CN108452826A - A kind of catalytic cracking catalyst - Google Patents
A kind of catalytic cracking catalyst Download PDFInfo
- Publication number
- CN108452826A CN108452826A CN201710093369.5A CN201710093369A CN108452826A CN 108452826 A CN108452826 A CN 108452826A CN 201710093369 A CN201710093369 A CN 201710093369A CN 108452826 A CN108452826 A CN 108452826A
- Authority
- CN
- China
- Prior art keywords
- weight
- molecular sieve
- content
- modified zeolite
- magnesium
- 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
-
- 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
-
- 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
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of catalytic cracking catalyst contains Modified Zeolite Y, alumina binder and clay containing magnesium；The rare earth oxide content of the magnesium-modified high silicon super-stable Y molecular sieves is 4 weight of weight %~10 %, content of magnesia is 0.1~4 weight %, sodium oxide content is 0.3 weight of weight %~0.8 %, 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%~30%, lattice constant is 2.440nm~2.455nm, in the Modified Zeolite Y non-framework aluminum content account for total aluminium content percentage be not higher than 20%, lattice collapse temperature be not less than 1045 DEG C.The Modified Zeolite Y has higher heavy oil conversion activity and lower coke selectivity, has higher diesel yield, yield of light oil and total liquid yield.
Description
Technical field
The Modified Zeolite Y of high stability and preparation method thereof containing magnesium that the present invention relates to a kind of.
Background technology
Include the catalytic cracking catalyst of the Y-type high-Si zeolite containing magnesium, it can increasing output of diesel oil for heavy oil conversion.Currently, industrial
On produce Y-type high-Si zeolite mainly use hydro-thermal method：NaY zeolite is subjected to multiple rare earth ion exchanged and the roasting of multiple high temp hydro-thermal
It burns, the Y-type high-Si zeolite containing rare earth can be prepared, this is also to prepare Y-type high-Si zeolite method the most conventional, but hydro-thermal
Method prepares rare-earth type high-silicon gamma-zeolite and is disadvantageous in that：Since excessively harsh hydrothermal conditions can destroy the knot of zeolite
Structure cannot obtain the very high y-type zeolite of silica alumina ratio；Though the generation of the outer aluminium of skeleton is to improving the stability of zeolite and forming new acid
Center is beneficial, but the excessive outer aluminium of skeleton reduces the selectivity of zeolite；In addition, many dealuminzation holes in zeolite cannot be timely
It is filled by the silicon migrated out on skeleton, often results in the lattice defect of zeolite, the crystal retention of zeolite is relatively low；Therefore, hydro-thermal
The heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that method is prepared are poor, show that its lattice collapse temperature is low, through hydro-thermal
Its crystallinity retention rate and specific surface area retention rate are low after 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.United States Patent (USP) US5340957 and US5206194 are provided
Method in, the SiO of raw material NaY zeolite2/Al2O3Than being 6.0, cost is higher.The method is also that NaY is carried out rare earth exchanged
Afterwards, the shortcomings that then carrying out hydro-thermal process, equally exist aforesaid U.S. Patent 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.
US4273753, US4438178, CN1382525A, CN1194941A, CN1683244A, which are disclosed, utilizes SiCl4Gas chemistry is de-
The method of aluminum ultrastable.But the prior art does not propose how that further increasing gas phase super stable molecular sieve heavy oil splits
Change activity.
Existing high-silicon Y-Zeolite Cracking catalyst its heavy oil cracking activity containing magnesium is not high, and diesel oil selectivity is not high.
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, which contains the Modified Zeolite Y (Y type molecular sieve is also referred to as y-type zeolite) containing magnesium, has higher heavy oil
Cracking activity and higher diesel oil selectivity.The invention solves second technical problem be to provide a kind of catalytic cracking and urge
The preparation method of agent.
The present invention provides a kind of catalytic cracking catalyst, contain in terms of butt 10 weight of weight %~50 % containing magnesium
The weight of the alumina binder of the weight % of Modified Zeolite Y, in terms of aluminium oxide 10 weight~40 and in terms of butt 10 weight~80
Measure the clay of %：The rare earth oxide content of the Modified Zeolite Y containing magnesium is 4~11 weight %, content of magnesia 0.1
~4 weight %, sodium oxide content are 0.3~0.8 weight %, and total pore volume is 0.33~0.39mL/g, the Modified Zeolite Y
The percentage that the pore volume for the second hole that aperture is 2nm~100nm accounts for the Modified Zeolite Y total pore volume is 10%~
30%, lattice constant is 2.440nm~2.455nm, and non-framework aluminum content accounts for the percentage of total aluminium content in the Modified Zeolite Y
Than being not higher than 20%, lattice collapse temperature is not less than 1045 DEG C.
Modified Zeolite Y provided by the invention, lattice collapse temperature are not less than 1045 DEG C, it is preferred that the molecular sieve is brilliant
1045 DEG C~1075 DEG C, for example, 1050~1070 DEG C of lattice collapse temperature.
In catalytic cracking catalyst provided by the invention, content of magnesia is preferred in the Modified Zeolite Y containing magnesium
0.5~3 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium, lattice constant is
2.440nm~2.455nm is, for example, 2.441~2.453nm or 2.442~2.451nm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium is high-Si Y-type molecular sieve,
Its framework si-al ratio (SiO2/Al2O3Molar ratio) it is 7.3~14, for example,：7.8~13.2 or 8.5~12.6.
In catalytic cracking catalyst provided by the invention, non-framework aluminum content accounts in the Modified Zeolite Y containing magnesium
The percentage of 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 containing magnesium, 800 DEG C, normal pressure, 100
It is, for example, 30~45% or 32~40% that crystal retention under volume % water vapour atmospheres after aging 17 hours, which is 30% or more,
Or 35~44% or 38~43%.The normal pressure is 1atm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium, relative crystallinity is not low
In 55%, it is preferred that the relative crystallinity of the Modified Zeolite Y provided by the invention be 55~68%, for example, 58~
66%.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium, a kind of embodiment,
Specific surface area is 600~670m2/ g is, for example, 610~660m2/ g or 620~655m2/ g or 630~650m2/g。
In catalytic cracking catalyst provided by the invention, it is preferred that the Modified Zeolite Y total pore volume containing magnesium is
0.33~0.39mL/g is, for example, 0.35~0.39mL/g or 0.35~0.37mL/g.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium, aperture (referring to diameter) is
The percentage that the pore volume of the second hole of 2.0nm~100nm accounts for total pore volume is 10%~30%, for example, 15~25% or 17
~22% or 20~28%.
In catalytic cracking catalyst provided by the invention, contain rare earth element in the Modified Zeolite Y containing magnesium, it should
With RE in Modified Zeolite Y containing magnesium2O3The rare earth oxide content of meter is that 4~11 weight % are preferably 4.5~10 weight %
Such as it is 5~9 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y containing magnesium, sodium oxide content is no more than
0.8%, can be, for example, 0.5~0.80 weight % or 0.4~0.6 weight % for 0.3~0.8 weight %.
In catalytic cracking catalyst provided by the invention, the content of the Modified Zeolite Y containing magnesium is in terms of butt
10~50 weight % are preferably that 15~45 weight % are, for example, 25~40 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 %.
Catalyst provided by the invention also contains other molecular sieves other than the Modified Zeolite Y containing magnesium, with
On the basis of the weight of the catalyst, in terms of butt the content of its described molecular sieve be, for example, 0~40 weight % be, for example, 0~
30 weight % or 1~20 weight %.The molecular sieve that other molecular sieves use in catalytic cracking catalyst, such as with
The one or more of MFI structure zeolite, Beta zeolites, other y-type zeolites, non-zeolite molecular sieve.Preferably, described in terms of butt
The content of other Y type molecular sieves for example can be 1~40 weight % no more than 40 weight % or be 0~20 weight %.It is described its
It is one or more in its y-type zeolite such as REY, REHY, DASY, SOY, PSRY, MFI structure zeolite such as HZSM-5, ZRP,
It is one or more in ZSP, beta zeolites such as H β, non-zeolite molecular sieve such as aluminium phosphate molecular sieve (AlPO molecular sieves), silicon
It is one or more in aluminium phosphorus molecular sieve (SAPO molecular sieve).
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.Generally include to be formed including containing magnesium Modified Zeolite Y, binder, clay and
Slurries, spray drying, optionally washing and the step of drying of water.Spray drying, washing, drying are the prior art, and the present invention does not have
There is particular/special requirement.
The present invention provides a kind of preparation method of catalytic cracking catalyst, including prepares the Modified Zeolite Y containing magnesium, will
Include the steps that Modified Zeolite Y, alumina binder, the raw material of clay and water containing magnesium form slurries, spray drying；
The Modified Zeolite Y preparation method containing magnesium 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 preferably, SiCl4：The Y type molecular sieve that the lattice constant that the step of in terms of butt (2) obtains reduces
Weight ratio=0.1~0.7：1, in 10 minutes to 5 hours reaction time, then washed, filtering, optionally drying obtains super steady
Modified Zeolite Y；Wherein, the water content for the Y type molecular sieve sample that the lattice constant reduces is preferably more than 1 weight %；
If water content does not surpass (in the Y type molecular sieve sample that roasting obtains) in the Y type molecular sieve sample that step (2) modification obtains
1 weight % is crossed, is used directly for contacting the progress reaction with silicon tetrachloride, if step (2) roasts obtained Y type molecules
Water content is more than 1 weight % in sieve sample, the Y type molecular sieve sample of the lattice constant reduction that step (2) roasting obtains into
Row is dry to make its water content be less than 1 weight %；
(4) the super steady Modified Zeolite Y that step (3) obtains is contacted with magnesium compound and carries out magnesium-modified processing.
Catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking, the cracking of the more existing Y type molecular sieve containing magnesium
Catalyst has higher heavy oil conversion activity and lower coke selectivity, has higher diesel yield, has higher light
Matter oil yield and total liquid yield.Catalytic cracking catalyst provided by the invention can be used for heavy oil or poor oil conversion.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y preparation method, can prepare
The high silicon superstable gamma-type molecule containing magnesium with certain two level pore structure of high-crystallinity, high thermal stability and high hydrothermal stability
It sieves, aluminium is evenly distributed in the molecular sieve, and non-framework aluminum content is few.
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
The alumina binder of the weight % of the Modified Zeolite Y containing magnesium of~50 weight %, in terms of aluminium oxide 10 weight~40 and with
The clay of the weight % of 10 weight of butt meter~80.Preferably, the catalytic cracking catalyst contain in terms of butt 25 weight %~
The alumina binder of the weight % of Modified Zeolite Ys of the 40 weight % containing magnesium, in terms of aluminium oxide 20 weight~35 and with butt
Count the clay of the weight % of 30 weight~50.
In catalytic cracking catalyst provided by the invention, contain the Modified Zeolite Y containing magnesium, a kind of embodiment, institute
The Modified Zeolite Y containing magnesium is stated, rare earth oxide content is 4~11 weight %, preferably 4.5~10 weight %, magnesia
Content be 0.1~4 weight % such as 0.5~3 weight %, sodium oxide content be 0.3~0.8 weight %, preferably 0.35~
0.75 weight % such as 0.4~0.6 weight %, total pore volume are 0.33~0.39mL/g, and aperture is the two level of 2nm~100nm
The pore volume in hole account for total pore volume percentage be 10%~30%, preferably 15%~25%, lattice constant be 2.440nm~
2.455nm, framework si-al ratio (SiO2/Al2O3Molar ratio) be：7~14, non-framework aluminum content accounts for total aluminium content in the molecular sieve
Percentage be not higher than 20%, preferably 13~19, relative crystallinity not less than 55% be, for example, 55~68%, lattice avalanche temperature
Degree is 1045 DEG C~1075 DEG C such as 1047~1065 DEG C.
Catalytic cracking catalyst provided by the invention, the Modified Zeolite Y preparation process containing magnesium 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, the Modified Zeolite Y preparation method containing magnesium
In, NaY molecular sieve and earth solution are subjected to ion-exchange reactions in step (1), it is dilute to obtain containing for sodium oxide content reduction
The Y type molecular sieve of the conventional unit cell dimension of soil.The NaY molecular sieve, can be commercially available or prepares, Yi Zhongshi according to existing method
Mode is applied, 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 %.Step (1)
The NaY molecular sieve carries out ion-exchange reactions with earth solution, and it is, for example, 65~95 that exchange temperature, which is preferably 15~95 DEG C,
DEG C, swap time is preferably such as 45~90 minutes 30~120 minutes.NaY molecular sieve (in terms of butt):Rare-earth salts is (with RE2O3
Meter):H2O=1:0.01~0.18:5~15 weight ratios.A kind of embodiment, the NaY molecular sieve are carried out with earth solution
Ion-exchange reactions includes, according to NaY molecular sieve:Rare-earth salts:H2O=1:0.01~0.18:5~15 weight ratio is by NaY points
Son sieve (also referred to as NaY zeolite), rare-earth salts and water form mixture, in 15~95 DEG C of such as 65~95 DEG C stirrings, preferably stir 30
~120 minutes progress rare earth ions are exchanged with sodium ion.NaY molecular sieve, rare-earth salts and water are formed into mixture, can be incited somebody to action
NaY molecular sieve and water form slurries, and the aqueous solution of rare-earth salts and/or rare-earth salts is then added in the slurries, described
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.The rare earth is for example
It is one or more in La, Ce, Pr, Nd and mischmetal, it is preferred that contain La, Ce, Pr and Nd in the mischmetal
In it is one or more, or also contain at least one of rare earth in addition to La, Ce, Pr and Nd.Washing described in step (1)
It washs, 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
(1) content of rare earth of the Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content obtained reduces is with RE2O3It is calculated as
4.5~13 weight % are, for example, 5.5~13 weight or 5.5~12 weight %, and sodium oxide content is, for example, no more than 9.5 weight %
5.5~9.5 weight %, lattice constant are 2.465nm~2.472nm.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y preparation method containing magnesium
In, 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 in step (2)
It roasts 4.5~7 hours and is handled under steam atmosphere, it is preferred that the calcination temperature described in step (2) is 380~460 DEG C, roasting
Burning atmosphere is 40~80 volume % water vapour atmospheres (water vapour containing 40-80 volumes % in atmosphere), and roasting time is 5~6
Hour.In the water vapour atmosphere contain 30~90 volume % vapor, also contain other gases, such as air, helium or
It is one or more in nitrogen.The Y type molecular sieve that lattice constant described in step (2) reduces, lattice constant 2.450nm
~2.462nm.It is preferred that also the molecular sieve that roasting obtains is dried in step (2), so that the Y that the lattice constant reduces
Water content in type molecular sieve is preferably more than 1 weight %.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y preparation method containing magnesium
In, in step (3), 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 excellent
350~500 DEG C are selected as, conventional washing methods may be used in the washing methods described in step (3), and such as exhaustion of yang can be washed with water
Ionized 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
The condition of washing 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 is preferably 2.5~5.0, and wash temperature is 30~60 DEG C.Preferably, the washing makes to examine in the cleaning solution after washing
Free Na is not measured+, Cl-And Al3+Plasma, usually Na in the sieve sample after washing+, Cl-And Al3+Ion is respective
Content is no more than 0.05 weight %.
Catalytic cracking catalyst preparation method provided by the invention, the Modified Zeolite Y preparation method containing magnesium
In, the super steady Modified Zeolite Y that step (3) obtains is carried out magnesium-modified processing by step (4) with magnesium compound.A kind of embodiment party
Formula, sample, which is added, after including the super steady Modified Zeolite Y filter cake samples for obtaining step (3) or being dry contains magnesium compound example
As magnesium salts solution in, stir 10~120 minutes under conditions of 5~50 DEG C, then, ammonium hydroxide be added, the PH for adjusting solution is
7.5~10, after stirring evenly, neutrality water wash be used in combination in filtering, later, filtration cakes torrefaction is placed in Muffle furnace in 500~
650 DEG C of roastings such as 1~5 hour or 2~3 hours 1 hour or more, obtain magnesium-modified high silicon super-stable Y molecular sieves.Wherein,
In the dosage of magnesium-containing compound solution and molecular sieve, make the weight ratio of water and molecular sieve (in terms of butt) be 1~6, preferably 1.5~
3.5, magnesium (in terms of magnesia) and the weight ratio of molecular sieve (in terms of butt) are：0.001~0.04, preferably 0.005~0.035；
Preferably, the magnesium salts is magnesium chloride and/or magnesium nitrate.
Catalytic cracking catalyst preparation method provided by the invention, the preparation side of the Modified Zeolite Y containing magnesium
Method, a kind of embodiment include 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 the super steady Modified Zeolite Y filter cake of gas phase；
(4) the super steady Modified Zeolite Y filter cake of gas phase that step (3) obtains is mixed with magnesium salt solution, at 5~50 DEG C
Under conditions of stir 10~120 minutes, then, ammonium hydroxide is added, the PH for adjusting solution is 7.5~10, after stirring evenly, filtering,
Neutral water wash is used in combination, later, 1~3 hour hour will be roasted in 500~650 DEG C after filtration cakes torrefaction, it is super to obtain magnesium-modified high silicon
Stabilization Y-type molecular sieve.Wherein, in the mixture that the super steady Modified Zeolite Y of the aqueous solution of magnesium salts and gas phase is formed, water and molecule
The weight ratio of sieve is 1~6, preferably 1.5~3.5, and magnesium (in terms of magnesia) and the weight ratio of molecular sieve are：0.001~0.04, it is excellent
It is selected as 0.005~0.035.
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.
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
Lattice 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, Jin Erji with the XRF total silica alumina ratios measured
Calculate the ratio of non-skeleton Al and total Al.Crystal structure collapse temperature is measured by differential thermal analysis (DTA).
In each comparative example and embodiment, 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 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 20 liters of decationized Y sieve water
Washing, is then filtered, and molecular sieve filter cake samples is added in the solution containing magnesium chloride, wherein the weight ratio of water and molecular sieve
It is 2.5, magnesium (in terms of magnesia) and the weight ratio of molecular sieve are：0.01；It stirs 40 minutes under conditions of 25 DEG C, then, adds
Enter ammonium hydroxide, it is 8.5 to adjust pH value, is stirred evenly, and filters, deionized water water wash is used in combination, later, by after filtration cakes torrefaction in 550
DEG C roasting 2 hours, obtain it is provided by the invention containing magnesium Modified Zeolite Y (also referred to as magnesium-modified high silicon superstable gamma-type molecule
Sieve), it is denoted as SZ1.Its physico-chemical property is listed in Table 1 below, by SZ1 naked state through 800 DEG C, 1atm, 100% vapor aging 17
After hour, 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 is protected
Office Copy 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 in 8146 grams of decationized Y sieve water, the hydrochloric acid of a concentration of quality of 210ml 36% is added under stirring,
Scattered kaolin slurry is added in acidification after sixty minutes, and levigate SZ1 molecular sieves 1500 grams (butts) are then added, and stirring is equal
After even, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as SC1.Contain SZ1 in obtained SC1 catalyst
30 weight % of molecular sieve, 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 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
Under conditions of 480 DEG C, reacts 1.5 hours, later, with 20 liters of decationized Y sieve water washings, then filter, by molecular sieve filter cake samples
It is added in the solution containing magnesium nitrate, wherein the usage ratio of solution and molecular sieve containing magnesium nitrate is the weight of water and molecular sieve
Than being 2.3, magnesium (in terms of magnesia) and the weight ratio of molecular sieve are amount：0.02, then stirred 35 minutes under conditions of 30 DEG C,
Then, ammonium hydroxide is added, the PH for adjusting solution is 9, and after stirring evenly, filtering is used in combination deionized water to elute, later, filter cake is done
Dry be placed in Muffle furnace roasts 2 hours in 590 DEG C, obtains magnesium-modified high silicon super-stable Y molecular sieves, is denoted as SZ2.Its object of SZ2
Change property to be listed in Table 1 below, by SZ2 in naked state through 800 DEG C, (100% water steams within 17 hours for 100% vapor aging in 17 hours
Gas aging refers to aging 17 hours under 100% water vapour atmosphere) after, the zeolite before and after analyzing SZ2 agings with the method for XRD
Crystallinity and calculate 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 to obtain kaolin slurry in 60 minutes.Take 2049 grams of aluminium oxide
The boehmite that content is 61 weight % is added in 8146 grams of decationized Y sieve water, and it is a concentration of that 210ml is added under stirring
The hydrochloric acid of quality 36%, acidification are added the kaolin slurry, 1500 grams of levigate SZ2 molecular sieves are then added after sixty minutes
(butt) after stirring evenly, carries out spray drying and carrying out washing treatment, and drying obtains catalyst, is denoted as SC2.Obtained SC2 is urged
Contain 30 weight % of SZ2 molecular sieves, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol in agent.
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 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 20 liters of decationized Y sieve water washings, then filter, then, by molecular sieve filter cake
Sample is added in the solution containing magnesium chloride, is stirred under conditions of 20 DEG C 45 minutes, then, ammonium hydroxide is added, adjusts solution
PH is 9.2, and after stirring evenly, water wash is used in combination in filtering, later, filtration cakes torrefaction is placed in Muffle furnace and roasts 2 in 580 DEG C
Hour, obtain magnesium-modified high silicon super-stable Y molecular sieves.Wherein, in the mixture that the solution of magnesium chloride and molecular sieve are formed, water
Weight ratio with molecular sieve is 3.2, and magnesium (in terms of magnesia) and the weight ratio of molecular sieve are：0.025, it is denoted as SZ3.Its materialization
Matter is listed in Table 1 below, and by SZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, SZ3 is analyzed with the method for XRD
The crystallinity of zeolite before and after aging 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 to obtain scattered kaolin slurry in 60 minutes.Take 2049
The boehmite that gram alumina content is 61 weight % is added in 8146 grams of decationized Y sieve water, is added under stirring
The hydrochloric acid of a concentration of quality of 210ml 36%, acidification are added scattered kaolin slurry, are then added levigate after sixty minutes
SZ3 molecular sieves 1500 grams (butts) after stirring evenly, carry out spray drying and carrying out washing treatment, and drying obtains catalyst, is denoted as
SC3.Contain 30 weight % of SZ3 molecular sieves, 42 weight % of kaolin, boehmite 25 in wherein obtained SC3 catalyst
Weight %, 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
Hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) is carried out afterwards, later, is added to 20 liters of decationized Y sieves
Stirring makes it be uniformly mixed in aqueous solution, 1000 grams of (NH4)2SO4, stirring is warming up to 90~95 DEG C and kept for 1 hour, then mistake
Filter is washed, second of hydrothermal modification treatment of progress after filter cake is dry in 120 DEG C, 650 DEG C of temperature, is roasted under 100% water vapour
5 hours, ion exchange super steady hydro-thermal super-stable Y molecular sieves without rare earth of hydro-thermal twice twice are obtained, DZ1 is denoted as.Its object
Change property to be listed in Table 1 below, by DZ1 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, with the method point of XRD
It has analysed the crystallinity of the zeolite before and after DZ1 agings and has calculated 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, the condition of hydrothermal modification treatment：It is roasted 5 hours under 650 DEG C of temperature, 100% water vapour atmosphere, it
Afterwards, being added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and the RE (NO of 200ml are added3)3Solution is (with RE2O3
It is a concentration of to count earth solution：319g/L) and 900 grams of (NH4)2SO4, stirring is warming up to 90~95 DEG C and kept for 1 hour, then mistake
Filter is washed, second of hydrothermal modification treatment of progress after filter cake is dry in 120 DEG C, 650 DEG C of temperature, is roasted 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.
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 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RE (NO of 650ml3)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, then, the addition of molecular sieve filter cake samples is contained into magnesium chloride
In solution, being stirred under conditions of 20 DEG C 45 minutes, then, ammonium hydroxide is added, the PH for adjusting solution is 9.2, after stirring evenly, mistake
Filter, is used in combination water wash, later, filtration cakes torrefaction is placed in Muffle furnace and is roasted 2 hours in 580 DEG C, it is super to obtain magnesium-modified high silicon
Stabilization Y-type molecular sieve.Wherein, in the mixture that the solution of magnesium chloride and molecular sieve are formed, the weight ratio of water and molecular sieve is
3.2, magnesium (in terms of magnesia) and the weight ratio of molecular sieve are：0.025, it is 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, the zeolite before and after analyzing DZ3 agings with the method for XRD
Crystallinity 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
Embodiment 4~6 illustrates the catalytic cracking activity and its stability of Modified Zeolite Y provided by the invention.
Respectively by SC1, SC2 and SC3 catalyst after 800 DEG C, 4 hours or 17 hours 100% vapor agings, evaluation is urged
The light oil microactivity of agent, evaluation result are 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
Comparative example 4~6 illustrate comparative example 1~3 provide method prepare super-stable Y molecular sieves catalytic cracking activity and
Its stability.
It is micro- to evaluate its light oil after 800 DEG C, 4 hours or 17 hours 100% vapor agings for DC1, DC2 and DC3 catalyst
Anti- activity.Evaluation method is shown in embodiment 6, and evaluation result is listed in Table 3 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
Embodiment 7~9
Embodiment 7~9 illustrates the catalytic cracking reaction performance of catalytic cracking catalyst provided by the invention.
It is anti-in small fixed flowing bed by SC1, SC2, SC3 catalyst after 800 DEG C, 100% vapor aging 17 hours
It answers and evaluates its catalytic cracking reaction performance on device (ACE), cracked gas and product oil are not collected by gas chromatographic analysis.Catalyst
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 be shown in Table
4, evaluation result is shown in Table 5.
Comparative example 7~9
Comparative example 7~9 illustrates the catalytic cracking reaction performance for the catalytic cracking catalyst that comparative example 1~3 provides.
DC1, DC2 and DC3 catalyst are under 800 DEG C, 100% steam atmosphere after aging 17 hours, in small-sized fixed stream
Its catalytic cracking reaction performance is evaluated on fluidized bed reactor (ACE), evaluation method is shown in that embodiment 7, the feedstock property of ACE experiments are shown in
Table 4, evaluation result is listed in Table 5 below.
4 ACE of table 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 | 1.39 | 1.41 | 1.38 | 1.55 | 1.48 | 1.47 |
| Liquefied gas | 15.87 | 15.87 | 16.04 | 16.86 | 15.33 | 16.03 |
| Coke | 4.48 | 4.61 | 4.32 | 8.33 | 7.61 | 6.15 |
| Gasoline | 45.29 | 44.91 | 43.99 | 38.55 | 43.91 | 49.19 |
| Diesel oil | 25.35 | 26.69 | 26.46 | 20.17 | 19.25 | 18.88 |
| Heavy oil | 7.62 | 6.51 | 7.81 | 14.54 | 12.42 | 8.28 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio/weight % | 67.03 | 66.8 | 65.73 | 65.29 | 68.33 | 72.84 |
| Coke selectivity/weight % | 6.68 | 6.90 | 6.57 | 12.76 | 11.14 | 8.44 |
| Yield of light oil/weight % | 70.64 | 71.6 | 70.45 | 58.72 | 63.16 | 68.07 |
| Total liquid yield/weight % | 86.51 | 87.47 | 86.49 | 75.58 | 78.49 | 84.1 |
| Diesel and gasoline ratio | 0.56 | 0.59 | 0.60 | 0.52 | 0.44 | 0.38 |
By table 3 and table 5 as it can be seen that catalytic cracking catalyst provided by the invention has higher hydrothermal stability, have bright
Lower coke selectivity is shown, there is considerably higher liquid to receive, yield of light oil is considerably higher, and diesel yield improves, diesel and gasoline ratio
Higher, heavy oil conversion activity higher.
Claims (18)
1. a kind of catalytic cracking catalyst, the Modified Zeolite Y containing magnesium containing in terms of butt 10 weight of weight %~50 %,
The clay of the weight % of the alumina binder of the weight % of in terms of aluminium oxide 10 weight~40 and in terms of butt 10 weight~80；, institute
The rare earth oxide content for stating the Modified Zeolite Y containing magnesium is the 4 weight % of weight %~11, and content of magnesia is 0.1~4 weight
% is measured, sodium oxide content is the 0.3 weight % of weight %~0.8, and total pore volume is 0.33mL/g~0.39mL/g, modification Y types
The percentage that the pore volume for the second hole that the aperture of molecular sieve is 2nm~100nm accounts for total pore volume is 10%~30%, and structure cell is normal
Number is 2.440nm~2.455nm, and non-framework aluminum content accounts for the percentage of total aluminium content and is not higher than in the Modified Zeolite Y
20%, lattice collapse temperature is not less than 1045 DEG C.
2. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y hole containing magnesium
The percentage that the pore volume for the second hole that diameter is 2nm~100nm accounts for total pore volume is 15%~25%.
3. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that in the Modified Zeolite Y containing magnesium
The percentage that non-framework aluminum content accounts for total aluminium content is 13~19%, and framework si-al ratio is with SiO2/Al2O3Molar ratio computing 7~14.
4. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y containing magnesium is brilliant
1045 DEG C~1075 DEG C of lattice collapse temperature.
5. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that in the Modified Zeolite Y containing magnesium
Content of magnesia is 0.5~3 weight %.
6. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that 800 DEG C, normal pressure, 100% vapor gas
After atmosphere aging in 17 hours, the opposite crystal retention of the Modified Zeolite Y containing magnesium be 30% or more be, for example, 30~
45%.
7. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y containing magnesium
Relative crystallinity is 55~68%.
8. according to any catalytic cracking catalyst of claim 1~7, which is characterized in that the modification Y types containing magnesium point
The rare earth oxide content of son sieve is 4.5~10 weight %, and sodium oxide content is 0.4~0.6 weight %, lattice constant 2.442
~2.451nm, framework si-al ratio are 8.5~12.6.
9. a kind of preparation method of catalytic cracking catalyst, including will include Modified Zeolite Y, alumina binder containing magnesium
The step of slurries, spray drying being formed with the raw material and water of clay；The Modified Zeolite Y preparation method containing magnesium includes
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) Y type molecular sieve for reducing the lattice constant and silicon tetrachloride gas haptoreaction, washing and filtering, obtain height
Silicon super-stable Y molecular sieves；The haptoreaction, SiCl4：The weight for the Y type molecular sieve that the lattice constant in terms of butt reduces
Measure ratio=0.1~0.7：1, reaction temperature is 200 DEG C~650 DEG C, the reaction time is 10 minutes to 5 hours；
(4) the high silicon super-stable Y molecular sieves that step (3) obtains are modified processing with magnesium compound.
10. according to the method described in claim 9, 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 9.5 weight %.
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 is 5~
9.5 weight % are, for example, 5.5~9.0 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 will
NaY molecular sieve, rare-earth salts and water form 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, 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.
15. 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, the water content in the Y type molecular sieve that the lattice constant reduces
No more than 1 weight %.
16. according to the method described in claim 9, it is characterized in that, the washing methods described in step (3) is washed to be washed with water
The condition of washing is molecular sieve：H2O=1:6~15, pH value the most 2.5~5.0, wash temperature is 30~60 DEG C.
17. according to the method described in claim 9, it is characterized in that, being modified processing with magnesium compound described in step (4)
Including：Molecular sieve is added in the solution containing magnesium salts, stirs under conditions of 5~50 DEG C 10~120 minutes, then, is added
Ammonium hydroxide, the PH for adjusting solution is 7.5~10, and after stirring evenly, water wash is used in combination in filtering, later, by filtration cakes torrefaction in 500~
650 DEG C roast at least 1 hour, obtain magnesium-modified high silicon super-stable Y molecular sieves, wherein the solution and molecular sieve containing magnesium salts
In the mixture of formation, the weight ratio of water and molecular sieve is 1~6, preferably 1.5~3.5, magnesium salts and molecular sieve in terms of magnesia
Weight ratio is：0.001~0.04, preferably 0.005~0.035.
18. according to the method described in claim 9, it is characterized in that, the rare-earth salts is that rare earth chloride and/or nitric acid are dilute
Soil；The magnesium compound is magnesium chloride and/or magnesium nitrate.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710093369.5A CN108452826B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
| JP2019545357A JP7163298B2 (en) | 2017-02-21 | 2018-02-12 | MAGNESIUM-MODIFIED Y-TYPE MOLECULAR SIEVE, METHOD FOR PRODUCTION THEREOF, AND CATALYST CONTAINING THE SAME |
| RU2019127289A RU2770421C2 (en) | 2017-02-21 | 2018-02-12 | Magnesium-modified y-type molecular sieve, production thereof and catalyst containing same |
| US16/484,880 US11053129B2 (en) | 2017-02-21 | 2018-02-12 | Magnesium modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| MYPI2019004663A MY195283A (en) | 2017-02-21 | 2018-02-12 | Magnesium Modified Y-Type Molecular Sieve, Preparation Thereof and Catalyst Comprising the same |
| PCT/CN2018/076431 WO2018153303A1 (en) | 2017-02-21 | 2018-02-12 | Modified y-type molecular sieve containing magnesium, preparation method therefor, and catalyst containing modified y-type molecular sieve |
| TW107105497A TWI778020B (en) | 2017-02-21 | 2018-02-14 | Magnesium-containing modified Y-type molecular sieve, its preparation method and catalyst comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710093369.5A CN108452826B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108452826A true CN108452826A (en) | 2018-08-28 |
| CN108452826B CN108452826B (en) | 2020-03-24 |
Family
ID=63221986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710093369.5A Active CN108452826B (en) | 2017-02-21 | 2017-02-21 | Catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108452826B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020508214A (en) * | 2017-02-22 | 2020-03-19 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and method for producing the same |
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055000A (en) * | 1990-03-17 | 1991-10-02 | 中国石油化工总公司抚顺石油化工研究院 | A kind of rare-earth, dealuminium zeolite Y and method for making thereof |
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1362366A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of small cell Y-zeolite |
| CN1362472A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of catalytic cracking catalyst |
| 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 |
| CN103159227A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
-
2017
- 2017-02-21 CN CN201710093369.5A patent/CN108452826B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055000A (en) * | 1990-03-17 | 1991-10-02 | 中国石油化工总公司抚顺石油化工研究院 | A kind of rare-earth, dealuminium zeolite Y and method for making thereof |
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1362366A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of small cell Y-zeolite |
| CN1362472A (en) * | 2001-01-04 | 2002-08-07 | 中国石油化工股份有限公司 | Prepn of catalytic cracking catalyst |
| 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 |
| CN103159227A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020508214A (en) * | 2017-02-22 | 2020-03-19 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and method for producing the same |
| JP7083360B2 (en) | 2017-02-22 | 2022-06-10 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and its production method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108452826B (en) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108452827B (en) | Catalytic cracking catalyst | |
| CN108452830A (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 | |
| TWI778020B (en) | Magnesium-containing modified Y-type molecular sieve, its preparation method and catalyst comprising the same | |
| CN108452829B (en) | Catalytic cracking catalyst | |
| CN108452837A (en) | A kind of catalytic cracking catalyst | |
| TW201833029A (en) | Catalytic cracking catalyst and preparation method therefor | |
| CN108452833A (en) | A kind of catalytic cracking catalyst | |
| CN108452838A (en) | A kind of catalytic cracking catalyst | |
| CN108452832A (en) | A kind of phosphorous and rare earth modified Y type molecular sieve and preparation method thereof rich in second hole | |
| CN108452835A (en) | A kind of catalytic cracking catalyst | |
| CN104014361B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN101147875A (en) | Catalytic cracking catalyst | |
| CN108452834A (en) | A kind of catalytic cracking catalyst | |
| CN110193377A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN110193376A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN108452826A (en) | A kind of catalytic cracking catalyst | |
| CN105618107B (en) | A kind of catalytic cracking catalyst 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 | |
| CN108452828B (en) | Ultrastable Y-type molecular sieve containing phosphorus and rare earth and its preparing process | |
| TW202000594A (en) | Modified y type molecular sieve, catalytic cracking catalyst having same, and preparation method therefor and application thereof | |
| CN110841695B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN108455625B (en) | High-stability modified Y-type molecular sieve and preparation method thereof | |
| CN105983432B (en) | A kind of preparation method of the catalytic cracking catalyst containing silicon substrate | |
| CN110653001B (en) | Catalytic cracking catalyst |
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 |