CN106179457A - A kind of catalytic cracking catalyst and its preparation method and application - Google Patents
A kind of catalytic cracking catalyst and its preparation method and application Download PDFInfo
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- CN106179457A CN106179457A CN201510214215.8A CN201510214215A CN106179457A CN 106179457 A CN106179457 A CN 106179457A CN 201510214215 A CN201510214215 A CN 201510214215A CN 106179457 A CN106179457 A CN 106179457A
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Abstract
The invention provides a kind of catalytic cracking catalyst and its preparation method and application.On the basis of the gross weight of catalytic cracking catalyst, catalytic cracking catalyst contains the mesoporous active materials of 1-50 weight %；Mesoporous active materials with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.2) Na2O·(40-85)Al2O3·(10-55)SiO2·(0.5-10)P2O5·(0.5-10)MxOy, wherein metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, and y is that metal M maximum when forming oxide closes valence state, and the numerical value of x and y makes the quantivalence of M and O balance.This catalyst has relatively low coke selectivity, higher catalytic cracking activity during RFCC, and can also effectively reduce FCC gasoline sulfur content.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, the preparation method of described catalytic cracking catalyst and
The application in RFCC of the described catalytic cracking catalyst.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, occupies act foot in petroleum refining industry
The status of weight.In catalytic cracking process, heavy end is (such as vacuum distillate or the slag of more heavy constituent
Oil) react in the presence of a catalyst, it is converted into the high value added products such as liquefied gas, gasoline, diesel oil,
Typically require in this process and use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material
Owing to having excellent shape selective catalysis performance and the highest cracking reaction activity, it is widely used in oil refining
In system and processing industry.Along with the requirement of the aspects such as the day by day exhausted of petroleum resources and environmental conservation, special
It not that crude oil becomes heavy growth trend and the market wilderness demand to light-end products, increasingly in PETROLEUM PROCESSING work
Industry is increasingly paid attention to the deep processing to heavy oil and residual oil.
For improving conversion ratio, strengthen heavy oil conversion performance, reduce intermediate oil and Petroleum simultaneously
Converting further, traditional micro porous molecular sieve catalysis material is less due to its duct, to bigger raw molecule
Demonstrate and significantly limit diffusion so that simple micro porous molecular sieve catalysis material be less suitable for for
The catalytic cracking of the heavy distillate such as heavy oil and residual oil, so that use that aperture is relatively big, divide reactant
Son does not has diffusion-restricted and has the material of higher cracking activity.Therefore, mesoporous and macropore catalysis material
Research and development are increasingly subject to people's attention.Additionally, in catalytic cracking field, silica-alumina material has due to it
Stronger acid centre and good cracking performance is had to be widely applied.
CN1565733A discloses a kind of mesoporous silicon aluminum, and this mesoporous silicon aluminum has the thin water aluminum of plan
Stone crystal phase structure, with the anhydrous chemical expression of the mass ratio range of oxide be:
(0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2, its specific surface area is 200-400m2/ g, pore volume is
0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.This mesoporous silicon aluminum
Preparation be not required to use organic formwork agent, synthesis low cost, and the mesoporous silicon aluminum obtained have high
Cracking activity and hydrothermal stability, show good macromole cracking performance in catalytic cracking reaction.
CN1854258A discloses a kind of fluid cracking catalyst, and this fluid cracking catalyst contains 3-20
The mesoporous silica-alumina materials through acid treatment of weight %, this mesoporous silica-alumina materials has boehmite crystalline phase knot
Structure, with the anhydrous chemical expression of the mass ratio range of oxide be:
(0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2, specific surface area is 200-400m2/ g, pore volume is
0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.
CN1978593A discloses a kind of Cracking catalyst, containing a kind of mesoporous material in this Cracking catalyst
Material, the anhydrous compound composition of described mesoporous material with the mass ratio range of oxide is
(0-0.3)Na2O·(40-85)Al2O3·(10-55)SiO2·(1-20)MxOy, wherein, metal M is selected from element week
In phase Table II A, IB, IIB, IVB, VB, VIB, VIIB, VIIIB or lanthanide series rare-earth elements one
Kind, this mesoporous material has boehmite crystal phase structure, and specific surface area is 200-400m2/ g, pore volume
For 0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.This catalyst is permissible
It is directly used in catalytic cracking reaction, under conventional FCC operating condition, both can improve crude oil and weight
Oil conversion ratio, can effectively reduce again FCC gasoline sulfur content.
CN102078821A discloses a kind of Cracking catalyst containing mesoporous silica-alumina materials, and wherein, this splits
Change catalyst to be made up of cracking activity constituent element, clay, binding agent and mesoporous silica-alumina materials, described mesoporous silicon
Aluminum has boehmite crystal phase structure, with the anhydrous chemical expression of the mass ratio range of oxide
For: (0-0.3) Na2O·(40-90)Al2O3·(10-60)SiO2, specific surface area is 200-400m2/ g, pore volume is
0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm, and described binding agent is silicon
Colloidal sol and/or Alumina gel.Although this Cracking catalyst is compared with the conventional catalyst using boehmite,
Have that production cost is low, the more preferable advantage of converting crude oil ability, but its coke selectivity is poor.
Summary of the invention
The invention aims to provide a kind of and new there is relatively low coke selectivity, higher cracking
Activity, and also can effectively reduce FCC (catalytic cracking) content of sulfur in gasoline catalytic cracking catalyst,
The preparation method of described catalytic cracking catalyst and described catalytic cracking catalyst are at RFCC
In application.
To this end, according to an aspect of the invention, it is provided a kind of catalytic cracking catalyst, wherein, with
On the basis of the gross weight of described catalytic cracking catalyst, described catalytic cracking catalyst contains 1-60 weight %
Cracking activity constituent element, the mesoporous active materials of 1-50 weight %, the clay of 1-70 weight % and 1-70 weight
The binding agent of amount %；Described mesoporous active materials has boehmite crystal phase structure, described mesopore activity
In material, the anhydrous chemical expression of mass ratio range with oxide is: (0-0.2) Na2O·(40-85)
Al2O3·(10-55)SiO2·(0.5-10)P2O5·(0.5-10)MxOy, wherein metal M is selected from
Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and in lanthanide series rare-earth elements
Planting or multiple, y is that maximum during metal M formation oxide closes valence state, and the numerical value of x and y makes
The quantivalence of M and O balances, and the specific surface area of described mesoporous active materials is 200-500m2/ g, hole
Hold for 0.5-1.5cm3/ g, average pore size is 8-18nm.
According to another aspect of the present invention, additionally provide the preparation method of described catalytic cracking catalyst,
The method includes the mixing making beating of described cracking activity constituent element, mesoporous active materials, clay and binding agent,
Carry out the most successively being spray-dried, wash, filter and being dried.
Additionally, according to a further aspect of the invention, described catalytic cracking catalyst is additionally provided at heavy oil
Application in catalytic cracking.
The catalytic cracking catalyst that the present invention provides is by by specific mesoporous active materials and cracking activity
Constituent element, clay and binding agent with the use of, add the content of catalytic cracking catalyst mesopore, be conducive to
The diffusion of heavy oil macromole and cracking, this catalytic cracking catalyst is particularly well-suited to RFCC,
Can show higher coke selectivity during RFCC, higher catalytic cracking is lived
Property, and also FCC (catalytic cracking) content of sulfur in gasoline can be effectively reduced.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the X-ray diffraction spectrogram of the mesoporous active materials obtained by preparation example 1.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of catalytic cracking catalyst, wherein, total with described catalytic cracking catalyst
On the basis of weight, described catalytic cracking catalyst contains the cracking activity constituent element of 1-60 weight %, 1-50
The mesoporous active materials of weight %, the clay of 1-70 weight % and the binding agent of 1-70 weight %；In described
Hole active material has boehmite crystal phase structure, with the weight of oxide in described mesoporous active materials
Than the anhydrous chemical expression of meter it is: (0-0.2) Na2O·(40-85)Al2O3·(10-55)SiO2·
(0.5-10)P2O5·(0.5-10)MxOy, wherein metal M selected from Mg, periodic table of elements IIB,
IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, y is metal M
Maximum when forming oxide closes valence state, and the numerical value of x and y makes the quantivalence of M and O balance,
And the specific surface area of described mesoporous active materials is 200-500m2/ g, pore volume is 0.5-1.5cm3/ g, averagely
Aperture is 8-18nm.
In the present invention, described specific surface area, pore volume and average pore size all use nitrogen absorption under low temperature-desorption
Method is measured, and the instrument used is the physical and chemical adsorption instrument of Micro meritics company of the U.S.
ASAP2400。
The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that in described mesoporous active materials
With the anhydrous chemical expression of the mass ratio range of oxide it is: (0.06-0.17) Na2O·(49.5-74.5)
Al2O3·(15.3-45.6)SiO2·(0.6-7.5)P2O5·(2.5-8.5)MxOy。
The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that be catalyzed with described catalytic cracking
On the basis of the gross weight of agent, described catalytic cracking catalyst contain 10-50 weight % cracking activity constituent element,
The mesoporous active materials of 5-40 weight %, the clay of 10-60 weight % and the binding agent of 10-60 weight %,
The content of above-mentioned each component is controlled the catalytic cracking catalyst enabled in the range of this is preferred
There is more preferable combination property.
The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that described mesoporous active materials
Specific surface area is 300-450m2/ g, pore volume is 0.7-1.2cm3/ g, average pore size is 10-15nm.
According to the present invention provide above-mentioned catalytic cracking catalyst, it is preferable that described metal M selected from IIB,
During IIIB, IVB, VIIB race metal, the preferably mixing of one or more in Zn, Y, Ti, Mn,
The mixing of the mixing of described various metals such as Ti and Mn, the mixing of Mn and Zn.Described metal
M when lanthanide series rare-earth elements, preferably lanthanum, cerium or containing lanthanum and the mischmetal of cerium.
According to the present invention provide above-mentioned catalytic cracking catalyst, preferably metal M is Mg, Zn, Y,
The mixing of one or more in Ti, Mn, La and Ce.
The above-mentioned catalytic cracking catalyst provided according to the present invention, wherein mesoporous active materials is referred to existing
Technique is had to be prepared, it is preferable that the most described mesoporous active materials is according to including following step
Rapid method prepares:
(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11,
Obtain plastic serosity；
(2) according to SiO2: Al2O3=1:(0.6-9) weight ratio in described plastic serosity, add silicon
Source, is aged 1-5 hour at room temperature to 90 DEG C, obtains the first solid sediment；
(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get oxidation
Sodium content is less than the second solid sediment of 0.3 weight %；
(4) described second solid sediment, phosphorus source and the compound of metal M, according to P2O5: MxOy:
The precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): the weight ratio of 1
Contact processes, and product of contact is dried, wherein metal M selected from Mg, periodic table of elements IIB, IIIB,
IVB, VIIB race element, and one or more in lanthanide series rare-earth elements.
Specifically, described in above-mentioned steps (1), aluminum source can be existing various can be converted into oxygen
Change the material of aluminum, for example, it is possible to one or more in aluminum nitrate, aluminum sulfate and aluminum chloride.
Described in above-mentioned steps (1), alkaline solution can be the existing various material presenting alkalescence,
For example, it is possible to be selected from ammonia, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution one
Plant or multiple.Wherein, the concentration of described alkaline solution can be the conventional selection of this area, does not makees at this
Repeat.
Described in above-mentioned steps (2), silicon source can be the existing various thing that can be converted into silicon oxide
Matter, for example, it is possible to selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, four propoxyl group
One or more in silicon, four butoxy silicon and silicon oxide.
The present invention is to described first solid sediment contacts in above-mentioned steps (3) side processed with ammonium salt
Method is not particularly limited, for example, it is possible to include the first solid sediment by its precipitate butt: ammonium
Salt: H2O=1:(0.1-1): the weight ratio of (5-30) swaps at room temperature to 100 DEG C.Wherein,
The number of times of described contact can be 1-3 time, and each time of contact can specifically should with 0.5-1 hour
The content of sodium oxide in the solid product obtained is made to be as the criterion less than 0.3 weight %.
Additionally, the kind of ammonium salt can be the conventional selection of this area described in above-mentioned steps (3),
For example, it is possible to the one or many in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate
Kind.
The present invention method to described first solid sediment being contacted with acid solution in above-mentioned steps (3)
It is not particularly limited, for example, it is possible to include described first solid sediment by its precipitate butt:
Acid: H2O=1:(0.03-0.3): the weight ratio of (5-30) exchanges at least 0.2 at room temperature to 100 DEG C
Hour.
Additionally, the kind of acid solution can be the conventional selection of this area described in above-mentioned steps (3),
Usually mineral acid, such as, the acid in described acid solution can be selected from sulphuric acid, hydrogen chloride and nitric acid
One or more.
By the contact of the compound of the second solid sediment, phosphorus source and metal M in above-mentioned steps (4)
Processing procedure can have a various ways, such as following a), b), c), d) during any one:
A) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mix making beating with water, then the compound of phosphorus source and metal M is added sequentially in above-mentioned serosity, in room
At warm to 90 DEG C, contact processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, more preferably contacts
Process 0.5-3 hour, be dried 10-20 hour at 100 DEG C-150 DEG C after filtering washing；
B) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mixing making beating with water, then phosphorus source joined in above-mentioned serosity, at room temperature to 90 DEG C, contact processes at least
0.2 hour, preferably contact processed 0.2-5 hour, and more preferably contact processes 0.5-3 hour, straight after filtration
Connect the compound with metal M to be mixed in proportion, at 100 DEG C-150 DEG C, after grinding uniformly, be dried 10-20
Hour；
C) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mix making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity,
Room temperature to contact at 90 DEG C processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, more preferably connects
Synapsis is managed 0.5-3 hour, obtains the 3rd solid sediment after filtration, then by direct for the 3rd solid sediment
Mix with the second metal M, at 100 DEG C-150 DEG C, after grinding uniformly, be dried 10-20 hour, wherein,
The compound of described the first metal M is identical or different with the compound of the second metal M；
D) described second solid sediment is directly mixed in proportion with phosphorus source and metal M compound, grinds
It is dried 10-20 hour at 100 DEG C-150 DEG C after mill is uniform.
In aforesaid way c), for compound and the change of the second metal M of the first metal M
Concrete material and the consumption of material included in compound do not have particular/special requirement, as long as enabling to institute
State the second solid sediment and phosphorus source and the compound of metal M, be finally according to P2O5: MxOy: institute
State precipitate butt=(0.005-0.1): (0.005-0.1) of the second solid sediment: the weight ratio of 1 is mixed
Close.
Further, optionally, the preparation method at above-mentioned mesoporous active materials can also include desciccate
Carrying out the step of roasting, the condition of described roasting generally includes sintering temperature can be 500-700 DEG C, roasting
The burning time can be 1-4 hour.
Described in above-mentioned steps (4), the kind of phosphorus source can be the conventional selection of this area, such as,
One or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid can be selected from.
Described in above-mentioned steps (4), the compound of metal M can be any one water miscible chemical combination
Thing.
Described in above-mentioned steps (4), the compound of metal M is the nitrate of metal, sulfate or chlorine
Compound.Such as, magnesium source can be selected from one or more in magnesium nitrate, magnesium chloride and magnesium sulfate.
The catalytic cracking catalyst provided according to the present invention, described cracking activity constituent element usually contains Y type and divides
Son sieve.Wherein, the kind of described Y type molecular sieve can be the conventional selection of this area, for example, it is possible to
For the Y type molecular sieve (such as REHY molecular sieve) containing rare earth, phosphorous and rare earth Y type molecular sieve (as
DOSY molecular sieve), ultra-steady Y molecular sieve (such as DASY molecular sieve), phosphorous and/or rare earth super steady
One or more in Y molecular sieve etc..Moreover it is preferred that in addition to Y type molecular sieve, described in split
Change active component possibly together with faujasite, Beta zeolite, MFI structure molecular sieve (such as ZRP-1 molecular sieve)
With one or more in modenite.Wherein, on the basis of the gross weight of described cracking activity constituent element,
The content of described Y type molecular sieve can be more than 75 weight %, more than preferably 90 weight %, more excellent
Elect more than 95 weight % as；Described faujasite, Beta zeolite, MFI structure molecular sieve and mercerising boiling
The total content of stone can be below 25 weight %, below preferably 10 weight %, and more preferably 5 weight %
Below.
Described clay can be the existing various clay that can be used in catalytic cracking catalyst, such as,
Can be selected from Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite,
One or more in meerschaum, attapulgite, brucite and bentonite.
Described binding agent can be the existing various binding agent that can be used in catalytic cracking catalyst, example
As, one or more in Ludox, Alumina gel and boehmite can be selected from.
Additionally, described catalytic cracking catalyst can also contain additional rare earth.Described additional rare earth is in system
Formed by extra addition rare earth chloride during standby described catalytic cracking catalyst.Urge described
In fluidized cracking catalysts, described additional rare earth is generally with rare earth oxide (RE2O3Presented in).
Described additional rare earth on the basis of the butt weight of described catalytic cracking catalyst, in terms of rare earth oxide
Content can be 0-3 weight %, preferably 0.5-2 weight %.Wherein, dilute in described additional rare earth
Earth elements refers to the rare earth element of the various routines related in catalytic cracking catalyst field, such as, can be
Lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium etc..
The preparation method of catalytic cracking catalyst that the present invention provides include by above-mentioned cracking activity constituent element, in
Hole active material, clay and binding agent mixing making beating, carry out the most successively being spray-dried, wash, mistake
Filter and be dried.Additionally, when described catalytic cracking catalyst is possibly together with additional rare earth, the present invention provides
The preparation method of catalytic cracking catalyst also include by described rare earth chloride and described cracking activity constituent element, in
Hole active material, clay and binding agent are mixed together making beating, carry out the most successively being spray-dried, wash,
Filter and be dried.
The preparation method of catalytic cracking catalyst provided according to the present invention, by described cracking activity constituent element,
The rare earth chloride mixing making beating that mesoporous active materials, clay and binding agent and selectivity contain, Yi Jihou
Continuous spray drying, washing, filter and be dried, the implementation of these operations all can use conventional side
Method implement, their specific implementation method such as CN1916166A, CN1098130A,
CN1362472A, CN1727442A, CN1132898C and CN1727445A have detailed retouching
State, the most in the lump in the introducing present invention by reference.Typically also, after described spray drying,
Before washing, the preparation method of described catalytic cracking catalyst the most also includes carrying out Spray dried products
The step of roasting.The condition of described roasting generally includes sintering temperature can be 500-700 DEG C, during roasting
Between can be 1-4 hour.
Additionally, present invention also offers the application in RFCC of the above-mentioned catalytic cracking catalyst.
Hereinafter will be described the present invention by embodiment.
The raw material used in following example and comparative example is as follows:
Hydrochloric acid is produced by Beijing Chemical Plant, chemical pure, and concentration is 36 weight %；
Sodium silicate is commercially available, SiO2Concentration is 26.0 weight %, and modulus is 3.2；
Kaolin is Kaolin of Suzhou Products, and solid content is 74.0 weight %；
Boehmite is Shandong Aluminum Plant's industrial products, and solid content is 62.0 weight %；
Alumina gel is Sinopec catalyst asphalt in Shenli Refinery product, Al2O3Content is 21.5 weight %；
DASY molecular sieve (solid content is 92.0 weight %), (solid content is 97.8 to ZRP-1 molecular sieve
Weight %), REHY molecular sieve (solid content is 88.0 weight %), (solid content is 95.2 to Beta molecular sieve
Weight %), DOSY molecular sieve (solid content is 93.5 weight %) is by Sinopec catalyst Shandong
Branch company produces；
Rare earth chloride be purchased from Xitu Hi-Tech skill limited company of Baogang, rare earth element therein be La and
Ce。
In following example and comparative example:
Specific surface area, pore volume and average pore size all use nitrogen absorption under low temperature-desorption method to be measured, and are adopted
The physical and chemical adsorption instrument ASAP2400 that instrument is Micro meritics company of the U.S..Mesopore activity
Na in material2O、Al2O3、SiO2、P2O5, MgO and metal-oxide (MxOy) content X
(seeing " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui is fixed for ray fluorescence mensuration
Compiling, Science Press, nineteen ninety publishes).
Preparation example 1
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) it is first 90gAl by concentration2O3The Al of/L2(SO4)3Solution is placed in beaker, by dense under stirring
Spending and add for 25wt.% ammonia, until system pH=10.0, keeping gelling temperature is 40 DEG C, collects meter
Amount plastic serosity；(2) under agitation according to SiO2: Al2O3The weight ratio of=1:3 is to becoming rubber cement
Adding concentration in liquid is 60gSiO2The waterglass of/L, is warming up to 80 DEG C and is aged 1 hour, obtain first solid
Body precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H2O=1:0.08:
The weight ratio of 12 exchanges 30 minutes at 50 DEG C, and filtration washing obtains sodium oxide content and is less than 0.3%
Second solid sediment；(4) by the second solid sediment by its precipitate butt: H2O=1:10's
Weight ratio mixes making beating with water, and presses P2O5: MgO:TiO2: the precipitate of the second solid sediment
The weight ratio of butt=0.075:0.017:0.012:1 is sequentially added into ammonium phosphate, magnesium nitrate and titanium sulfate,
React 2 hours at 60 DEG C, be dried at 120 DEG C after filtering washing and within 10 hours, i.e. obtain the present invention and carry
The phosphorus of confession, metal-modified mesoporous silicon aluminum.It is designated as A-1.
A-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry consists of 0.08Na2O·74.2Al2O3·15.3SiO2·7.3P2O5·1.5MgO·1.0TiO2；Ratio
Surface area 455m2/ g, pore volume 1.24cm3/ g, average pore size 10.9nm.
Preparation example 2
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) with concentration as 90gAl2O3The Al of/L2(SO4)3Solution and concentration are 102gAl2O3/ L, severe
Property than be 2.5 NaAlO2Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down
Row mixing plastic, controlling system temperature is 40 DEG C, system pH=10.5, collects metering plastic serosity；(2)
Under agitation according to SiO2: Al2O3The weight ratio of=1:1.2 adds concentration in plastic serosity
100gSiO2The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3)
By described first solid sediment by its precipitate butt: HCl:H2The weight ratio of O=1:0.08:15
Exchange 30 minutes at 60 DEG C, filter washing and obtain the sodium oxide content the second solid precipitation less than 0.3%
Thing；(4) P is pressed2O5: TiO2: MnO2: the precipitate butt=0.015:0.035 of the second solid sediment:
Second solid sediment is mixed by the weight ratio of 0.049:1 with ammonium dihydrogen phosphate, titanium sulfate and manganese chloride
Close, be dried 15 hours at 120 DEG C after grinding uniformly, within 4 hours, i.e. obtain the present invention then at 600 DEG C of roastings
The phosphorus provided, metal-modified mesoporous silicon aluminum.It is designated as A-2.
A-2 has boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its
Elementary analytical chemistry consists of 0.17Na2O·55.1Al2O3·34.4SiO2·1.5P2O5
·3.5TiO2·4.9MnO2；Specific surface area 312m2/ g, pore volume 0.87cm3/ g, average pore size 11.1nm.
Preparation example 3
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) with concentration as 90gAl2O3The Al of/L2(SO4)3Solution and the ammonia that concentration is 24wt.% are
Reaction raw materials, uses and flows plastic mode, is stirred vigorously lower by Al2(SO4)3Solution and ammonia mix
Rubber polymer, controlling system temperature is 50 DEG C, system pH=9.5, collects metering plastic serosity；(2) and
Under agitation according to SiO2: Al2O3The weight ratio of=1:1.8 adds concentration in plastic serosity
60gSiO2The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours, obtain the first solid sediment；(3)
By described first solid sediment by its precipitate butt: ammonium salt: H2The weight ratio of O=1:1:12 exists
Exchange 1 hour at 60 DEG C, filter washing and obtain the sodium oxide content the second solid sediment less than 0.3%；
(4) by the precipitate butt of the second solid sediment: H2The weight ratio of O=1:10 is by solid for gained second
Body precipitate mixes making beating with water, and presses P2O5: Y2O3: the precipitate butt of the second solid sediment=
The weight ratio of 0.038:0.032:1 adds phosphoric acid and yttrium nitrate solution mixes, anti-at 70 DEG C
Answering 2 hours, filtration is dried at 120 DEG C after washing and within 15 hours, i.e. obtains the phosphorus of present invention offer, metal changes
The mesoporous silicon aluminum of property.It is designated as A-3.
A-3 has boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its
Elementary analytical chemistry consists of 0.12Na2O·65.4Al2O3·27.2SiO2·3.7P2O5·3.1Y2O3；Compare table
Area 418m2/ g, pore volume 1.09cm3/ g, average pore size 10.4nm.
Preparation example 4
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) it is 102gAl by concentration2O3/ L, Crater corrosion are 2.5NaAlO2Solution is placed in beaker, stirs
Mixing lower is 90gAl by concentration2O3The Al of/L2(SO4)3Add, until system pH=8.5, keep plastic temperature
Degree is 40 DEG C, collects metering plastic serosity；(2) according to SiO under stirring2: Al2O3The weight of=1:2.1
It is 100gSiO that amount adds concentration than in plastic serosity2The waterglass of/L, is warming up to 70 DEG C of ageings 2 little
Time, obtain the first solid sediment；(3) by the first solid sediment by its precipitate butt: NH4Cl:
H2The weight ratio of O=1:1:10 exchanges 1 hour at 60 DEG C, and it is low that filtration washing obtains sodium oxide content
In second solid sediment of 0.3%；(4) by the second solid sediment by its precipitate butt: H2O=
The weight ratio of 1:8 mixes making beating with water, and presses P2O5: MgO:TiO2: MnO2: ZnO: the second
The weight ratio of the precipitate butt=0.012:0.01:0.012:0.012:0.01:1 of solid sediment adds
Enter phosphoric acid, magnesium nitrate, titanium sulfate, manganese chloride and zinc nitrate, react 2 hours at 70 DEG C, filter
The phosphorus i.e. obtaining the present invention for 10 hours and providing, metal-modified mesoporous silicon aluminium are provided after washing at 120 DEG C
Material.It is designated as A-4.
A-4 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its yuan
Element analytical chemistry consists of 0.06Na2O·68.2Al2O3·26.1SiO2·1.1P2O5·0.9MgO·1.1TiO2
·1.2MnO2·0.8ZnO；Specific surface area 408m2/ g, pore volume 1.03cm3/ g, average pore size 10.1nm.
Preparation example 5
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) using concentration is 90gAl2O3The Al of/L2(SO4)3Solution and concentration are 102gAl2O3/L、
Crater corrosion is the NaAlO of 2.52Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down
Carrying out mixing plastic, controlling system temperature is 35 DEG C, system pH=9.5, collects metering plastic serosity,
(2) under agitation according to SiO2: Al2O3The weight ratio of=1:1 adds concentration in plastic serosity
60gSiO2The waterglass of/L, is warming up to 70 DEG C and is aged 1 hour, obtain the first solid sediment；(3)
After filtering washing, by the precipitate butt of the first solid sediment: ammonium salt: H2The weight of O=1:1:10
Ratio and NH4Cl and deionized water mixing, carry out ion exchange at 55 DEG C and obtain sodium oxide content and be less than
Second solid sediment of 0.3%；(4) by the second solid sediment reslurry, and MgO is pressed: the
The weight ratio of the precipitate butt=0.025:1 of two solid sediments adds magnesium nitrate, reacts 1 at 65 DEG C
Hour, filter and be dried 10 hours in 120 DEG C, obtain the 3rd solid sediment；By the 3rd solid precipitation
The precipitate butt of thing: P2O5: La2O3The weight ratio of=1:0.007:0.010 is by drying sample and phosphorus
Acid and lanthanum chloride solution mix, and are dried 10 hours in 120 DEG C, then at 550 DEG C of roastings 2 after grinding uniformly
Hour i.e. obtain phosphorus, metal-modified mesoporous silicon aluminum that the present invention provides.It is designated as A-5.
A-5 has boehmite phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its
Elementary analytical chemistry consists of 0.13Na2O·49.8Al2O3·45.6SiO2·0.7P2O5·2.5MgO·1.0
La2O3；Specific surface area 360m2/ g, pore volume 0.93cm3/ g, average pore size 10.3nm.
Preparation example 6
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) it is 90gAl by concentration2O3The Al of/L2(SO4)3Solution is placed in beaker, and the lower addition of stirring is dense
Degree is the ammonia of 25wt.%, until system pH=9.0, keeping gelling temperature is 40 DEG C, collects metering
Plastic serosity；(2) under agitation according to SiO2: Al2O3The weight ratio of=1:3 is to plastic serosity
Middle addition concentration is 60gSiO2The waterglass of/L, is warming up to 60 DEG C and is aged 2 hours, obtain the first solid
Precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H2O=1:0.08:
The weight ratio of 10 exchanges 1 hour at 50 DEG C, filters washing and obtains Na2O content less than 0.3% the
Two solid sediments；(4) by the second solid sediment reslurry and by the precipitation of the second solid sediment
Thing butt: P2O5The weight ratio of=1:0.6 mixes with phosphoric acid, stirs 1 hour at 70 DEG C, filters also
It is dried 10 hours in 120 DEG C, obtains the 3rd solid sediment；The 3rd solid sediment and the chlorine that will obtain
Change rare earth (containing La and Ce) solution, by the precipitate butt of the 3rd solid sediment: RE2O3=1:
The weight ratio of 5.5 with mix, be dried 10 hours in 120 DEG C after grinding uniformly, then at 550 DEG C of roastings 2
Hour i.e. obtain phosphorus, metal-modified mesoporous silicon aluminum that the present invention provides.It is designated as A-6.
A-6 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with special shown in Fig. 1
Levy；Its elementary analytical chemistry consists of 0.11Na2O·72.4Al2O3·21.2SiO2·0.6P2O5
·5.3RE2O3；Specific surface area 396m2/ g, pore volume 0.96cm3/ g, average pore size 9.7nm.
Preparation example 7
This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides
Method.
(1) using concentration is 90gAl2O3The Al of/L2(SO4)3Solution and concentration are 102gAl2O3/ L,
Crater corrosion is the NaAlO of 2.52Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down
Carrying out mixing plastic, controlling system temperature is 35 DEG C, system pH=9.5, collects metering plastic serosity,
(2) under agitation according to SiO2: Al2O3The weight ratio of=1:1.3 adds concentration in plastic serosity
60gSiO2The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3)
After filtering washing, by the precipitate butt of the first solid sediment: ammonium salt: H2The weight of O=1:1:15
Ratio and NH4Cl and deionized water mixing, carry out ion exchange at 65 DEG C and obtain sodium oxide content and be less than
Second solid sediment of 0.3%；(4) P is pressed2O5: the precipitate of the MgO: the second solid sediment is done
Second solid sediment is mixed by the weight ratio of base=0.015:0.035:1 with phosphoric acid and magnesium nitrate,
Being dried 10 hours at 120 DEG C after grinding uniformly, within 2 hours, i.e. obtaining the present invention then at 600 DEG C of roastings provides
Phosphorus, metal-modified mesoporous silicon aluminum.It is designated as A-7.
A-7 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry consists of 0.16Na2O·55.4Al2O3·38.1SiO2·1.5P2O5·3.5MgO；Specific surface area
329m2/ g, pore volume 0.88cm3/ g, average pore size 10.7nm.
Contrast preparation example 1
This contrast preparation example is used for mesoporous silicon aluminum and preparation method thereof is described.
Prepare mesoporous silicon aluminum according to the method for preparation example 1, except for the difference that, do not include step (4),
But the product obtained after being directly dried 10 hours at 120 DEG C by the second solid sediment is as reference
Mesoporous silicon aluminum, be designated as DA-1.
DA-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides
Analysis chemical composition is 0.19Na2O·81.9Al2O3·16.7SiO2；Specific surface area 514m2/ g, pore volume 1.45
cm3/ g, average pore size 11.3nm.
Contrast preparation example 2
This contrast preparation example is for mesoporous silicon aluminum that P Modification is described and preparation method thereof.
Mesoporous silicon aluminum is prepared, except for the difference that, in step (4) not according to the method for preparation example 1
Add magnesium nitrate and titanium sulfate；Its precipitate butt: H will be pressed by second solid sediment2O=1:10
Weight ratio mix making beating with water, and press P2O5: precipitate butt=0.075 of the second solid sediment:
The weight ratio of 1 adds ammonium phosphate, reacts 2 hours at 60 DEG C, dry at 120 DEG C after filtering washing
The product obtained after dry 10 hours, as the mesoporous silicon aluminum of the P Modification of reference, is designated as DA-2.
DA-2 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides
Analysis chemical composition is 0.08Na2O·76.6Al2O3·15.8SiO2·7.3P2O5；Specific surface area 469m2/ g,
Pore volume 1.31cm3/ g, average pore size 11.0nm.
Contrast preparation example 3
This contrast preparation example is used for metal-modified mesoporous silicon aluminum and preparation method thereof is described.
Mesoporous silicon aluminum is prepared, except for the difference that, in step (4) not according to the method for preparation example 1
Add ammonium phosphate；Its precipitate butt: H will be pressed by gained the second solid sediment2The weight of O=1:10
Amount mixes making beating than with water, and presses MgO:TiO2: precipitate butt=0.017 of the second solid sediment:
The weight ratio of 0.012:1 adds magnesium nitrate and titanium sulfate, reacts 2 hours at 60 DEG C, filters washing
After at 120 DEG C, be dried the product that obtains after the 10 hours metal-modified mesoporous silicon aluminium as reference
Material, is designated as DA-3.
DA-3 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides
Analysis chemical composition is 0.08Na2O·77.2Al2O3·15.9SiO2·1.5MgO·1.0TiO2；Specific surface area 496
m2/ g, pore volume 1.38cm3/ g, average pore size 11.2nm.
Embodiment 1
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
The boehmite of 20 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining
Serosity in add hydrochloric acid peptization, acid aluminum ratio (weight ratio) be 0.20:1, then temperature is risen to 65 DEG C
Being acidified 1 hour, (solid content is then to be separately added into the serosity of 28 parts by weight kaolin clay in terms of butt
25 weight %), the Alumina gel of 13 weight portions in terms of butt and 10 weight portions in terms of butt by
Preparation example 1 preparation phosphorus, (solid content is 18 weights to the serosity of metal-modified mesoporous silicon aluminum A-1
Amount %), stir 20 minutes, be added thereto to the described DASY of 29 weight portions in terms of butt the most again
Molecular sieve pulp (solid content is 35 weight %), is spray-dried after continuing stirring and makes microspherical catalyst.
Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then with (NH at 60 DEG C4)2SO4Solution
Washing (wherein, (NH4)2SO4: microspherical catalyst: H2O=0.05:1:10) to Na2O content is little
In 0.25 weight %, then with deionized water drip washing and filter, dry at 110 DEG C afterwards, obtain
Catalytic cracking catalyst C1, wherein, on the basis of the gross weight of described catalytic cracking catalyst C1, institute
State in catalytic cracking catalyst C1 containing the mesoporous active materials of 10 weight %, the DASY of 29 weight %
Molecular sieve, the Kaolin of 28 weight %, the Al of 33 weight %2O3Binding agent.
Comparative example 1
This comparative example is for catalytic cracking catalyst that reference is described and preparation method thereof.
Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1
Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 1 prepare
Mesoporous silicon aluminum DA-1 replace, obtain reference catalytic cracking catalyst CB1, wherein, with described
On the basis of the gross weight of reference catalytic cracking catalyst CB1, described reference catalytic cracking catalyst CB1
In containing the mesoporous silicon aluminum of 10 weight %, the DASY molecular sieve of 29 weight %, 28 weight %
Kaolin, the Al of 33 weight %2O3Binding agent.
Comparative example 2
This comparative example is for catalytic cracking catalyst that reference is described and preparation method thereof.
Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1
Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 2 prepare
The mesoporous silicon aluminum DA-2 of P Modification replace, obtain reference catalytic cracking catalyst CB2, wherein,
On the basis of the gross weight of described reference catalytic cracking catalyst CB2, described reference catalytic cracking is catalyzed
In agent CB2 containing the mesoporous silicon aluminum of 10 weight %, the DASY molecular sieve of 29 weight %, 28
The Kaolin of weight %, the Al of 33 weight %2O3Binding agent.
Comparative example 3
This comparative example is for catalytic cracking catalyst that reference is described and preparation method thereof.
Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1
Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 3 prepare
Metal-modified mesoporous silicon aluminum DA-3 replace, obtain reference catalytic cracking catalyst CB3, its
In, on the basis of the gross weight of described reference catalytic cracking catalyst CB3, described reference catalytic cracking
In catalyst CB3 containing the mesoporous silicon aluminum of 10 weight %, the DASY molecular sieve of 29 weight %,
The Kaolin of 28 weight %, the Al of 33 weight %2O3Binding agent.
Comparative example 4
This comparative example is for catalytic cracking catalyst that reference is described and preparation method thereof.
Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, be added without phosphorus, metal
Modified mesoporous silicon aluminum A-1, and by phosphorus, metal-modified mesoporous silicon aluminum A-1 with identical dry
The Kaolin of basic weight amount substitutes, and obtains reference catalytic cracking catalyst CB4, wherein, urges with described reference
On the basis of the gross weight of fluidized cracking catalysts CB4, described reference catalytic cracking catalyst CB4 contains
The DASY molecular sieve of 29 weight %, the Kaolin of 38 weight %, the Al of 33 weight %2O3Binding agent.
Embodiment 2
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
20 parts by weight kaolin clay in terms of butt are mixed making beating with deionized water, adds in terms of butt
The boehmite of 20 weight portions, and in the serosity obtained, add hydrochloric acid peptization, acid aluminum ratio (weight
Amount) it is 0.20:1, then temperature is risen to 65 DEG C and is acidified 1 hour, be then separately added in terms of butt
The Alumina gel of 5 weight portions, the phosphorus prepared by preparation example 2 of 30 weight portions in terms of butt, metal
The serosity (solid content is 20 weight %) of modified mesoporous silicon aluminum A-2, stirs 20 minutes, it
After be added thereto to the described DASY molecular sieve of 20 weight portions in terms of butt, 5 in terms of butt again
The mixed serum (solid content is 35 weight %) of the described ZRP-1 molecular sieve of weight portion, after continuing stirring
Spray drying makes microspherical catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then
With (NH at 60 DEG C4)2SO4Solution washing (wherein, (NH4)2SO4: microspherical catalyst: H2O=0.05:
1:10) to Na2O content is less than 0.25 weight %, then with deionized water drip washing and filter, the most again
Dry at 110 DEG C, obtain catalytic cracking catalyst C2, wherein, with described catalytic cracking catalyst
On the basis of the gross weight of C2, described catalytic cracking catalyst C2 contains the mesopore activity of 30 weight %
Material, the DASY molecular sieve of 20 weight %, the ZRP-1 molecular sieve of 5 weight %, the height of 20 weight %
Ridge soil, the Al of 25 weight %2O3Binding agent.
Embodiment 3
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
28 parts by weight kaolin clay in terms of butt are mixed making beating with deionized water, adds in terms of butt
The boehmite of 30 weight portions, and in the serosity obtained, add hydrochloric acid carry out peptization, acid aluminum ratio
(weight) is 0.20:1, then temperature rises to 65 DEG C and is acidified 1 hour, is then separately added into dry
The phosphorus prepared by preparation example 3 of 20 weight portions of base meter, metal-modified mesoporous silicon aluminum A-3
Serosity (solid content is 25 weight %), stirs 20 minutes, is added thereto in terms of butt the most again
The described REHY molecular sieve of 15 weight portions and the described Beta molecular sieve of 5 weight portions in terms of butt
The chlorination of mixed serum (solid content is 35 weight %) and 2 weight portions in terms of rare earth oxide is dilute
Soil solution, is spray-dried after continuing stirring and makes microspherical catalyst.Then by this microspherical catalyst at 500 DEG C
Lower roasting 1 hour, then with (NH at 60 DEG C4)2SO4Solution washing (wherein, (NH4)2SO4: microsphere
Catalyst: H2O=0.05:1:10) to Na2O content is less than 0.25 weight %, then uses deionization
Water wash also filters, and dries afterwards, obtain catalytic cracking catalyst C3 at 110 DEG C, wherein, with
On the basis of the gross weight of described catalytic cracking catalyst C3, described catalytic cracking catalyst C3 contains
The mesoporous active materials of 20 weight %, the REHY molecular sieve of 15 weight %, the Beta of 5 weight % divide
Son sieve, the Kaolin of 28 weight %, the Al of 30 weight %2O3Binding agent, the rare earth oxide of 2 weight %.
Embodiment 4
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
By the Alumina gel of the Kaolin of 40 weight portions in terms of butt and 15 weight portions in terms of butt and
The phosphorus prepared by preparation example 4 of 15 weight portions in terms of butt, metal-modified mesoporous silicon aluminum A-4
Serosity (solid content is 20 weight %) mixing making beating, stir 120 minutes, add the most wherein
Enter the described DOSY molecular sieve pulp (solid content is 35 weight %) of 30 weight portions in terms of butt,
It is spray-dried after continuing stirring and makes microspherical catalyst.Then by the roasting at 500 DEG C of this microspherical catalyst
1 hour, then with (NH at 60 DEG C4)2SO4Solution washing (wherein, (NH4)2SO4: microspherical catalyst:
H2O=0.05:1:10) to Na2O content is less than 0.25 weight %, then with deionized water drip washing also
Filter, dry at 110 DEG C afterwards, obtain catalytic cracking catalyst C4, wherein, with described catalysis
On the basis of the gross weight of Cracking catalyst C4, containing 15 weight % in described catalytic cracking catalyst C4
Mesoporous active materials, the DOSY molecular sieve of 30 weight %, the Kaolin of 40 weight %, 15 weight %
Al2O3Binding agent.
Embodiment 5
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
(1) Ludox is prepared:
1.7L hydrochloric acid 8.0kg decationized Y sieve water is diluted, by 7.7kg sodium silicate 8.0kg
Decationized Y sieve water is diluted, and the sodium silicate diluted is slowly added under stirring above-mentioned hydrochloric acid weak solution
In, obtain SiO2Concentration be 7.8 weight %, pH value be the Ludox of 2.8.
(2) catalytic cracking catalyst is prepared:
The height of 10 weight portions in terms of butt is added in the above-mentioned Ludox of 20 weight portions in terms of butt
Ridge soil, phosphorus, the metal prepared by preparation example 5 that add 40 weight portions in terms of butt after stirring 1h change
Property mesoporous silicon aluminum A-5 serosity (solid content is 18 weight %) mixing making beating, the most again to
(solid content is 30 weights wherein to add the described DASY molecular sieve pulp of 30 weight portions in terms of butt
Amount %), it is spray-dried after continuing stirring and makes microspherical catalyst.Then by this microspherical catalyst at 60 DEG C
Lower with (NH4)2SO4Solution washing (wherein, (NH4)2SO4: microspherical catalyst: H2O=0.05:1:
10) to Na2O content is less than 0.25 weight %, then with deionized water drip washing and filter, afterwards then at
Dry at 110 DEG C, obtain catalytic cracking catalyst C5, wherein, with described catalytic cracking catalyst C5
Gross weight on the basis of, in described catalytic cracking catalyst C5 containing 40 weight % mesoporous active materials,
The DASY molecular sieve of 30 weight %, the Kaolin of 10 weight %, the SiO of 20 weight %2Binding agent.
Embodiment 6
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
The boehmite of 18 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining
Serosity in add hydrochloric acid peptization, acid aluminum ratio (weight) be 0.20:1, then temperature is risen to 65 DEG C
Being acidified 1 hour, (solid content is then to be separately added into the serosity of 30 parts by weight kaolin clay in terms of butt
25 weight %), the Alumina gel of 7 weight portions in terms of butt and 5 weight portions in terms of butt by making
The phosphorus of standby example 6 preparation, the serosity (solid content is 20 weight %) of metal-modified mesoporous silicon aluminum A-6,
Stir 20 minutes, be added thereto to the most again the DOSY molecular sieve of 18 weight % in terms of butt with
The mixed serum (solid content is 35 weight %) of the DASY molecular sieve of 22 weight portions of butt meter, continues
It is spray-dried after continuous stirring and makes microspherical catalyst.Then by the roasting 1 at 500 DEG C of this microspherical catalyst
Hour, then with (NH at 60 DEG C4)2SO4Solution washing (wherein, (NH4)2SO4: microspherical catalyst:
H2O=0.05:1:10) to Na2O content is less than 0.25 weight %, then with deionized water drip washing also
Filter, dry at 110 DEG C afterwards, obtain catalytic cracking catalyst C6, wherein, with described catalysis
On the basis of the gross weight of Cracking catalyst C6, containing 5 weight % in described catalytic cracking catalyst C6
Mesoporous active materials, the DOSY molecular sieve of 18 weight %, the DASY molecular sieve of 22 weight %, 30
The Kaolin of weight %, the Al of 25 weight %2O3Binding agent.
Embodiment 7
Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.
Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1
Standby phosphorus, the phosphorus prepared by preparation example 7 of metal-modified mesoporous silicon aluminum A-1 identical weight part,
Metal-modified mesoporous silicon aluminum A-7 replaces, and obtains catalytic cracking catalyst C7, wherein, with institute
On the basis of stating the gross weight of catalytic cracking catalyst C7, containing 10 in described catalytic cracking catalyst C7
The mesoporous active materials of weight %, the DASY molecular sieve of 29 weight %, the Kaolin of 28 weight %, 33
The Al of weight %2O3Binding agent.
Embodiment 8-14
The test of the catalytic cracking catalyst performance that embodiment 8-14 provides for the present invention is described.
Respectively by the catalytic cracking catalyst C1-C7 of above-mentioned preparation 800 DEG C, the condition of 100% water vapour
Under aging 17 hours, be filled in small fixed flowing bed ACE device (purchased from KTI company of the U.S.) afterwards
In, amount of fill is each 9g.Then, reaction temperature be 500 DEG C, air speed be 16h-1, agent oil weight
Amount ratio for carrying out catalytic cracking reaction to the raw oil shown in table 1 under conditions of 6:1, reaction result arranges
In table 2 and table 3.Wherein, coke selectivity refers to the ratio of coke yield and conversion ratio.
Comparative example 5-8
Comparative example 5-8 is for illustrating the test of the catalytic cracking catalyst performance of reference.
According to the method for embodiment 8-14, raw oil is carried out catalytic cracking reaction, except for the difference that, will urge
Fluidized cracking catalysts C1-C7 respectively with the catalytic cracking catalyst CB1 of reference of identical weight part, CB2,
CB3 and CB4 substitutes, and reaction result is shown in Table 2.
Table 1
Table 2
Table 3
The result explanation of table 2 and table 3, identical with zeolite content but without the catalyst of mesoporous active materials
CB4 compares, and the catalyst that the present invention provides can be obviously improved the selectivity of coke, and vapour is greatly lowered
Oil sulfur content, the most also has higher cracking activity；Identical with each constituent content but use without phosphorus and
The catalyst CB1 of metal-modified mesoporous active materials compares, the coke of the catalyst that the present invention provides
Productivity reduces, and coke selectivity is obviously improved, and content of sulfur in gasoline is greatly lowered；With respectively
Constituent content is identical but uses the catalyst CB2 of the mesoporous active materials of P Modification to compare, and the present invention carries
The content of sulfur in gasoline of the catalyst of confession is greatly lowered；Identical with each constituent content but use metal-modified
The catalyst CB3 of mesoporous active materials compares, and the coke yield of the catalyst that the present invention provides reduces,
Coke selectivity is obviously improved, and also has the effect preferably reducing content of sulfur in gasoline.
As can be seen here, the catalytic cracking catalyst that the present invention provides can during RFCC
Show more preferable coke selectivity and higher catalytic cracking activity, and can effectively reduce FCC
Content of sulfur in gasoline.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (21)
1. a catalytic cracking catalyst, it is characterised in that with the gross weight of described catalytic cracking catalyst
On the basis of amount, described catalytic cracking catalyst contains the cracking activity constituent element of 1-60 weight %, 1-50 weight %
Mesoporous active materials, the clay of 1-70 weight % and the binding agent of 1-70 weight %；Described mesopore activity
Material has boehmite crystal phase structure, with the mass ratio range of oxide in described mesoporous active materials
Anhydrous chemical expression is: (0-0.2) Na2O·(40-85)Al2O3·(10-55)SiO2·(0.5-10)
P2O5·(0.5-10)MxOy, wherein metal M selected from Mg, periodic table of elements IIB, IIIB, IVB,
VIIB race element, and one or more in lanthanide series rare-earth elements, y is that metal M forms oxide
Time maximum close valence state, and the numerical value of x and y make M and O quantivalence balance and described mesopore
The specific surface area of active material is 200-500m2/ g, pore volume is 0.5-1.5cm3/ g, average pore size is
8-18nm。
Catalytic cracking catalyst the most according to claim 1, wherein, urges with described catalytic cracking
On the basis of the gross weight of agent, described catalytic cracking catalyst contains the cracking activity group of 10-50 weight %
Unit, the mesoporous active materials of 5-40 weight %, the clay of 10-60 weight % and the bonding of 10-60 weight %
Agent.
Catalytic cracking catalyst the most according to claim 1, wherein, described mesoporous active materials
Specific surface area be 300-450m2/ g, pore volume is 0.7-1.2cm3/ g, average pore size is 10-15nm.
Catalytic cracking catalyst the most according to claim 1, wherein, described metal M be Mg,
The mixing of one or more in Zn, Y, Ti, Mn, La and Ce.
5. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, described
Mesoporous active materials prepares in accordance with the following methods:
(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11,
Obtain plastic serosity；
(2) according to SiO2: Al2O3=1:(0.6-9) weight ratio in described plastic serosity, add silicon
Source, is aged 1-5 hour at room temperature to 90 DEG C, obtains the first solid sediment；
(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get oxidation
Sodium content is less than the second solid sediment of 0.3 weight %；
(4) by described second solid sediment, phosphorus source and the compound of metal M, according to P2O5:
MxOy: the precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): 1
Weight ratio contact processes, and product of contact is dried.
Catalytic cracking catalyst the most according to claim 5, wherein, aluminum described in step (1)
One or more in aluminum nitrate, aluminum sulfate and aluminum chloride of source；Described alkaline solution selected from ammonia,
One or more in sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution.
Catalytic cracking catalyst the most according to claim 5, wherein, silicon described in step (2)
Source is selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy
One or more in silicon and silicon oxide.
Catalytic cracking catalyst the most according to claim 5, wherein, by described in step (3)
It is by the first solid precipitation of step (2) gained that first solid sediment contacts the process processed with ammonium salt
Thing is by its precipitate butt: ammonium salt: H2O=1:(0.1-1): the weight ratio of (5-30) is in room temperature to 100 DEG C
Lower exchange, until sodium oxide content is less than 0.3 weight % in solid sediment.
Catalytic cracking catalyst the most according to claim 5, wherein, ammonium described in step (3)
One or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate of salt.
Catalytic cracking catalyst the most according to claim 5, wherein, by institute in step (3)
State the first solid sediment and contact the process processed with acid solution, be solid by the first of step (2) gained
Body precipitate presses its precipitate butt: acid: H2O=1:(0.03-0.30): the weight ratio of (5-30) exists
Room temperature exchanges at least 0.2 hour at 100 DEG C.
11. catalytic cracking catalysts according to claim 5, wherein, described in step (3)
One or more in sulphuric acid, hydrogen chloride and nitric acid of acid in acid solution.
12. catalytic cracking catalysts according to claim 5, wherein, by institute in step (4)
State the second solid sediment, phosphorus source contacts processing procedure with the compound of metal M, selected from following a), b),
C), d) during one:
A) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mix making beating with water, then the compound of phosphorus source and metal M is added sequentially in above-mentioned serosity, in room
At warm to 90 DEG C, contact processes at least 0.2 hour, is dried 10-20 after filtering washing at 100 DEG C-150 DEG C
Hour；
B) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mixing making beating with water, then phosphorus source joined in above-mentioned serosity, at room temperature to 90 DEG C, contact processes at least
0.2 hour, after filtration, the direct compound with metal M was mixed in proportion, at 100 DEG C after grinding uniformly
It is dried 10-20 hour at-150 DEG C；
C) by described second solid sediment by its precipitate butt: H2O=1:(5-20) weight ratio
Mix making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity,
Room temperature processes at least 0.2 hour to contact at 90 DEG C, obtains the 3rd solid sediment after filtration, then by the
Three solid sediments directly mix with the compound of the second metal M, at 100 DEG C after grinding uniformly
10-20 hour, wherein, the compound of described the first metal M and the second metal it is dried at-150 DEG C
The compound of M is identical or different；
D) direct for described second solid sediment and phosphorus source and genus M compound is mixed in proportion, grinds
It is dried 10-20 hour at 100 DEG C-150 DEG C after mill is uniform.
13. catalytic cracking catalysts according to claim 5, wherein, described in step (4)
After drying steps, also include gained desciccate roasting 1-4 hour at 500 DEG C-700 DEG C.
14. catalytic cracking catalysts according to claim 5, wherein, described in step (4)
One or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid of phosphorus source.
15. catalytic cracking catalysts according to claim 5, wherein, described in step (4)
The compound of metal M is water miscible compound.
16. catalytic cracking catalysts according to claim 5, wherein, described in step (4)
The compound of metal M is the nitrate of metal M, sulfate or chloride.
17. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, described
Cracking activity constituent element contains Y type molecular sieve.
18. catalytic cracking catalysts according to claim 17, wherein, described cracking activity group
Unit is possibly together with one or more in faujasite, Beta zeolite, MFI structure molecular sieve and modenite.
19. catalytic cracking catalysts according to claim 18, wherein, with described cracking activity
On the basis of the gross weight of constituent element, the content of described Y type molecular sieve is more than 75 weight %, described octahedral
The total content of zeolite, Beta zeolite, MFI structure molecular sieve and modenite is below 25 weight %.
The preparation method of catalytic cracking catalyst described in any one in 20. claim 1-19, should
Method includes the mixing making beating of described cracking activity constituent element, mesoporous active materials, clay and binding agent, so
After carry out the most successively being spray-dried, wash, filter and being dried.
In 21. claim 1-19, the catalytic cracking catalyst described in any one is at RFCC
In application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457668A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | High specific heat capacity matrix material and preparation method and application thereof |
| CN113457699A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | Phosphorus-containing matrix material and preparation method and application thereof |
| CN114425295A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking multifunctional metal trapping agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030166453A1 (en) * | 2002-02-25 | 2003-09-04 | Kuvettu Mohan Prabhu | Stabilized dual zeolite single particle catalyst composition and a process thereof |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN102079986A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Cracking method of heavy hydrocarbon oil |
| CN102078821A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Cracking catalyst containing mesoporous silica-alumina materials |
| CN102974383A (en) * | 2011-09-06 | 2013-03-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
-
2015
- 2015-04-29 CN CN201510214215.8A patent/CN106179457B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030166453A1 (en) * | 2002-02-25 | 2003-09-04 | Kuvettu Mohan Prabhu | Stabilized dual zeolite single particle catalyst composition and a process thereof |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN102079986A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Cracking method of heavy hydrocarbon oil |
| CN102078821A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Cracking catalyst containing mesoporous silica-alumina materials |
| CN102974383A (en) * | 2011-09-06 | 2013-03-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457668A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | High specific heat capacity matrix material and preparation method and application thereof |
| CN113457699A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | Phosphorus-containing matrix material and preparation method and application thereof |
| CN113457668B (en) * | 2020-03-31 | 2023-08-08 | 中国石油化工股份有限公司 | High specific heat capacity matrix material and preparation method and application thereof |
| CN113457699B (en) * | 2020-03-31 | 2023-11-10 | 中国石油化工股份有限公司 | Phosphorus-containing matrix material and preparation method and application thereof |
| CN114425295A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking multifunctional metal trapping agent and preparation method thereof |
| CN114425295B (en) * | 2020-09-23 | 2023-11-10 | 中国石油化工股份有限公司 | Multifunctional catalytic cracking metal trapping agent and preparation method thereof |
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