) described calcination temperature be 380~460 DEG C, institute
It is 40~80% water vapour atmospheres to state calcination atmosphere, and the roasting time is 5~6 hours.
16. according to the method described in claim 9, it is characterized in that, the Y that the lattice constant obtained in step (2) reduces
The lattice constant of type molecular sieve is 2.450nm~2.462nm.
17. according to the method described in claim 9, wherein, the P Modification treatment conditions described in step (3) are：By the structure cell
The Y type molecular sieve sample that constant reduces is contacted with the exchange liquid containing phosphorus compound, exchange reaction under conditions of 15~100 DEG C
It 10~100 minutes, filters, washing；Wherein, the weight ratio for exchanging water and molecular sieve in liquid is 2~5 preferably 3~4, with P2O5Meter
Phosphorus and the weight ratio of molecular sieve be：0.0005~0.10 preferably 0.001~0.05.
18. according to the method described in claim 9, it is characterized in that, the Y types that step (3) the phosphorous lattice constant reduces
Water content in molecular sieve is no more than 1 weight %.
19. according to the method described in claim 9, it is characterized in that, the washing methods described in step (4) is washed to be washed with water
The condition of washing is：Molecular sieve：H2Weight ratio=1 O:6~15, pH value is 2.5~5.0, and wash temperature is 30~60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710093670.6A CN108452827B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710093670.6A CN108452827B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108452827A true CN108452827A (en) | 2018-08-28 |
| CN108452827B CN108452827B (en) | 2020-03-24 |
Family
ID=63228881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710093670.6A Active CN108452827B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108452827B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252385A (en) * | 2019-06-17 | 2019-09-20 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking catalyst |
| WO2020035014A1 (en) * | 2018-08-17 | 2020-02-20 | 中国石油化工股份有限公司 | Modified y molecular sieve, catalytic cracking catalyst containing same, and preparation therefor and application thereof |
| WO2020038350A1 (en) * | 2018-08-20 | 2020-02-27 | 中国石油化工股份有限公司 | Modified y-shaped molecular sieve, catalytic cracking catalyst containing same, preparation method and application thereof |
| CN112717985A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof |
| CN113318778A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN115594193A (en) * | 2022-10-26 | 2023-01-13 | 山东齐鲁华信高科有限公司（Cn） | High-hydrophobicity mesoporous Y-type molecular sieve and preparation method thereof |
| CN116020522A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN116037196A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Super-stable modified Y-type molecular sieve containing phosphorus and preparation method thereof |
| CN116037195A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Low-coke catalytic cracking catalyst and preparation method thereof |
Citations (2)
| 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 |
| 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 |
-
2017
- 2017-02-21 CN CN201710093670.6A patent/CN108452827B/en active Active
Patent Citations (2)
| 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 |
| 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 |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11517887B2 (en) | 2018-08-17 | 2022-12-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof |
| WO2020035014A1 (en) * | 2018-08-17 | 2020-02-20 | 中国石油化工股份有限公司 | Modified y molecular sieve, catalytic cracking catalyst containing same, and preparation therefor and application thereof |
| WO2020038350A1 (en) * | 2018-08-20 | 2020-02-27 | 中国石油化工股份有限公司 | Modified y-shaped molecular sieve, catalytic cracking catalyst containing same, preparation method and application thereof |
| US11541377B2 (en) | 2018-08-20 | 2023-01-03 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof |
| CN110252385A (en) * | 2019-06-17 | 2019-09-20 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking catalyst |
| CN112717985A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof |
| CN112717985B (en) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof |
| CN113318778A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN113318778B (en) * | 2020-02-28 | 2023-10-13 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN116020522A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN116037196A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Super-stable modified Y-type molecular sieve containing phosphorus and preparation method thereof |
| CN116037195A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Low-coke catalytic cracking catalyst and preparation method thereof |
| CN115594193A (en) * | 2022-10-26 | 2023-01-13 | 山东齐鲁华信高科有限公司（Cn） | High-hydrophobicity mesoporous Y-type molecular sieve and preparation method thereof |
| CN115594193B (en) * | 2022-10-26 | 2023-08-15 | 山东齐鲁华信高科有限公司 | High-hydrophobicity mesoporous Y-type molecular sieve and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108452827B (en) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108452827A (en) | A kind of catalytic cracking catalyst | |
| CN108452830A (en) | A kind of catalytic cracking catalyst | |
| JP7083360B2 (en) | Catalytic cracking catalyst and its production method | |
| CN108452837A (en) | A kind of catalytic cracking catalyst | |
| TW201833028A (en) | Modified y-type molecular sieve, preparation method therefor, and catalyst containing same | |
| CN108452832A (en) | A kind of phosphorous and rare earth modified Y type molecular sieve and preparation method thereof rich in second hole | |
| CN108452838A (en) | A kind of catalytic cracking catalyst | |
| CN108452829A (en) | A kind of catalytic cracking catalyst | |
| CN108452833A (en) | A kind of catalytic cracking catalyst | |
| CN108452825A (en) | Magnesium-modified high silicon super-stable Y molecular sieves of one kind and preparation method thereof | |
| CN100537029C (en) | Catalytic cracking catalyst | |
| CN108452834A (en) | A kind of catalytic cracking catalyst | |
| CN110193376A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN108452835A (en) | A kind of catalytic cracking catalyst | |
| CN110193377A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN107971000A (en) | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof | |
| CN108452831A (en) | It is a kind of to contain rare earth modified Y type molecular sieve and preparation method thereof rich in second hole | |
| CN108452828A (en) | A kind of phosphorous and rare earth super-stable Y molecular sieves and preparation method thereof | |
| CN108452826A (en) | A kind of catalytic cracking catalyst | |
| CN110841695B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN108455625B (en) | High-stability modified Y-type molecular sieve and preparation method thereof | |
| CN110841693B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110652998B (en) | High-stability modified Y-type molecular sieve for producing more isomeric hydrocarbon and preparation method thereof | |
| CN108452836A (en) | A kind of catalytic cracking catalyst | |
| CN110841690B (en) | Modified Y-type molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |