CN106140254B - Modified Y zeolite, preparation method and the Cracking catalyst containing the modified Y zeolite - Google Patents
Modified Y zeolite, preparation method and the Cracking catalyst containing the modified Y zeolite Download PDFInfo
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Abstract
Modified Y zeolite, preparation method and the Cracking catalyst containing the modified Y zeolite, the modified Y zeolite contain the Group IVB metal oxide of 1~15 weight %, the rare earth oxide containing 1~15 weight %；The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is (0.2~0.8) in the modified Y zeolite lattice structure：1, zeolite surface Group IVB tenor and the ratio of zeolite interior Group IVB tenor are not higher than 0.5.The zeolite preparation method include the steps that rare earth ion exchanged roasting, in organic solvent impregnating metal, handle the impregnating metal in organic solvent zeolite and roasting.The Cracking catalyst contains the binder of modified Y zeolite, the clay of 10~60 weight % and 5~50 weight % described in 10~60 weight %.The modified Y zeolite has higher heavy oil cracking ability, yield of gasoline and lower coke yield for catalytic cracking.
Description
Technical field
The present invention relates to a kind of modified Y zeolites.
Background technology
With the increasing weight of catalytic cracking feedstock oils, it is desirable that catalytic cracking catalyst should have both simultaneously it is higher activity and
Higher hydrothermal stability, to improve heavy oil conversion and resistance to heavy metal pollution, it is therefore desirable to the master of catalytic cracking catalyst
It wants active group member Y zeolites that there is very high heat and hydrothermal stability, and keeps suitable acidic and active center distribution.In order to obtain
Artificial synthesized NaY zeolite, is usually modified by the Y zeolites for obtaining the performance.Common method of modifying include ion exchange,
Super stabilizing processing and it is rare earth modified.Wherein rare earth modified Y zeolites have higher heat and hydrothermal stability, are widely used in
In FCC catalyst.Generally, it is considered that rare earth ion can significantly increase the structural stability of Y zeolites, rare earth ion is with hydrated ion shape
Formula exists, such as RE (H2O)n 3+, in roasting and hydrothermal treatment process, part rare earth ion goes hydration to generate RE (OH)2+, and by Y
Zeolite supercage is migrated and is positioned into β cages, and support and stabilization are played to Y skeleton structure of zeolite.Rare earth ion can also modulation Y
The acidity of zeolite, rare earth ion effectively attract OH by polarization to hydrone and inducing action-, while discharging H+。
However, rare earth rapid rise of price causes FCC catalyst cost to steeply rise in recent years.How FCC catalyst is reduced
In content of rare earth become current problem in the urgent need to address.Therefore, other metal-modified Y zeolites of the exploitation in addition to rare earth
With important research significance.CN1350887A disclose it is a kind of simultaneously containing noble metal and non-noble metal modified Y zeolite and its
Preparation method, by carrying out noble metal and non-noble metal ion exchange, hydro-thermal process and ammonium salt exchange etc. to NaY zeolite raw material
The noble metal containing 0.05 weight %~2.0 weights %, the non-noble metal modified Y of 0.5 weight %~15.0 weights % is finally made in step
Zeolite.CN1765492A discloses a kind of alumina support of the zeolite containing Y and preparation method thereof, and wherein modified Y zeolite is to use
Group VIB and/or one or more of group VIII metal W, Ni, Co, Fe, Mo are changed in such a way that cation exchanges
Property.US2007010698A1 discloses a kind of carbon monoxide-olefin polymeric, including a kind of using lanthanide series and group VIIIB metal exchange
Y zeolites, the group VIIIB metal is mainly selected from platinum and palladium, using ion exchange and dipping method that lanthanide series salt is water-soluble
Liquid and group VIIIB aqueous metal salt handle Y zeolites.
The preparation method for the metal-modified Y zeolites that the above patent of invention provides mainly uses ion exchange and dipping method
Y zeolites are handled with aqueous metal salt, and then improve the performance of Y zeolites.It is split however, metal-modified Y zeolites are applied to catalysis
Change process then needs molecular sieve to have higher hydrothermal stability.Compared with rare earth modified Y zeolites, above-mentioned metal-modified Y zeolites
Heat and hydrothermal stability it is poor, to affect its application in catalytic cracking catalyst.
CN101898144A and CN101134576A, which provides a kind of appropriate hetero atom of selection, to carry out skeleton to Y zeolites and changes
Property, the method for raising Y zeolites heat and hydrothermal stability.This method includes using Direct Hydrothermal crystallization synthetic method, and addition is suitable
Hetero atom prepares the MY type zeolites containing cage heteroatom, and MY zeolites are carried out secondary NH4 +Ion exchange and after baking,
A small amount of hetero atom of the same race is added before after baking processing, obtains super steady heteroatom zeolite USMY, thermal stability and hydrothermally stable
Property significantly improved than conventional USY zeolite.However the modified Y zeolite Cracking catalyst yield of gasoline is not high.
Invention content
The invention solves first technical problem be deficiency for existing modified Y zeolite, a kind of modified Y boilings are provided
Stone and preparation method thereof, the modified Y zeolite contain IV B races metal and rare earth metal.The invention solves other technical problem
It is to provide the application process of the modified Y zeolite.
The present invention provides a kind of modified Y zeolite, on the basis of the dry weight of the modified Y zeolite, the modified Y zeolite
Group IVB metal oxide containing 1 weight of weight %~15 %, the rare earth oxide containing 1 weight of weight %~15 % are described
The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is (0.2~0.8) in modified Y zeolite lattice structure：1.
Preferably, the cell parameter of the modified Y zeolite is 2.448~2.458nm, 600~850m of specific surface area2/g。
Preferably, the ratio of the modified Y zeolite surface Group IVB tenor and zeolite interior Group IVB tenor is not
Higher than 0.5.
In modified Y zeolite provided by the invention, containing Group IVB metallic element, the Group IVB metal be selected from Ti, Zr, Hf,
One or more of Rf preferably includes one or both of Ti, Zr.The content of the Group IVB metal oxide is preferably 1
The weight of weight %~10 %.The content of the Group IVB metal oxide is with MO2Meter, wherein M indicate the Group IVB metal.
Modified Y zeolite provided by the invention, containing thulium, the rare earth metal generally comprise La, Ce, Pr,
One or more of Nd preferably includes one or both of La, Ce.The content of the rare earth oxide is preferably 1 weight
Measure the weight of %~10 %.The content of the rare earth oxide is with RE2O3Meter, wherein RE indicate rare earth.
In the modified Y zeolite lattice structure ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum be (0.2~
0.8)：1, for example, (0.3~0.6):1.The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is used27Al MAS NMR methods
The ratio of spectral peak area and spectral peak area at chemical shift 60 indicates at the chemical shift 40 measured.
The modified Y zeolite provided by the invention, IV B races metal ion are predominantly located in zeolite interior, a small amount of to be located at boiling
Stone surface, IV B races tenor of zeolite surface and the ratio of IV B races tenor of zeolite interior are not higher than 0.5, for example,
0.001~0.5 or be 0.2~0.5.IV B races tenor of zeolite surface refers to being existed using X-ray photoelectron spectroscopy (XPS)
The IV B races tenor measured is analyzed within the scope of 2~5nm of zeolite surface.IV B races tenor of zeolite interior refers to zeolite ontology
The difference of IV B races tenor and IV B races tenor of zeolite surface, wherein IV B races tenor of zeolite ontology is passing through
The content of IV B races metal in the zeolite that method is analyzed.
The modified Y zeolite, 2.448~2.458nm of cell parameter, such as cell parameter can be 2.450~
2.455nm；600~850m of specific surface area2/ g, specific surface area are preferably 600~750m2/ g,.
The preparation method of modified Y zeolite provided by the invention includes the following steps：
(1) mixed solution of Y zeolites rare-earth salt solution or rare-earth salts and inorganic ammonium salt is subjected to ion exchange, then mistake
Filter, washing, roast 0.5~5 hour under 300~700 DEG C, 1~100% water vapour, obtain rare earth modified Y zeolites, water contains
Amount is not higher than 5 weight %；
(2) the rare earth modified Y zeolites that step (1) obtains are impregnated into IV B races metal in organic solvent；
(3) the Y zeolites for obtaining step (2) and organic solvent according to solid and liquid weight than 1：(5~50) are mixed in reactor
Close, be filled with it is one or more in inert gas such as nitrogen, helium, in 0.0~2.0MPa of pressure (gauge pressure), room temperature~200
At least 1 hour, such as 1~48 hour are kept at DEG C；Optionally filtering, optionally drying are preferably filtered and dry；
(4) zeolite for passing through step (3) processing roasts in an inert gas atmosphere, 300~700 DEG C of calcination temperature, roasting
Time is 0.5 hour or more, such as 0.5~5 hour.
In the preparation method of the modified Y zeolite provided by the invention, Y zeolites described in step (1) can be selected from NaY,
NaHY、NaNH4Y、NH4Y, HY, USY, one hand over a roasting Y zeolites, DASY zeolites, two that two roasting Y zeolites, two is handed over to hand in a roasting Y zeolites
It is one or more, preferred NaY zeolite.The wherein described one roasting Y zeolites of a friendship are, for example, that NaY zeolite exchanges and primary roasting by primary
Obtained Y zeolites are burnt, DASY zeolites are, for example, the Y zeolites that Y zeolites roast in the presence of water vapor, and two hand over two roasting Y zeolites
For example, NaY zeolite by exchanging the Y zeolites obtained with double roasting twice；Two friendships, one roasting Y zeolites are, for example, that NaY zeolite is passed through
It exchanges twice and once roasts obtained Y zeolites, it is preferred that is described to be exchanged for using H+And/or NH4 +It swaps.
In the preparation method of the modified Y zeolite provided by the invention, the ion exchange described in step (1) is according to dilute
Earth salt is (with RE2O3Meter)：Ammonium salt：Y zeolites (in terms of butt)：Deionized water=0.01~0.15：0~0.6：1：1~50, preferably
0.01~0.10：0~0.4：1：Rare-earth salts, ammonium salt, Y zeolites and deionized water are mixed with beating uniformly by 2~30 weight ratio, are adjusted
The pH value for saving slurries is 2.0~10.0, preferably 2.0~8.0, and it is small that 0.5~5 is exchanged at 25~150 DEG C, at preferably 25~90 DEG C
When, preferably 0.5~3 hour.
In the preparation method of the modified Y zeolite provided by the invention, ammonium salt described in step (1) is selected from ammonium chloride, sulphur
It is one or several kinds of in sour ammonium, ammonium hydrogen sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate.The rare earth
Salt is one or more, the preferably chloride of rare earth in the chloride, nitrate and sulfate of rare earth.Wherein the rare earth is excellent
It is selected as lanthanum and/or cerium.
In the preparation method of the modified Y zeolite provided by the invention, rare earth modified Y zeolites that step (1) obtains
Water content be not higher than 5 weight %, preferably no greater than 3 weight %.
In the preparation method of the modified Y zeolite provided by the invention, step (1) is set to obtain described in step (2)
Zeolite impregnating metal in organic solvent includes the boiling that will be obtained dissolved with the organic solvent of IV B races metallic compound and step (1)
Stone mixes, and keeps under stirring or standing (without stirring) such as 0.5~12 hour 0.5 hour or more, such as keep under stiring
0.5~12 hour, the process for then carrying out next step for example carried out step (3) or repeats the dipping described in step (2).Wherein Y
The solid-to-liquid ratio (for weight ratio) of zeolite and organic solvent can be 1：(0.5~5) is, for example, 1：(1~2).It can be by primary or more
Secondary be immersed in introduces the Group IVB metal in Y zeolites.The one kind or several of the Group IVB metal in Ti, Zr, Hf, Rf
Kind, preferably one or both of Ti, Zr, IV B races metallic compound are the change of the compound, the compound of Zr, Hf of Ti
Close one or more for example, compounds of Ti and/or the compound of Zr in the compound of object, Rf.The IV B races metal
Compound can be the inorganic salts and/or organo-metallic compound of IV B races metal, for example, titanium compound can be titanium sulfate,
It is one or more in titanyl sulfate, titanium tetrachloride, titanium trichloride, butyl titanate, ammonium titanium fluoride.The compound of zirconium can be
It is one or more in zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide.
In the preparation method for inventing the modified Y zeolite provided, the water content of organic solvent described in step (2) is less than
5 weight %, preferably more than 3 weight % are for example no more than 1 weight %.Organic solvent can be alkane, aromatic hydrocarbon, alcohol, ketone,
One or more of ether, ester, halogenated alkane, preferably 40~100 DEG C of the normal boiling point of the organic solvent.It is described organic molten
One kind in the preferred n-hexane of agent, hexamethylene, heptane, benzene, toluene, methanol, ethyl alcohol, isopropanol, acetone, butanone, chloroform
Or it is a variety of.
Invent provide the modified Y zeolite preparation method in, step (2) described dipping, wherein zeolite with it is organic molten
The solid-to-liquid ratio of agent can be 1:(1~4) weight ratio, for example, 1：(1.1~1.6).Temperature when dipping makes organic solvent be liquid
State.Equi-volume impregnating or excessive impregnation method may be used in the dipping.Dipping temperature does not have particular/special requirement for example can be
It impregnates at room temperature.
In the preparation method that the modified Y zeolite provided is provided, the boiling after the dipping that step (3) obtains step (2)
Stone sample and organic solvent set the one kind or more being filled in a reaction vessel such as an autoclave in inert gas such as nitrogen, helium
Kind, kept at least 1 hour under standing or stir at pressure (gauge pressure) 0.0~2.0MPa, room temperature~200 DEG C, usually 1~48
Hour is, for example, 2~24 hours；The pressure is preferably 0.5~1.5MPa, the temperature be, for example, room temperature~150 DEG C for example
For room temperature to 90 DEG C, the time is preferably 4~24 hours.Then optional filtration and or drying preferably filters and dry, will
Zeolite is detached with organic solvent, and the filtering, drying can be carried out according to existing method, and existing drying means such as gas can be used
Flow drying, expansion drying, spray drying, drying, such as the drying temperature can be 100~200 DEG C, the drying when
Between can be 1s~2 day, such as can dry 6~24 hours.The solid-to-liquid ratio for the zeolite and organic solvent that wherein step (2) obtains
It is 1：(5~50) weight ratio, such as 1：(5~30) or 1：(5~10).In general, organic solvent used in step (3) and step (2)
Organic solvent used is organic solvent of the same race.
The obtained product of step (3) is roasted in step (4), the roasting carries out in an inert gas atmosphere, roasts
Temperature is 300~700 DEG C, and roasting time is 0.5~5 hour, such as calcination temperature is 450~650 DEG C or 500~600 DEG C, roasting
It is 1~4 hour to burn the time.It is one or more in the inert gas such as nitrogen, helium.
A kind of catalytic cracking catalyst of present invention offer changes containing 10~60 weight % based on the total catalyst weight
Property Y zeolites, the clay of 10~60 weight % and 5~50 weight % binder；Wherein, with the dry weight of the modified Y zeolite
On the basis of, the modified Y zeolite contains the Group IVB metal oxide of 1 weight of weight %~15 %, contains 1 weights of weight %~15
The rare earth oxide for measuring %, the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum in the modified Y zeolite lattice structure
For (0.2~0.8)：1.Preferably, zeolite surface Group IVB tenor and the ratio of zeolite interior Group IVB tenor is not high
In 0.5；The cell parameter of the modified Y zeolite is 2.448~2.458nm, and specific surface area is 600~850m2/g。
Catalytic cracking catalyst provided by the invention contains IV B races metal and the composite modified Y zeolites of rare earth, wherein described
IV B races metal is selected generally from one or more of Ti, Zr, Hf, Rf, preferably one or both of Ti, Zr.The modified Y
The content of IV B family metal oxides described in zeolite is preferably the 1 heavy % in weight %~10.The rare earth metal be selected generally from La, Ce,
One or more of Pr, Nd, preferably one or both of La, Ce.The content of the rare earth oxide be preferably 1 heavy %~
10 heavy %.
Catalytic cracking catalyst provided by the invention, in the modified Y zeolite lattice structure distorted tetracoordinate skeleton aluminum with
The ratio of four-coordinate skeleton aluminum is (0.2~0.8)：1, for example, (0.3~0.6):1.Distorted tetracoordinate skeleton aluminum and four-coordination
The ratio of framework aluminum is used27Spectral peak area and spectral peak area at chemical shift 60 at the chemical shift 40 that Al MAS NMR methods measure
Ratio indicates.IV B races tenor of zeolite surface and the ratio of IV B races tenor of zeolite interior are not higher than 0.5, for example,
0.001~0.5 is, for example, 0.2~0.5.IV B races tenor of zeolite surface refers to using X-ray photoelectron spectroscopy (XPS)
The IV B races tenor measured is analyzed within the scope of 2~5nm of zeolite surface.IV B races tenor of zeolite interior refers to zeolite sheet
The difference of IV B races tenor of body and IV B races tenor of zeolite surface, wherein IV B races tenor of zeolite ontology is to pass through
The content of IV B races metal in the zeolite that chemical method is analyzed.2.448~2.458nm of cell parameter of the modified Y zeolite,
600~850m of specific surface area2/ g, specific surface area are preferably 600~750m2/ g, cell parameter can be 2.450~2.455nm.
Catalytic cracking catalyst provided by the invention, preparation method include by clay, binder and the modified Y zeolite
The step of being mixed with beating, being spray-dried, wherein the preparation method of the modified Y zeolite includes the following steps：
(1) mixed solution of Y zeolites rare-earth salt solution or rare-earth salts and inorganic ammonium salt is subjected to ion exchange, then mistake
Filter, washing, roast 0.5~5 hour under 300~700 DEG C, 1~100% water vapour, obtain rare earth modified Y zeolites, water
Content is not higher than 5 weight %；
(2) the Y zeolites that step (1) obtains are impregnated into IV B races metal in organic solvent；
(3) the Y zeolites for obtaining step (2) and organic solvent according to solid and liquid weight than 1：(5~50) are mixed in reactor
It closes, is filled with one or more in inert gas such as nitrogen, helium, protected at 0.0~2.0MPa of pressure, room temperature~200 DEG C
Hold at least 1 hour, such as 1~48 hour；Optionally filtering, optionally drying are preferably filtered and dry；
(4) zeolite for passing through step (3) processing roasts in an inert gas atmosphere, 300~700 DEG C of calcination temperature, roasting
Time is 0.5 hour or more, such as 0.5~5 hour.
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, step (1)
Described in Y zeolites can be selected from NaY, NaHY, NaNH4Y、NH4Y, HY, USY, one hand over a roasting Y zeolites, DASY zeolites, two to hand over two roasting Y
Zeolite, two hand over one or more, preferred NaY zeolite in a roasting Y zeolites.The wherein described one roasting Y zeolites of a friendship are, for example, NaY boilings
Stone exchanges and once roasts obtained Y zeolites by primary, and DASY zeolites are, for example, that Y zeolites roast obtain in the presence of water vapor
Y zeolites, two to hand over two roasting Y zeolites be, for example, NaY zeolite by the Y zeolites that exchange twice and double roasting obtains；Two hand over a roasting Y
Zeolite is, for example, NaY zeolite by exchanging twice and once roasting obtained Y zeolites, it is preferred that described to be exchanged for using H+With/
Or NH4 +It swaps.
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, step (1)
Described in ion exchange be according to rare-earth salts (with RE2O3Meter)：Ammonium salt：Y zeolites：Deionized water=0.01~0.15：0~
0.6：1：1~50, preferably 0.01~0.10：0~0.4：1：2~30 weight ratio is by rare-earth salts, ammonium salt, Y zeolites and deionization
It is 2.0~10.0, preferably 2.0~8.0 that water, which is mixed with beating and uniformly adjusts the pH value of slurries, in 25~150 DEG C, preferably 25~90
0.5~5 hour, preferably 0.5~3 hour are exchanged at DEG C.Ammonium salt described in step (1) is selected from ammonium chloride, ammonium sulfate, hydrogen sulfate
It is one or several kinds of in ammonium, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate.The rare-earth salts is the chlorine of rare earth
One or more, preferably chloride in compound, nitrate and sulfate.Wherein the rare earth is preferably lanthanum and/or cerium.Step
(1) water content of rare earth modified Y zeolites described in is not higher than 5 weight %, preferably no greater than 3 weight %.
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, step (2)
Described in make zeolite that step (1) obtains impregnating metal in organic solvent, including will be organic dissolved with IV B races metallic compound
Solvent is mixed with the zeolite that step (1) obtains, and is kept under stirring or standing (without stirring) 0.5 hour or more such as 0.5~12
Hour, such as keep under stiring 0.5~12 hour, the process for then carrying out next step for example carries out step (3) or repeats to walk
Suddenly the dipping described in (2).Wherein the solid-to-liquid ratio (for weight ratio) of Y zeolites and organic solvent can be 1：(0.5~5) is, for example, 1：
(1~2).The modification Group IVB metal can be introduced in Y zeolites by one or many be immersed in.The Group IVB metal is selected from
One or more of Ti, Zr, Hf, Rf, preferably one or both of Ti, Zr, IV B races metallic compound are the change of Ti
Close object, the compound of Zr, the compound of Hf, one or more in the compound of Rf be, for example, Ti compounds and/or Zr
Compound.The IV B races metallic compound can be the inorganic salts and/or organo-metallic compound of IV B races metal, such as titanium
Compound can be one kind in titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, butyl titanate, ammonium titanium fluoride or
It is a variety of.The compound of zirconium can be one kind in zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide
Or it is a variety of.
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, step (2)
Described in organic solvent water content be less than 5 weight %, preferably more than 3 weight % are for example no more than 1 weight %.Organic solvent
Can be one or more of alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane, the normal boiling point of the organic solvent
It is preferred that 40~100 DEG C.The preferred n-hexane of the organic solvent, hexamethylene, heptane, benzene, toluene, methanol, ethyl alcohol, isopropanol, third
It is one or more in ketone, butanone, chloroform.Step (2) described dipping, the wherein solid-to-liquid ratio of zeolite and organic solvent can be with
It is 1:(1~4) weight ratio, for example, 1：(1.1~1.6).Temperature when dipping makes organic solvent be liquid.The dipping can be with
Using equi-volume impregnating or excessive impregnation method.It can be to impregnate at room temperature that dipping temperature, which does not have particular/special requirement for example,.
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, it is preferable that
Step (3) by after dipping that step (2) obtains zeolite sample and organic solvent set in a reaction vessel such as an autoclave, be filled with lazy
It is one or more in property gas such as nitrogen, helium, in inert atmosphere, pressure (gauge pressure) 0.0~2.0MPa, room temperature~200
Lower holding at least 1 hour is stood or stirred at DEG C, and usually 1~48 hour is, for example, 2~24 hours；The pressure is preferably
0.5~1.5MPa, the temperature are, for example, room temperature~150 DEG C such as room temperature to 90 DEG C, and the time is preferably 4~24 hours.
Then optional filtration and or drying preferably filters and dry, zeolite is detached with organic solvent, it is described filter, drying can be with
It is carried out according to existing method, existing drying means such as pneumatic conveying drying, expansion drying, spray drying, drying, such as institute can be used
It can be 100~200 DEG C to state dry temperature, and time of the drying can be 1s~2 day, such as can to dry 6~24 small
When.Wherein the solid-to-liquid ratio of zeolite and organic solvent is 1：(5~50), such as 1：(5~30) or 1：(5~10).In general, step
(3) organic solvent used in is organic solvent of the same race with organic solvent used in step (2).
Catalytic cracking catalyst preparation method provided by the invention, in the preparation method of the modified Y zeolite, step (4)
Middle to roast the obtained product of step (3), the roasting carries out in an inert gas atmosphere, and calcination temperature is 300~700
DEG C, roasting time is 0.5~5 hour, such as calcination temperature is 450~650 DEG C or 500~600 DEG C, roasting time is 1~4 small
When.It is one or more in the inert gas such as nitrogen, helium.
Catalytic cracking catalyst preparation method provided by the invention, the clay are selected from kaolin, halloysite, tired support
One or several kinds of mixtures in soil, diatomite, montmorillonite, bentonite, sepiolite.These clays are people in the art
Known in member.
Catalytic cracking catalyst preparation method provided by the invention, binder of the present invention refer to roasting after can be formed it is resistance to
The substance of hot inorganic oxide, wherein heat-resistant inorganic oxide are aluminium oxide, silica, one kind in amorphous silicon aluminium or several
Kind, preferably aluminium oxide.The preferred hydrated alumina of the binder, Aluminum sol, boehmite, boehmite, three aqua oxidations
One or more of aluminium, monohydrate alumina, amorphous hydroted alumina, these be not both form binder roasting after with
γ-Al2O3Form exists.These binders are known to those skilled in the art.
Catalytic cracking catalyst preparation method provided by the invention mixes deionized water, molecular sieve, clay and binder
Mashing, can be in any way.It is then added into gained slurries for example, deionized water, clay and binder are mixed with beating
Modified Y zeolite, spray drying, roasting.Spray drying of the present invention, roasting.
Modified Y zeolite provided by the invention, a Group IVB metal part enter in zeolite surface high degree of dispersion, another part
Zeolite interior and skeleton [AlO4] interaction, without in zeolite surface aggregation characteristic.Modified Y zeolite provided by the invention, has
High heat and hydrothermal stability has higher cracking activity, higher gasoline yield, preferable coke selectivity.With it is existing
Rare earth modified Y zeolites are compared, when total metal oxide (rare earth oxide and Group IVB metal oxide) content is suitable, this hair
The modified Y zeolite of bright offer has quite even preferably hydrothermal stability, rare earth modified Y zeolites can be substituted, to reduce
Rare Earths in Catalyst content reduces catalyst production cost.
In modified Y zeolite preparation method provided by the invention, to treated Y zeolites, first aqueous solution ion is used to hand over
The mode changed introduces rare earth, and the method for then using organic solvent dipping introduces the IV B races metal and is further processed, can
To obtain the modified Y zeolite with high hydrothermal stability, prepared modified Y zeolite has higher crystallinity, higher water
Thermal stability, the specific surface area of bigger.
Compared with prior art, Cracking catalyst provided by the invention is used for the catalytic cracking of hydro carbons, has higher split
Change activity, the heavy oil yield of catalytic cracking reduces, and gasoline yield increases, while coke yield declines, and coke selectivity significantly changes
It is kind.Catalytic cracking catalyst provided by the invention can be used for hydrocarbon ils especially heavy oil catalytic cracking.
Description of the drawings
The XRD spectra for the modified Y zeolite that Fig. 1 is embodiment 1, prepared by embodiment 2, comparative example 3~4.
The modified Y zeolite that Fig. 2 is embodiment 2, prepared by comparative example 1, comparative example 327Al-NMR spectrograms.
Specific implementation mode
Catalytic cracking catalyst provided by the invention, containing 10~60 weight % modified Y zeolites, 10~60 weight % clay and
The binder of 5~50 weight %, the modified Y zeolite content are, for example, 20~60 weight %, such as catalytic cracking catalysis
Agent, which contains or organizes, becomes 20~55 weight % modified Y zeolites, the binder of the clay of 15~60 weight % and 10~40 weight %.Institute
It is one or more in the binder stated such as alumina binder, silica binder, silica-alumina binder.Institute
The alumina binder stated can be selected from hydrated alumina, Aluminum sol, boehmite, boehmite, monohydrate alumina, three water
Close one or more of aluminium oxide, amorphous hydroted alumina.
The following examples illustrate the present invention further, it is intended to reader be helped to more fully understand the reality of the present invention
Where matter and caused advantageous effect, but should not be construed as to the present invention can practical range any restriction.
In each embodiment and comparative example, the lattice constant (cell parameter) and crystallinity of zeolite use PHILIPS X '
Pert type x-ray powder diffraction instruments measure, Cu K alpha rays, tube voltage 40kV, tube current 40mA, 2 °/min of sweep speed, scanning
2 θ=5~70 ° of range；Wherein crystal retention is the ratio of crystallinity and crystallinity before aging after zeolite aging, specific surface area
Reservation degree be zeolite aging before with the ratio after aging.Constituent content is by x-ray fluorescence spectrometry.Crystal structure avalanche temperature
Degree is measured by differential thermal analysis (DTA).The room temperature can be 15-40 DEG C.
The ratiometric method of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum in the modified Y zeolite lattice structure
It is：It uses first27Al MAS NMR methods obtain the spectrogram of sample, then measure spectral peak area and chemistry at chemical shift 40
Spectral peak area at displacement 60, the ratio of the two indicate the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum.Wherein27Al
MAS NMR analysis conditions are with reference to as follows：Using U.S.'s VARIAN INOVA 300M type NMR spectrometer with superconducting magnet, solid double resonance
Probe, 6mm ZrO2Rotor, magic angle rotating speed 4kHz,27It is 78.155MHz, sampling time 0.02s, arteries and veins that Al, which detects nuclear resounce frequency,
0.3 μ s are rushed, are scanned 2000 times.
It is raw materials used in embodiment and comparative example：NaY zeolite and one hands over a roasting Y zeolites, neat by Sinopec catalyst
Shandong branch company provides, and property is shown in Table 1.
Prepare raw materials used in catalyst be described as follows：Kaolin is produced by Kaolin of Suzhou company, and solid content is 76 weights
Measure %；Alumina content in Aluminum sol is 21.5 weight %；Boehmite is produced by Shandong Aluminum Plant, and solid content is 62.0 weights
Measure %；Acidification (hydrochloric acid acidification) boehmite solid content is 12.0 weight %, and the molar ratio of acid and aluminium oxide is when acidification
0.15；NaY zeolite used is produced for Shandong catalyst plant, solid content 75.0%, lattice constant 2.466nm, with weight hundred
Divide than content meter, Na2O content is 12.8%, Si/Al molar ratios 2.5.Remaining reagent is by Sinopharm Chemical Reagent Co., Ltd.
Production, specification are that analysis is pure.
Table 1
| Raw material | NaY | One hands over a roasting |
| Element forms, weight % | ||
| Na2O | 12.8 | 3.7 |
| Al2O3 | 21.9 | 23.4 |
| SiO2 | 65.4 | 72.0 |
| Lattice constant, nm | 2.466 | 2.453 |
| Crystallinity, % | 81.6 | 78.0 |
| Total specific surface area, m2/g | 762 | 644 |
| Total pore volume, ml/g | 0.377 | 0.352 |
Embodiment 1
At room temperature, 200gNaY zeolites (75 weight % of butt) are taken, after being beaten with 1500g deionized waters, are added 45 grams
(NH4)2SO4With 45 milliliters of RECl3Solution (270 grams per liter), rare-earth salts is (with RE2O3Meter)：Ammonium salt：NaY zeolite：Deionized water
Weight ratio is 0.08：0.3：1；10, the pH value that slurries are adjusted with 5% dilute hydrochloric acid is 3.8, and it is small to be then warming up to 90 DEG C of exchanges 1
When, it filters and is washed with deionized, filter cake is roasted 2 hours in 600 DEG C, 100% water vapour, obtains rare earth modified Y
Zeolite, water content are 3 weight %.
By 5.23g zirconium nitrate Zr (NO3)4·5H2O, which is dissolved in 200g ethyl alcohol (purity 99.9%), is made maceration extract, gained leaching
Stain liquid is uniformly mixed with treated Y zeolites, keeps 1h at room temperature, and then products therefrom is mixed with 800ml ethyl alcohol, transfer
Into autoclave, and nitrogen is poured, it is 0.5MPa to make pressure, is then kept for 12 hours at room temperature, filtering, 100 DEG C of drying 24
Hour, it is roasted 4 hours at nitrogen atmosphere, 500 DEG C.The Y zeolites of rare earth and modified zirconia are obtained, RE (8)-Zr (1)-Y is denoted as,
Property is shown in Table 2.
Embodiment 2~7
Prepare molecular sieve according to the method provided by the invention, the property of operating condition and product is shown in Table 2.
Table 2
* in 2~table of table 8, w% refers to weight %, is weight percentage.
Comparative example 1
The comparative example illustrates the preparation of rare earth modified Y zeolites.
At room temperature, 200gNaY zeolites (75 heavy % of butt) are taken, after being beaten with 2250g deionized waters, 45 grams of ammonium chlorides are added
With 45 milliliters of RECl3Solution (270 grams per liter), rare-earth salts is (with RE2O3Meter)：Ammonium salt：NaY zeolite：The weight ratio of deionized water is
0.08：0.3：1：15, be then warming up to 90 DEG C exchange 1 hour, filter and be washed with deionized, by filter cake 600 DEG C,
It is roasted 2 hours in 100% water vapour.
Then gained Y zeolites 2250g deionized waters are beaten, 45 grams of ammonium chlorides is added, slurry is adjusted with 5% dilute hydrochloric acid
The pH value of liquid be 3.8, be warming up to 90 DEG C exchange 1 hour after, be filtered, washed, filter cake roasted in 600 DEG C, 100% water vapour
2 hours.Rare earth modified RE (8)-Y zeolites are finally obtained, property is shown in Table 3.
Comparative example 2
According to the method for comparative example 1, the difference is that, rare-earth salts is (with RE2O3Meter)：Ammonium salt：NaY zeolite：The weight of deionized water
Amount is than being 0.04：0.3：1：15.Rare earth modified RE (4)-Y zeolites are finally obtained, property is shown in Table 3.
Comparative example 3
The comparative example illustrates the modified zirconia Y zeolites prepared using aqueous solution infusion process.
According to the method for embodiment 2, the difference is that by the zirconium oxychloride ZrOCl of equivalent2·8H2O is dissolved in 200g deionized waters
In.RE (4)-Zr (W)-Y zeolites are finally obtained, property is shown in Table 3.
Comparative example 4
The comparative example illustrates the titanium modified Y zeolite prepared using aqueous solution ion-exchange.
After taking 200gNaY zeolites to be beaten with 2250 grams of deionized waters, 45g ammonium chlorides and 22.2 milliliters of RECl are added3Solution
(270 grams per liter), rare-earth salts is (with RE2O3Meter)：Ammonium salt：NaY zeolite：The weight ratio of deionized water is 0.02：0.3：1：15, it adjusts
The pH value of slurries be 3.8, be then warming up to 90 DEG C exchange 1 hour, filter and be washed with deionized, by filter cake 600 DEG C,
It is roasted 2 hours in 100% water vapour.
Molecular sieve after roasting is continued to be beaten with 2250 grams of deionized waters, 45g ammonium chlorides and tetra- chlorinations of 7.13g is added
Titanium, continue second of ion exchange, reaction temperature and time exchanges essentially identical with first time, is then filtered, washed,
Filter cake is roasted 2 hours under 600 DEG C, 100% water vapour, finally obtains RE (2)-Ti (J)-Y zeolites, property is shown in Table 3.
It can be seen that the modified Y zeolite prepared using the method for the invention from the XRD spectra of Fig. 1 modified Y zeolites, and
The spectrogram of standard Y zeolites is almost the same, does not find IV family metal oxides (such as TiO2、ZrO2) characteristic peak, show IV races metal
In zeolite surface high degree of dispersion or enter zeolite interior, does not assemble in zeolite surface.
From Fig. 2 modified Y zeolites27Al-NMR spectrograms find out that modified Y zeolite is primarily present four-coordination skeleton Al (chemical potentials
Move hexa-coordinate non-skeleton Al 60), a small amount of (chemical shift is 0).Compared with HY zeolites, prepared using organic solution infusion process
The four-coordination skeleton Al peak broadening of RE (4)-Zr (4)-Y zeolites, and moved to low chemical shift direction, show to enter zeolite interior
Zr and zeolitic frameworks [AlO4] interacted, this interaction causes four-coordinate framework AL spectrum peak to shift to High-Field,
Distort four-coordinate framework AL spectrum peak (chemical shift 40) significantly simultaneously, the ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum
It is 0.2~0.8.And RE (4)-Zr (the W)-Y zeolites for using aqueous solution infusion process to prepare, the variation of the peaks four-coordination skeleton Al are not shown
It writes, shows Zr or Ti and zeolitic frameworks [AlO4] interaction it is smaller, distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum
Ratio is relatively low.It can be seen that the modified Y zeolite prepared using the method for the present invention, is more advantageous to IV races metal ion and enters zeolite interior,
With zeolitic frameworks [AlO4] interaction, to play the role of molecular sieves stabilized skeleton structure.
The modified Y zeolite that it can be seen from 3 data of table prepared by 1~embodiment of embodiment 7 have larger specific surface area and
Lattice damage temperature.With the modified Y zeolite (comparative example 3 and right prepared using aqueous solution infusion process and aqueous solution ion-exchange
Ratio 4) compare, using organic solvent infusion process prepare modified Y zeolite have higher crystallinity, higher thermal stability,
It is smaller to skeleton structure of zeolite destruction, because IV B races metal ion can occur acutely to hydrolyze in aqueous solution, aqueous solution is made to present
Highly acid can destroy Y skeleton structure of zeolite.Compared with rare earth modified Y zeolites RE (8) Y, RE (4) Y, when total metal oxide is (dilute
Native oxide and Group IVB metal oxide) content it is suitable when, modified Y zeolite RE (4)-Zr (4)-Y provided by the invention, RE
(2)-Ti (2)-Y has quite even preferably thermal stability.
Table 3
Embodiment 8~14
Embodiment 8~14 illustrates the hydrothermal stability of modified Y zeolite prepared by the present invention.
Modified Y zeolite prepared by Examples 1 to 7 respectively under the conditions of 800 DEG C, 100% water vapour after aging 12 hours,
Its crystallinity and specific surface area are measured, and calculates crystal retention and specific surface area reservation degree, is as a result listed in table 4.
And carry out light oil microactivity evaluation, using RIPP92-90 standard method (see《Petrochemical analysis method》
(RIPP test methods) Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) light oil microactivity of evaluation sample, catalyst
Loading amount is 5.0g, and 460 DEG C of reaction temperature, feedstock oil is 235~337 DEG C of straight distillation light diesel oils of boiling range, and product is formed by gas-chromatography
Analysis calculates light oil microactivity according to product composition, is as a result listed in table 4.
Light oil microactivity (MA)=(gasoline production+gas yield+coke output for being less than 216 DEG C in product)/charging
Total amount × 100%
Comparative example 5~8
By 1~4 modified Y zeolite of comparative example respectively under the conditions of 800 DEG C, 100% water vapour after aging 12 hours, it is measured
Crystallinity and specific surface area, and crystal retention and specific surface area reservation degree are calculated, as a result it is listed in table 4.And according to embodiment 8
Method evaluates the light oil microactivity of sample, and the results are shown in Table 4.
From table 4, it can be seen that compared with rare earth modified Y zeolites (comparative example 5,6), modified Y zeolite tool provided by the invention
There are quite even slightly higher crystal retention, specific surface area reservation degree and micro-activity, shows modified Y zeolite provided by the invention
With quite even slightly higher hydrothermal stability.Compared with comparative example 7~8, the modified Y zeolite that the method for the present invention provides not only has
There are higher crystal retention and specific surface area reservation degree, and micro-activity also significantly improves.As it can be seen that prepared by the present invention
Modified Y zeolite has high hydrothermal stability.
Table 4
Embodiment 15
It is to live with modified Y zeolite RE (8)-Zr (1)-Y provided by the invention, RE (4)-Zr (4)-Y, RE (2)-Ti (2)-Y
Property constituent element, prepares catalyst according to the conventional catalytic cracking catalyst method.Preparation method is as follows：According to molecular sieve (with butt
Meter)：Kaolin (in terms of butt)：Boehmite is (with Al2O3Meter)：Aluminum sol is (with Al2O3Meter) it is 38：34：20：8 ratio
Example will be added Aluminum sol after kaolin and the mashing uniformly of decationized Y sieve water, be separately added into boehmite under constant stirring, stir
After mixing about 30 minutes, the slurries containing molecular sieve are added in colloid, after remixing uniformly, spray drying forming is catalyzed
Agent C1~C3.
Heavy oil cracking performance evaluation：Through 800 DEG C, 100% steam aging 8 is small for evaluation on small fixed fluidized bed unit
When after catalyst, feedstock oil is Zhenghai VGO and the normal slag of grand celebration (80：20) miscella, feedstock property are shown in Table 5, reaction temperature
It is 500 DEG C, weight (hourly) space velocity (WHSV) 16h-1, agent weight of oil ratio is 4, and evaluation result is shown in Table 6.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
The conversion ratio of coke selectivity=coke yield × 100/
Table 5
Comparative example 9
Comparative catalyst is prepared according to the method for embodiment 15, the difference is that respectively with equivalent RE (8) Y zeolites, equivalent RE
(4) Y zeolites, equivalent RE (4)-Zr (W)-Y zeolites replace RE therein (8)-Zr (1)-Y zeolites, respectively obtain comparison catalysis
Then agent DC1, DC2, DC3 evaluate DC1~DC3 according to the method for embodiment 15.Evaluation result is shown in Table 6.
Table 6
The catalyst prepared using modified Y zeolite provided by the invention it can be seen from 6 data of table is had higher heavy
Oily conversion capability, coke yield decline.Compared with the catalyst of the rare earth modified Y zeolites equal with total metal contents in soil, the present invention carries
There is quite or even slightly good cracking activity for catalyst, while coke selectivity significantly improves.
Embodiment 16
Rare earth and composite modified RE (3)-Zr (the 5)-Y zeolites of zirconium are prepared according to the method for embodiment 1, unlike, it is dilute
Earth salt is (with RE2O3Meter) with the weight ratios of Y zeolites it is 0.03：1, zirconium nitrate Zr (NO3)4·5H2O is (with ZrO2Meter) and Y zeolites
Weight ratio is 0.05：1.
323g boehmites (62 weight % of solid content) and 1343g deionized waters are mixed, stirring mixes after 15 minutes
Pseudoboehmite slurry uniformly is obtained, the pH value that slurries are adjusted with dilute hydrochloric acid is 3.5, at room temperature aging 6 hours；After weathering
Slurries in, 447g kaolin (76 weight % of solid content) and 372g Aluminum sols (21.5 weight % of alumina content) is added, stirs
It mixes 60 minutes；Addition 380g above-mentioned modified RE (3)-Zr (5)-Y zeolites (in terms of butt) in slurries are stated then up to go with 880g
Ionized water is beaten the slurries to be formed, and stirring obtains catalyst slurry after sixty minutes, the slurries spray drying forming that will be obtained, in
550 DEG C roast 1 hour, obtain Cracking catalyst C16 provided by the invention.XRF measures the ZrO of catalyst C162Content is 1.85
Weight %, RE2O3Content is 1.1 weight %.
Embodiment 17
Rare earth and composite modified RE (5)-Zr (the 3)-Y zeolites of zirconium are prepared according to the method for embodiment 3, unlike, it is dilute
Earth salt is (with RE2O3Meter) with the weight ratios of Y zeolites it is 0.05：1, zirconium iso-propoxide is (with ZrO2Meter) with the weight ratios of Y zeolites be
0.03：1.
421g kaolin (76 weight % of solid content), 465g Aluminum sols (21.5 weight % of alumina content) are gone with 732g
Ion is added in mashing tank and is beaten, be then added 1667g acidification pseudo-boehmites (hydrochloric acid is acidified, acid-aluminum ratio 0.15, HCl with
With alumina molar ratio, 12 weight % of solid content), after sixty minutes, 380g (butt) above-mentioned modified RE (5)-Zr is added in stirring
(3)-Y zeolites and 880g deionized waters are beaten the slurries to be formed, stir 60 minutes, obtain catalyst slurry, then will obtain
Slurries spray drying forming roasts 1 hour in 550 DEG C, obtains Cracking catalyst C17 provided by the invention.XRF measures catalyst
The ZrO of C172Content is 1.12 heavy %, RE2O3Content is 1.75 weight %.
Embodiment 18
Rare earth and composite modified RE (3)-Ti (the 2)-Y zeolites of titanium are prepared according to the method for embodiment 6, unlike, it is dilute
Earth salt is (with RE2O3Meter) with the weight ratios of Y zeolites it is 0.03：1, butyl titanate is (with TiO2Meter) with the weight ratios of Y zeolites be
0.02：1.
447g kaolin, 372g Aluminum sols and 800g deionized waters are mixed with beating 60 minutes, 1667g acidifications are then added
Boehmite continues stirring after sixty minutes, be added 380g (butt) above-mentioned modified RE (3)-Ti (2)-Y zeolites and 880g go from
Sub- water is beaten the slurries to be formed, and stirs the slurries spray drying forming that will be obtained after sixty minutes, roasts 2 hours, obtains in 650 DEG C
Cracking catalyst C18 provided by the invention.XRF measures the TiO of catalyst C182Content is 0.74 weight %, RE2O3Content is
1.12 weight %.
Embodiment 19
Rare earth and composite modified RE (3)-Ti (2)-Zr (the 3)-Y zeolites of titanium zirconium are prepared according to the method for embodiment 7, it is different
, rare-earth salts is (with RE2O3Meter) with the weight ratios of Y zeolites it is 0.02：1, butyl titanate is (with TiO2Meter) with the weights of Y zeolites
Amount is than being 0.02：1, zirconium nitrate is (with ZrO2Meter) with the weight ratios of Y zeolites it is 0.03：1.
355g boehmites and 1478g deionized waters are mixed, stirring obtains pseudoboehmite slurry after 30 minutes, uses
The pH value that suitable dilute hydrochloric acid adjusts entire slurries is 3.8, aging 2 hours at 60 DEG C；In the aged slurry, it is added
395g kaolin and 465g Aluminum sols continue stirring 60 minutes；Addition 380g (butt) above-mentioned modification in slurries is stated then up
RE (3)-Ti (2)-Zr (3)-Y zeolites are beaten the slurries to be formed with 880g deionized waters, stir the slurries that will be obtained after sixty minutes
Spray drying forming roasts 3 hours in 600 DEG C, obtains Cracking catalyst C19 provided by the invention.XRF measures catalyst C19
TiO2Content is 0.72 weight %, ZrO2Content is 1.14 weight %, RE2O3Content is 1.12 weight %.
Comparative example 10
Rare earth and composite modified RE (3)-Ti (w)-Zr (the w)-Y zeolites of titanium zirconium are prepared according to the method for embodiment 7, it is different
, rare earth modified Y zeolites are placed at room temperature in 3000g deionized waters and are stirred evenly, 12.8g is added into above-mentioned slurries
Butyl titanate and 15.8g zirconium nitrates.Wherein, rare-earth salts is (with RE2O3Meter) with the weight ratios of Y zeolites it is 0.03：1, four fourth of metatitanic acid
Ester is (with TiO2Meter) with the weight ratios of Y zeolites it is 0.02：1, zirconium nitrate is (with ZrO2Meter) with the weight ratios of Y zeolites it is 0.03：1.
Comparative catalyst is prepared according to the preparation method of 19 catalyst of embodiment, unlike, with RE (3)-Ti of equivalent
(w)-Zr (w)-Y zeolites replace RE (3)-Ti (2)-Zr (3)-Y zeolites.Obtain comparative catalyst DC10.XRF measures catalyst
The TiO of DC102Content is 0.73 weight %, ZrO2Content is 1.12 weight %, RE2O3Content is 1.12 weight %.
Comparative example 11
Composite modified Ti (w)-Zr (the w)-Y zeolites of titanium zirconium are prepared according to the method for embodiment 7.It is specific as follows：At room temperature,
200gNaY zeolites (75 heavy % of butt) are taken, after being beaten with 2250g deionized waters, 45 grams of ammonium sulfate are added, with 5% dilute hydrochloric acid
The pH value for adjusting slurries is 3.8, is then warming up to 80 DEG C and exchanges 3 hours, filters and be washed with deionized, filter cake is dried,
It repeats the above steps 3 times, is then roasted 5 hours in 500 DEG C, 100% water vapour, obtain Y zeolites, water content is 2 weights
Measure %.
The Y zeolites of above-mentioned modification are placed at room temperature in 3000g deionized waters and are stirred evenly, are added into above-mentioned slurries
12.8g butyl titanates and 15.8g zirconium nitrates, room temperature (26 DEG C) continue stirring 3 hours, filter cake are placed in 100 DEG C of bakings after filtering
It is 48 hours dry in case, then roasted 3 hours in 550 DEG C of nitrogen atmospheres.Obtain Ti (w)-Zr (w)-Y boilings of titanium and modified zirconia
Stone.
Comparative catalyst is prepared according to the preparation method of 19 catalyst of embodiment, unlike, with Ti (w)-Zr of equivalent
(w)-Y zeolites replace RE (3)-Ti (2)-Zr (3)-Y zeolites.Obtain comparative catalyst DC11.XRF measures catalyst DC11's
TiO2Content is 0.73 heavy %, ZrO2Content is 1.12 heavy %.
By the catalysis of catalyst C16~C19, DC10~DC11 after 800 DEG C, 100% steam aging 17 hours
Agent is evaluated on small fixed fluidized bed unit ACE, and feedstock oil force mixed three, raw material oil nature is shown in Table 7, reaction temperature 500
DEG C, agent weight of oil ratio is 5.Evaluation result is shown in Table 8.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Coke selectivity=100/ conversion ratios of coke yield *
Comparative example 12
By 200 grams of NH4USY (sial atomic ratio 5.2) is added to be formed in 500 grams of absolute ethyl alcohols with vigorous stirring and hang
Supernatant liquid is vigorously stirred lower butyl titanate-ethanol solution that 50 grams per liters are added (with TiO2Meter), under stiring in room temperature mistake
Night dries, and sample roasts 5 hours in 500 DEG C, obtains the titanium modified zeolite of the weight of Ti content 9.1 %, is denoted as DT9, property is shown in Table
3。
7 raw material oil nature of table
8 evaluation result of table
By table 8 as it can be seen that compared with using the catalyst of modified Y zeolite of existing method preparation, the present invention provides catalyst
Heavy oil conversion performance and gasoline yield increase substantially, show the method for the present invention prepare Cracking catalyst have it is higher
Activity and product selectivity.
Claims (25)
1. a kind of modified Y zeolite, which is characterized in that on the basis of the weight percent of the modified Y zeolite, the modified Y boilings
Stone contains the Group IVB metal oxide of 1 weight of weight %~15 %, the rare earth oxide containing 1 weight %~15 weights %, described
The ratio of distorted tetracoordinate skeleton aluminum and four-coordinate skeleton aluminum is (0.2~0.8) in modified Y zeolite lattice structure：1, the IVB
Race's metal is one or more in Ti, Zr, Hf and Rf；
The preparation method of the modified Y zeolite includes the following steps：
(1) mixed solution of Y zeolites rare-earth salt solution or rare-earth salts and inorganic ammonium salt is subjected to ion exchange, then filter,
Washing, roasts 0.5~5 hour under 300~700 DEG C, 1~100% water vapour, obtains rare earth modified Y zeolites, water content is not
Higher than 5 weight %；
(2) the Y zeolites that step (1) obtains are impregnated into IV B races metal in organic solvent, the organic solvent is alkane, fragrance
One or more of hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane；
(3) the Y zeolites for obtaining step (2) and organic solvent according to solid and liquid weight than 1：(5~50) mix in reactor,
It is kept at inert atmosphere, 0.0~2.0MPa of pressure, room temperature~200 DEG C at least 1 hour；Optionally filtering, optionally drying；
(4) zeolite that step (3) obtains roasts in an inert gas atmosphere, 300~700 DEG C of calcination temperature, roasting time 0.5
Hour or more.
2. modified Y zeolite described in accordance with the claim 1, which is characterized in that distort four in the modified Y zeolite lattice structure and match
The ratio of position framework aluminum and four-coordinate skeleton aluminum is (0.2~0.5)：1.
3. modified Y zeolite described in accordance with the claim 1, which is characterized in that zeolite surface Group IVB tenor and zeolite interior
The ratio of Group IVB tenor is not higher than 0.5；IV B races tenor of zeolite surface refers to being existed using X-ray photoelectron spectroscopy
The IV B races tenor measured is analyzed within the scope of 2~5nm of zeolite surface, IV B races tenor of zeolite interior refers to zeolite ontology
The difference of IV B races tenor and IV B races tenor of zeolite surface, wherein IV B races tenor of zeolite ontology is passing through
The content of IV B races metal in the zeolite that method is analyzed.
4. modified Y zeolite described in accordance with the claim 1, which is characterized in that the cell parameter 2.448 of the modified Y zeolite~
2.458nm, specific surface area are 600~850m2/g。
5. modified Y zeolite described in accordance with the claim 1, which is characterized in that IV B races metal oxygen described in the modified Y zeolite
The content of compound is 1~10 weight %, and the content of the rare earth oxide is 1~10 weight %.
6. modified Y zeolite described in accordance with the claim 1, which is characterized in that IV B races metal includes titanium and/or zirconium.
7. a kind of preparation method of modified Y zeolite, includes the following steps：
(1) mixed solution of Y zeolites rare-earth salt solution or rare-earth salts and inorganic ammonium salt is subjected to ion exchange, then filter,
Washing, roasts 0.5~5 hour under 300~700 DEG C, 1~100% water vapour, obtains rare earth modified Y zeolites, water content is not
Higher than 5 weight %；
(2) the Y zeolites that step (1) obtains are impregnated into IV B races metal in organic solvent, the organic solvent is alkane, fragrance
One or more of hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane；
(3) the Y zeolites for obtaining step (2) and organic solvent according to solid and liquid weight than 1：(5~50) mix in reactor,
It is kept at inert atmosphere, 0.0~2.0MPa of pressure, room temperature~200 DEG C at least 1 hour；Optionally filtering, optionally drying；
(4) zeolite that step (3) obtains roasts in an inert gas atmosphere, 300~700 DEG C of calcination temperature, roasting time 0.5
Hour or more.
8. according to the method for claim 7, which is characterized in that the Y zeolites described in step (1) are NaY, NaHY, NaNH4Y、
NH4Y, one or more in HY, DASY and USY zeolite.
9. according to the method for claim 7, which is characterized in that the ion exchange described in step (1) is：According to rare earth
Salt：Ammonium salt：Y zeolites：Deionized water=0.01~0.15：0~0.6：1：1~50 weight ratio by rare-earth salts, ammonium salt, Y zeolites and
Deionized water mixes, and adjusts the pH value of slurries and is exchanged 0.5~5 hour at 25~150 DEG C for 2.0~10.0；Wherein rare-earth salts
With RE2O3Meter, Y zeolites are in terms of butt.
10. according to the method for claim 7, which is characterized in that the water content of rare earth modified Y zeolites described in step (1)
Not higher than 3 weight %.
11. according to the method for claim 7, which is characterized in that described in step (2) in organic solvent impregnating metal packet
It includes：It will be mixed with the rare earth modified Y zeolites that step (1) obtains dissolved with the organic solvent of IV B races metallic compound, middle rare earth changes
Property Y zeolites and organic solvent solid and liquid weight ratio be 1：(0.5~5), is then stirred 0.5~12 hour or standing 0.5~12 is small
When.
12. according to the method for claim 11, which is characterized in that the solid-liquid weight of step (2) the Y zeolites and organic solvent
Amount is than being 1:1~2.
13. according to the method for claim 7, which is characterized in that the water content of the organic solvent is no more than 5 weight %.
14. according to the method for claim 7, which is characterized in that the water content of the organic solvent is no more than 3 weight %；
The water content of the Y zeolites is no more than 3 weight %.
15. according to the method for claim 7, which is characterized in that the normal boiling point of the organic solvent is 40~100 DEG C.
16. according to the method for claim 7, which is characterized in that the organic solvent be n-hexane, hexamethylene, heptane,
It is one or more in benzene, toluene, methanol, ethyl alcohol, isopropanol, acetone, butanone and chloroform.
17. according to the method for claim 7, which is characterized in that step (3) retention time is 1~48 hour.
18. according to the method for claim 7, which is characterized in that in step (3), the pressure is 0.5~1.5MPa, institute
It is room temperature~150 DEG C to state temperature, and the time is 4~24 hours, and the liquid-solid ratio weight ratio of organic solvent and zeolite is 5~30:
1。
19. according to the method for claim 7, which is characterized in that in step (4), the calcination temperature is 450~650 DEG C,
The roasting time is 1~4 hour.
20. according to the method for claim 7, which is characterized in that IV B races metallic compound be titanium compound and/
Or the compound of zirconium；The compound of the titanium is titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, butyl titanate, fluorine
It is one or more in titanium acid ammonium, the compound of the zirconium be zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium,
It is one or more in zirconium iso-propoxide.
21. a kind of catalytic cracking catalyst contains 10~60 weight %Y zeolites, 10~60 heavy % based on the total catalyst weight
Clay and 5~50 weight % binder, the Y zeolites be claim 1~6 any one of them modified Y zeolite.
22. according to the catalytic cracking catalyst described in claim 21, which is characterized in that the catalytic cracking catalyst contains 20
The binder of~60 weight % modified Y zeolites, the clay of 10~60 weight % and 5~50 weight %.
23. according to the catalytic cracking catalyst described in claim 21, which is characterized in that the catalytic cracking catalyst contains 20
~55 weight % modified Y zeolites, the binder of the clay of 15~60 weight % and 10~40 weight %.
24. a kind of preparation method of catalytic cracking catalyst, including modified Y zeolite is prepared, by the modified Y zeolite, clay, water
It is mixed with beating with binder, the step of spray drying, wherein the preparation method of the modified Y zeolite is claim 7~21
Any one of them method.
25. according to the method for claim 24, which is characterized in that the clay is selected from kaolin, halloysite, tired support
One or several kinds of mixtures in soil, diatomite, montmorillonite, bentonite, sepiolite；The binder be selected from Aluminum sol,
One or more of boehmite, boehmite, monohydrate alumina, hibbsite, amorphous hydroted alumina.
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| CN109499498B (en) * | 2019-01-14 | 2021-06-18 | 哈密市鲁江缘新材料有限公司 | Modified sol and preparation method and application thereof |
| CN116020526A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Reprocessing method of catalytic cracking balancing agent suitable for high nickel |
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