CN105312077B - 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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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 1 60 weight % cracking activity constituent element, 1 50 weight % mesopore activity silicon phosphor-aluminum material, 1 70 weight % clay and 1 70 weight % binding agent；Mesopore activity silicon phosphor-aluminum material has a boehmite crystal phase structure, and using the anhydrous chemical expression of the weight ratio meter of oxide as：(0‑0.2)Na2O·(50‑86)Al2O3·(12‑50)SiO2·(0.5‑10)P2O5, specific surface area is 200 600m2/ g, pore volume are 0.5 1.8cm3/ g, average pore size are 8 18nm；On the basis of the gross weight of cracking activity constituent element, cracking activity constituent element contains 50 95 weight % the first molecular sieve component and 5 50 weight % the second molecular sieve component.The catalytic cracking catalyst not only has relatively low coke selectivity and higher catalytic cracking activity during RFCC, but also can obtain higher yield of liquefied gas.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, the preparation method of the catalytic cracking catalyst and the catalysis
Application of the Cracking catalyst in RFCC.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, and very important status is occupied in petroleum refining industry.
In catalytic cracking process, heavy end (such as vacuum distillate or the residual oil of more heavy constituent) occurs instead in the presence of a catalyst
Should, the high value added products such as liquefied gas, gasoline, diesel oil are converted into, usually require to live using with high cracking in this process
The catalysis material of property.Micro-pore zeolite catalysis material due to excellent shape selective catalysis performance and very high cracking reaction activity,
It is widely used in petroleum refining and processing industry.With the increasingly depleted of petroleum resources and wanting for environmental protection etc.
Ask, particularly crude oil becomes the wilderness demand of growth trend and market to light-end products increasingly again, in PETROLEUM PROCESSING industry more
More to pay attention to the deep processing to heavy oil and residual oil.
For improving conversion ratio, strengthen heavy oil conversion performance, while reduce further turning for intermediate oil and naphtha
Change, traditional micro porous molecular sieve catalysis material shows obvious limitation diffusion to larger raw molecule because its duct is smaller
Effect so that simple micro porous molecular sieve catalysis material is less suitable for splitting for the catalysis of the heavy distillates such as heavy oil and residual oil
Change, thus need to use aperture is larger, reactant molecule is not spread limitation and with compared with high cracking activity material.Cause
This, mesoporous and macropore catalysis material research and development are increasingly valued by people.In addition, in catalytic cracking field, sial material
Material is widely applied because it has stronger acid centre and good cracking performance.
CN1565733A discloses a kind of mesopore silica-alumina material, and the mesopore silica-alumina material has boehmite crystalline phase knot
Structure, using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.3)Na2O·(40-90)Al2O3·(10-60)
SiO2, its specific surface area is 200-400m2/ g, pore volume 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-
15nm.The preparation of the mesopore silica-alumina material is without the use of organic formwork agent, and synthesis cost is low, and obtained mesopore silica-alumina material tool
There are high cracking activity and hydrothermal stability, good macromolecular cracking performance is shown in catalytic cracking reaction.
CN1854258A discloses a kind of fluid cracking catalyst, and the fluid cracking catalyst contains 3-20 weight % warp
The mesoporous silica-alumina materials of acid treatment, the mesoporous silica-alumina materials have boehmite crystal phase structure, with the weight ratio meter of oxide
Anhydrous chemical expression be：(0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2, specific surface area 200-400m2/
G, pore volume 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-15nm.
CN1978593A discloses a kind of Cracking catalyst, and a kind of mesoporous material is contained in the Cracking catalyst, is given an account of
The anhydrous compound of Porous materials is formed using the weight ratio meter of oxide as (0-0.3) Na2O·(40-85)Al2O3·(10-55)
SiO2·(1-20)MxOy, wherein, metal M is selected from the periodic table of elements IIA, IB, IIB, IVB, VB, VIB, VIIB, VIIIB or lanthanum
One kind in series rare earth element, the mesoporous material have boehmite crystal phase structure, specific surface area 200-400m2/ g, hole
Hold for 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-15nm.The catalyst is used directly for being catalyzed
In cracking reaction, under conventional FCC operating conditions, crude oil and heavy oil conversion ratio can be both improved, can effectively reduce FCC vapour again
Oily sulfur content.
CN102078821A discloses a kind of Cracking catalyst of containing mesopore silica-alumina material, wherein, the Cracking catalyst by
Cracking activity constituent element, clay, binding agent and mesoporous silica-alumina materials composition, the mesoporous silica-alumina materials have boehmite crystalline phase
Structure, using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.3)Na2O·(40-90)Al2O3·(10-60)
SiO2, specific surface area 200-400m2/ g, pore volume 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-
15nm, the binding agent are Ludox and/or Alumina gel.Although the Cracking catalyst and the Conventional catalytic using boehmite
Agent is compared, and has that production cost is low, the more preferable advantage of converting crude oil ability, but its coke selectivity is poor.
The content of the invention
The invention aims to provide a kind of new to have relatively low coke selectivity, compared with high cracking activity and energy
It is enough to obtain the higher catalytic cracking catalyst of yield of liquefied gas, the preparation method of the catalytic cracking catalyst and described urge
Application of the fluidized cracking catalysts in RFCC.
The invention provides a kind of catalytic cracking catalyst, wherein, using the gross weight of the catalytic cracking catalyst as base
Standard, the catalytic cracking catalyst contain 1-60 weight % cracking activity constituent element, 1-50 weight % mesopore activity silicon phosphorus aluminium
The binding agent of material, 1-70 weight % clay and 1-70 weight %；The mesopore activity silicon phosphor-aluminum material, which has, intends thin water aluminium
Stone crystal phase structure, in the mesopore activity silicon phosphor-aluminum material using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-
0.2)Na2O·(50-86)Al2O3·(12-50)SiO2·(0.5-10)P2O5, and the ratio of the mesopore activity silicon phosphor-aluminum material
Surface area is 200-600m2/ g, pore volume 0.5-1.8cm3/ g, average pore size 8-18nm；
With the gross weight benchmark of the cracking activity constituent element, the cracking activity constituent element contains the first of 50-95 weight %
Second molecular sieve component of molecular sieve component and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, second
One or more in Y type molecular sieve and the 3rd Y type molecular sieve, second molecular sieve component are the first MFI structure molecular sieve
And/or the second MFI structure molecular sieve；
First Y type molecular sieve is the DASY molecular sieves containing rare earth；
Second Y type molecular sieve is REY molecular sieves；
Using the content of rare earth that rare earth oxide is counted as 12-16 weight % in 3rd Y type molecular sieve, with P2O5The phosphorus of meter
Content is 0.5-7 weight %, the molecular sieve31In P MAS NMR spectras, chemical shift is that -14 ± 2ppm and -23 ± 2ppm are common
Shake signal peak area account for total peak area percentage be more than 85%, the molecular sieve27In Al MAS NMR spectras, chemical shift
The percentage of total peak area is accounted for more than 20% for the peak area of 0 ± 2ppm resonance signals；
In the first MFI structure molecular sieve using the anhydrous chemical expression of the molar ratio computing of oxide as：(0.01-
0.25)RE2O3·(0.005-0.02)Na2O·Al2O3·(0.2-1)P2O5·(35-120)SiO2, the molecular sieve is to n-hexane
Absorption weight ratio with hexamethylene is 4-5：1；
In the second MFI structure molecular sieve using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.3)
Na2O·(0.5-5.5)Al2O3·(1.3-10)P2O5·(0.7-15)M1xOy·(0.01-5)M2mOn·(70-97)SiO2, its
In, M1 Fe, Co or Ni, x represent M1 atomicity, and y represents the number for meeting M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or
Sn, m represent M2 atomicity, and n represents the number for meeting M2 oxidation state requisite oxygens.
Present invention also offers the preparation method of the catalytic cracking catalyst, this method is included the cracking activity group
Member, mesopore activity silicon phosphor-aluminum material, clay and binding agent are mixed with beating, be then spray-dried, washed successively again, being filtered and
Dry.
In addition, the application present invention also offers the catalytic cracking catalyst in RFCC.
Catalytic cracking catalyst provided by the invention is by by specific cracking activity constituent element, specific mesopore activity silicon phosphorus
Aluminum is used cooperatively with clay and binding agent, adds the content of catalytic cracking catalyst mesopore, is advantageous to heavy oil macromolecular
Diffusion and cracking, the catalytic cracking catalyst is especially suitable for RFCC, during RFCC not
Relatively low coke selectivity and higher catalytic cracking activity can be only shown, and higher liquefied gas can also be obtained
Yield.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X-ray diffraction spectrogram of the mesopore activity silicon phosphor-aluminum material obtained by preparation example 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of catalytic cracking catalyst, wherein, using the gross weight of the catalytic cracking catalyst as base
Standard, the catalytic cracking catalyst contain 1-60 weight % cracking activity constituent element, 1-50 weight % mesopore activity silicon phosphorus aluminium
The binding agent of material, 1-70 weight % clay and 1-70 weight %；The mesopore activity silicon phosphor-aluminum material, which has, intends thin water aluminium
Stone crystal phase structure, in the mesopore activity silicon phosphor-aluminum material using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-
0.2)Na2O·(50-86)Al2O3·(12-50)SiO2·(0.5-10)P2O5, and the ratio of the mesopore activity silicon phosphor-aluminum material
Surface area is 200-600m2/ g, pore volume 0.5-1.8cm3/ g, average pore size 8-18nm；
On the basis of the gross weight of the cracking activity constituent element, the cracking activity constituent element contains the of 50-95 weight %
Second molecular sieve component of one molecular sieve component and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, the
One or more in two Y type molecular sieves and the 3rd Y type molecular sieve, second molecular sieve component are the first MFI structure molecule
Sieve and/or the second MFI structure molecular sieve；
First Y type molecular sieve is the DASY molecular sieves containing rare earth；
Second Y type molecular sieve is REY molecular sieves；
Using the content of rare earth that rare earth oxide is counted as 12-16 weight % in 3rd Y type molecular sieve, with P2O5The phosphorus of meter
Content is 0.5-7 weight %, the molecular sieve31In P MAS NMR spectras, chemical shift is that -14 ± 2ppm and -23 ± 2ppm are common
Shake signal peak area account for total peak area percentage be more than 85%, the molecular sieve27In Al MAS NMR spectras, chemical shift
The percentage of total peak area is accounted for more than 20% for the peak area of 0 ± 2ppm resonance signals；
In the first MFI structure molecular sieve using the anhydrous chemical expression of the molar ratio computing of oxide as：(0.01-
0.25)RE2O3·(0.005-0.02)Na2O·Al2O3·(0.2-1)P2O5·(35-120)SiO2, the molecular sieve is to n-hexane
Absorption weight ratio with hexamethylene is 4-5：1；
In the second MFI structure molecular sieve using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.3)
Na2O·(0.5-5.5)Al2O3·(1.3-10)P2O5·(0.7-15)M1xOy·(0.01-5)M2mOn·(70-97)SiO2, its
In, M1 Fe, Co or Ni, x represent M1 atomicity, and y represents the number for meeting M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or
Sn, m represent M2 atomicity, and n represents the number for meeting M2 oxidation state requisite oxygens.
In the present invention, the specific surface area, pore volume and average pore size are surveyed using nitrogen absorption under low temperature-desorption method
Fixed, used instrument is the physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S..
According to catalytic cracking catalyst provided by the invention, it is preferable that using the gross weight of the catalytic cracking catalyst as
Benchmark, the catalytic cracking catalyst contain 10-50 weight % cracking activity constituent element, 5-40 weight % mesopore activity silicon phosphorus
The binding agent of aluminum, 10-60 weight % clay and 10-60 weight %, the content control of above-mentioned each component is preferred at this
In the range of the catalytic cracking catalyst that enables to there is more preferable combination property.
According to catalytic cracking catalyst provided by the invention, in order that obtaining the first molecular sieve component and the second molecular sieve component
More preferable coordinated effect can be played, it is preferable that on the basis of the gross weight of the cracking activity constituent element, the cracking is lived
Property constituent element contains 65-86 weight % the first molecular sieve component and 14-35 weight % the second molecular sieve component.
According to catalytic cracking catalyst provided by the invention, it is preferable that first molecular sieve component is the first Y types
At least two mixture in molecular sieve, second Y type molecular sieve and the 3rd Y type molecular sieve, second molecule
Screen banks is divided into the first MFI structure molecular sieve or the second MFI structure molecular sieve.
As described above, first Y type molecular sieve is the DASY molecular sieves containing rare earth.The DASY molecular sieves containing rare earth
Refer to the hydro-thermal super stable molecular sieve containing rare earth, wherein, with rare earth oxide (RE in the DASY molecular sieves containing rare earth2O3) meter
Content of rare earth can be 1.5-3 weight %.The DASY molecular sieves containing rare earth can be various commercially available prod, such as can be with
For purchased from the DASY2.0 molecular sieves of Sinopec catalyst asphalt in Shenli Refinery.
Second Y type molecular sieve is REY molecular sieves.The REY molecular sieves refer to rare earth Y type molecular sieve, and it can be
Various commercially available REY zeolite products, such as Sinopec catalyst asphalt in Shenli Refinery can be purchased from.
Using the content of rare earth that rare earth oxide is counted as 12-16 weight % in 3rd Y type molecular sieve, with P2O5The phosphorus of meter
Content is 0.5-7 weight %, the molecular sieve31In P MAS NMR spectras, chemical shift is that -14 ± 2ppm and -23 ± 2ppm are common
Shake signal peak area account for total peak area percentage be more than 85%, the molecular sieve27In Al MAS H NMR spectroscopies, chemical shift is
The percentage that the peak area of 0 ± 2ppm resonance signals accounts for total peak area is more than 20%.Preferably, in the 3rd Y type molecular sieve
With P2O5The phosphorus content of meter is 1-3 weight %.It is further preferred that the 3rd Y type molecular sieve31In P MASNMR spectrums, change
Displacement study is -14 ± 2ppm and the peak area of -23 ± 2ppm resonance signals accounts for the percentage of total peak area more than 90%.More preferably
Ground, the lattice constant of the 3rd Y type molecular sieve areIn addition, the 3rd Y type molecular sieve can be according to
Well known to a person skilled in the art various methods to be prepared, for example, being referred to the method system disclosed in CN101088917A
It is standby to obtain.
The x-ray diffraction spectra data of the first MFI structure molecular sieve are as shown in table 1 below：
Table 1
| D values (× 10-1Nanometer) | Relative intensity value (I/I0) |
| 11.2±0.2 | VS |
| 10.1±0.2 | M |
| 9.8±0.2 | VW |
| 3.85±0.04 | VS |
| 3.81±0.04 | S |
| 3.75±0.04 | W |
| 3.72±0.04 | M |
| 3.65±0.04 | M |
| 3.60±0.04 | W |
Relative intensity value in table 1 represented by each symbol is as follows：VS：80-100%；S：60-80%；M：40-60%；W：
20-40%；VW：<20%.
In addition, in the first MFI structure molecular sieve, it is transgranular that rare earth is included in molecular sieve, wherein, rare earth is from synthesis
The used faujasite seeds containing rare earth during the first MFI structure molecular sieve.In the first MFI structure molecular sieve
In, phosphorus is combined with the aluminum chemistry in framework of molecular sieve, and the first MFI structure molecular sieve exists27Have in Al H NMR spectroscopies and correspond to Al
Spectral peak that (4Si) is coordinated (i.e. Al is derived from forms tetrahedral structures by oxygen and four Si atoms), that chemical shift is 55ppm,
And it is coordinated (i.e. Al atoms pass through oxygen and four P atoms form tetrahedral structures), chemical shift with Al (4P) is corresponded to
For 39ppm spectral peak；The first MFI structure molecular sieve exists31In P H NMR spectroscopies then have correspond to P (4Al) coordination (i.e. there is
PO4Tetrahedron and adjacent AlO4Tetrahedral interaction), chemical shift be -29ppm spectral peak.Preferably, described first
Phosphorus in MFI structure molecular sieve is uniformly distributed in molecular sieve crystalline phase, is specifically reflected in：Transmission electron microscope-energy dispersive spectrum (TEM-
EDS analysis result) shows that the phosphorus content in any single crystal grain is close with the phosphorus content in molecular sieve body phase.
The first MFI structure molecular sieve is 4-5 to the absorption weight ratio of n-hexane and hexamethylene：1, be in adsorption temp
40 DEG C, adsorption time be 3 hours, absorption phase pressure P/P0Under conditions of=0.20-0.25, the first MFI structure molecular sieve pair
The adsorbance of n-hexane is 98-105 milligrams per grams, and the adsorbance to hexamethylene is 20-25 milligrams per grams.The absorption weight ratio
The absorption weight ratio (2-2.5) of (4-5) apparently higher than ZSM-5 zeolite.
In addition, the first MFI structure molecular sieve can be commercially available, can also be public according to those skilled in the art
The various methods known are prepared, for example, can be prepared according to the method disclosed in CN1147420A.
According to catalytic cracking catalyst provided by the invention, it is preferable that the second MFI structure molecular sieve is with oxide
The anhydrous chemical expression of weight ratio meter is (0-0.2) Na2O·(0.9-5)Al2O3·(1.5-7)P2O5·(0.9-10)
M1xOy·(0.5-2)M2mOn·(82-92)SiO2, wherein, M1 Fe, Co or Ni, x expression M1 atomicity, y represent to meet M1
The number of oxidation state requisite oxygen, M2 Zn, Mn, Ga or Sn, m represent M2 atomicity, and n represents to meet M2 oxidation state requisite oxygens
Number.It is particularly preferred that M1 is Fe, M2 Zn.
In addition, the second MFI structure molecular sieve can be commercially available, can also be public according to those skilled in the art
The various methods known are prepared, for example, can be prepared according to the method disclosed in CN1611299A.
According to catalytic cracking catalyst provided by the invention, it is preferable that the ratio surface of the mesopore activity silicon phosphor-aluminum material
Product is 250-550m2/ g, pore volume 0.6-1.6cm3/ g, average pore size 9-15nm.
The mesopore activity silicon phosphor-aluminum material can be prepared in accordance with the following methods：By silicon source and alkaline solution in room temperature
Plastic is neutralized to 85 DEG C, the pH value for controlling plastic is 7-11, according still further to SiO2：Al2O3=1：1-7.5 weight ratio is to plastic
Add silicon source in slurries, then in room temperature to 1-5 hours are aged at 90 DEG C, then will be aged obtained solid sediment and ammonium salt or
Filtered after acid solution contact, the solid product that sodium oxide content is less than 0.3 weight % is obtained, then again by the solid product
Contacted with phosphorus source, and product of contact is dried；Phosphorus source is with P2O5The dosage of meter and the weight of the butt of solid product ratio are
0.005-0.1：1.
In the preparation method of above-mentioned mesopore activity silicon phosphor-aluminum material, the step of obtaining before the solid product, can be with
Carried out with reference to the method disclosed in CN1565733A.
Specifically, source of aluminium can be the existing various materials that can be converted into aluminum oxide, for example, nitre can be selected from
One or more in sour aluminium, aluminum sulfate and aluminium chloride.
The alkaline solution can be the existing various materials that alkalescence is presented, for example, ammoniacal liquor, sodium hydroxide can be selected from
One or more in solution, potassium hydroxide solution and sodium aluminate solution.Wherein, the concentration of the alkaline solution can be this
The conventional selection in field, therefore not to repeat here.
The silicon source can be the existing various materials that can be converted into silica, for example, waterglass, silicon can be selected from
One or more in sour sodium, tetraethoxy-silicane and silica.
The present invention is not particularly limited to the method for contacting the solid sediment with ammonium salt, for example, can include
The solid sediment is pressed into its butt：Ammonium salt：H2O=1：0.1-1：5-30 weight ratio is in room temperature to being handed at 100 DEG C
Change.Wherein, the number of the contact can be 1-3 times, and each time of contact be able to should specifically make to obtain with 0.5-1 hours
Solid product in the content of sodium oxide molybdena be defined less than 0.3 weight %.
In addition, the species of the ammonium salt can be this area conventional selection, for example, can be selected from ammonium chloride, ammonium sulfate,
One or more in ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.
The present invention is not particularly limited to the method that contacts the solid sediment with acid solution, for example, can be with
Including the solid sediment is pressed into its butt：Acid：H2O=1：0.03-0.3：5-30 weight ratio is in room temperature to handing at 100 DEG C
Shift to few 0.2 hour.
In addition, the species of the acid solution can be the conventional selection of this area, usually inorganic acid, for example, described
Acid in acid solution can be selected from the one or more in sulfuric acid, hydrogen chloride and nitric acid.
According to catalytic cracking catalyst provided by the invention, wherein, contact between the solid product and phosphorus source can be with
Carry out in presence of water, the contact method includes：The solid product is pressed into its butt：Water=1：5-20 weight is than mixed
Mashing is closed, phosphorus source is added and in room temperature to reaction 0.2-5 hours, preferably 0.5-3 hours at 90 DEG C, is connect again by what is obtained afterwards
Tactile product is filtered, washed.In addition, contact between the solid product and phosphorus source can also be by the solid product with
Phosphorus source is mixed and ground.The condition that the product of contact of the solid product and phosphorus source is dried is generally included：Drying temperature
It can be 100-150 DEG C, drying time can be 10-20 hours.Further, optionally, the mesopore activity silicon phosphor-aluminum material
Preparation method can also include desciccate being calcined, and it can be 500- that the condition of the roasting, which generally includes sintering temperature,
700 DEG C, roasting time can be 1-4 hours.
The species of phosphorus source can be this area conventional selection, for example, can be selected from ammonium phosphate, diammonium hydrogen phosphate,
One or more in ammonium dihydrogen phosphate and phosphoric acid.
The clay can be the existing various clays that can be used in catalytic cracking catalyst, for example, can be selected from
Kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and swollen
One or more in profit soil.
The binding agent can be the existing various binding agents that can be used in catalytic cracking catalyst, for example, can be with
One or more in Ludox, Alumina gel and boehmite.
The preparation method of catalytic cracking catalyst provided by the invention is included above-mentioned cracking activity constituent element, mesopore activity silicon
Phosphor-aluminum material, clay and binding agent are mixed with beating, and are then spray-dried, washed, filtered and dried successively again.
According to the preparation method of catalytic cracking catalyst provided by the invention, by the cracking activity constituent element, mesopore activity
Silicon phosphor-aluminum material, clay and binding agent are mixed with beating, and follow-up spray drying, washing, filtering and drying, these processes
Implementation can use conventional method to implement, their specific implementation method for example CN1916166A, CN1098130A,
There is detailed description in CN1362472A, CN1727442A, CN1132898C and CN1727445A, introduce this hair in the lump here
In bright by reference.Typically also, after the spray drying, before washing, the preparation of the catalytic cracking catalyst
The step of method generally also includes Spray dried products being calcined.The condition of the roasting generally includes sintering temperature can be with
For 500-700 DEG C, roasting time can be 1-4 hours.
In addition, the application present invention also offers above-mentioned catalytic cracking catalyst in RFCC.
The present invention will be described in detail by way of examples below.
The raw material used in following preparation example, contrast preparation example, embodiment and comparative example is as follows：
Hydrochloric acid is produced by Beijing Chemical Plant, and chemistry is pure, and concentration is 36 weight %；
Sodium silicate is commercially available, SiO2Concentration is 26.0 weight %, modulus 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 %；
First Y type molecular sieve is DASY2.0 molecular sieves, is produced by Sinopec catalyst asphalt in Shenli Refinery；
Second Y type molecular sieve is REY molecular sieves, is produced by Sinopec catalyst asphalt in Shenli Refinery；
Method of 3rd Y type molecular sieve in CN101088917A embodiments 1 is made；
Method of the first MFI structure molecular sieve in CN1147420A embodiments 1 is made；
Method of the second MFI structure molecular sieve in CN1611299A embodiments 1 is made.
In following preparation example, contrast preparation example, embodiment and comparative example：
Specific surface area, pore volume and average pore size are measured using nitrogen absorption under low temperature-desorption method, and used instrument is
The physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S..Na in mesopore activity silicon phosphor-aluminum material2O、Al2O3、
SiO2、P2O5Content determined with x-ray fluorescence method (referring to《Petrochemical Engineering Analysis method (RIPP experimental methods)》, Yang Cui is fixed etc.
Compile, Science Press, nineteen ninety publishes).
Preparation example 1
The preparation example is used to illustrate mesopore activity silicon phosphor-aluminum material provided by the invention and preparation method thereof.
Using concentration as 90gAl2O3/ L Al2(SO4)3Solution and concentration are 102gAl2O3/ L, the NaAlO that Crater corrosion is 2.52
Solution is reaction raw materials, at 85 DEG C cocurrent plastic and control plastic pH value be 9.5, collect a certain amount of plastic slurries, stirring
SiO is pressed down2：Al2O3=1：It is 60gSiO that 6.56 ratio, which adds concentration,2/ L sodium silicate, it is warming up to 70 DEG C and is aged 2 hours,
Obtain solid sediment.Use NH4Cl solution presses solid sediment (butt)：NH4Cl：H2O=1：0.8：15 weight ratio is at 60 DEG C
Under to solid sediment carry out ion exchange to remove sodium ion, ion exchange repeats twice, every time carry out 0.5 hour,
The solid product that sodium oxide content is less than 0.3 weight % is obtained after filtering, it is then again that the solid product is (dry by solid product
Base)：H2O=1：8 weight ratio is mixed with beating with water, and presses P2O5：Solid product butt=0.022：1 weight is than adding phosphorus
The sour ammonium of hydrogen two, reacted 1 hour at 70 DEG C, filtering washing obtains mesopore activity silicon phosphorus aluminium after being dried 10 hours at 120 DEG C
Material, it is designated as A-1.
Mesopore activity silicon phosphor-aluminum material A-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is as shown in Figure 1.Using
X-ray fluorescence method measures, mesopore activity silicon phosphor-aluminum material A-1 using the chemical composition of the weight ratio meter of oxide as：
0.11Na2O·84.0Al2O3·12.8SiO2·2.1P2O5.Mesopore activity silicon phosphor-aluminum material A-1 specific surface area is 501m2/
G, pore volume 1.51cm3/ g, average pore size 12.1nm.
Preparation example 2
The preparation example is used to illustrate mesopore activity silicon phosphor-aluminum material provided by the invention and preparation method thereof.
Method according to preparation example 1 prepares mesopore activity silicon phosphor-aluminum material, unlike, the dosage of diammonium hydrogen phosphate causes
P2O5：Solid product butt=0.095：1, to be reacted 2 hours at 70 DEG C, filtering is washed after drying 10 hours at 120 DEG C,
Mesopore activity silicon phosphor-aluminum material is obtained, is designated as A-2.
Mesopore activity silicon phosphor-aluminum material A-2 has structure of similar to thin diaspore, its X-ray diffraction spectrogram and mesopore activity silicon phosphorus
Aluminum A-1 is similar.Measured using X-ray fluorescence method, mesopore activity silicon phosphor-aluminum material A-2 is with the weight ratio meter of oxide
Chemical composition be：0.09Na2O·78.1Al2O3·12.3SiO2·9.3P2O5.Mesopore activity silicon phosphor-aluminum material A-2 ratio table
Area is 487m2/ g, pore volume 1.33cm3/ g, average pore size 10.9nm.
Preparation example 3
The preparation example is used to illustrate mesopore activity silicon phosphor-aluminum material provided by the invention and preparation method thereof.
Using concentration as 90gAl2O3/ L Al2(SO4)3Solution and concentration are 102gAl2O3/ L, the NaAlO that Crater corrosion is 1.72
Solution is reaction raw materials, at 60 DEG C cocurrent plastic and control plastic pH value be 10.5, collect quantitative plastic slurries, stirring
SiO is pressed down2：Al2O3=1：It is 60gSiO that 2.47 ratio, which adds concentration,2/ L sodium silicate, it is warming up to 60 DEG C and is aged 3 hours,
Obtain solid sediment.Use NH4Cl solution presses solid sediment (butt)：NH4Cl：H2O=1：1：10 weight ratio is at 60 DEG C
Ion exchange is carried out to solid sediment to remove sodium ion, and is eluted to sodium oxide content and is less than with a large amount of deionized waters
0.3%, gained solid product is then pressed into solid product (butt)：H2O=1：10 weight ratio is mixed with beating with water, and is pressed
P2O5：Solid product butt=0.052：1 weight is reacted 2 hours, filtering washing than adding ammonium dihydrogen phosphate at 70 DEG C
After being dried 10 hours at 120 DEG C, mesopore activity silicon phosphor-aluminum material is obtained, is designated as A-3.
Mesopore activity silicon phosphor-aluminum material A-3 has structure of similar to thin diaspore, its X-ray diffraction spectrogram and mesopore activity silicon phosphorus
Aluminum A-1 is similar.Measured using X-ray fluorescence method, mesopore activity silicon phosphor-aluminum material A-3 is with the weight ratio meter of oxide
Chemical composition be：0.08Na2O·67.3Al2O3·27.3SiO2·5.1P2O5.Mesopore activity silicon phosphor-aluminum material A-3 ratio table
Area is 373m2/ g, pore volume 1.07cm3/ g, average pore size 11.5nm.
Preparation example 4
The preparation example is used to illustrate mesopore activity silicon phosphor-aluminum material provided by the invention and preparation method thereof.
Using concentration as 90gAl2O3/ L Al2(SO4)3Solution and concentration are 102gAl2O3/ L, the NaAlO that Crater corrosion is 1.72
Solution is reaction raw materials, the cocurrent plastic and to control plastic pH value be 9.0 at 40 DEG C, collects quantitative plastic slurries, under agitation
By SiO2：Al2O3=1：It is 60gSiO that 1.52 ratio, which adds concentration,2/ L sodium silicate, it is warming up to 80 DEG C and is aged 1.5 hours,
Obtain solid precipitated product.Use NH4Cl solution presses solid sediment (butt)：NH4Cl：H2O=1：1：12 weight ratio is at 60 DEG C
Under to solid sediment carry out ion exchange remove sodium ion, and with a large amount of deionized waters elute to sodium oxide content be less than 0.3
Weight %, solid product of the sodium oxide content less than 0.3 weight % is directly then pressed into P with phosphoric acid2O5：Solid product butt=
0.008：1 weight is uniformly dried 10 hours than mixing, grinding after 120 DEG C, obtains mesopore activity silicon phosphor-aluminum material.It is designated as A-
4。
Mesopore activity silicon phosphor-aluminum material A-4 has structure of similar to thin diaspore, its X-ray diffraction spectrogram and mesopore activity silicon phosphorus
Aluminum A-1 is similar.Measured using X-ray fluorescence method, mesopore activity silicon phosphor-aluminum material A-4 is with the weight ratio meter of oxide
Chemical composition be：0.14Na2O·59.3Al2O3·39.1SiO2·0.8P2O5.Mesopore activity silicon phosphor-aluminum material A-4 ratio table
Area is 320m2/ g, pore volume 0.78cm3/ g, average pore size 9.7nm.
Preparation example 5
The preparation example is used to illustrate mesopore activity silicon phosphor-aluminum material provided by the invention and preparation method thereof.
It is first 90gAl by quantitative concentrations2O3/ L Al2(SO4)3Solution is placed in beaker, with vigorous stirring by ammoniacal liquor by
Plastic is added dropwise to, until the pH value of system is 10.5, gelling temperature is 40 DEG C；Press SiO again under agitation2：Al2O3=1：1.05
Ratio concentration is added into obtained plastic slurries is 60gSiO2/ L sodium silicate, it is warming up to 70 DEG C and is aged 3 hours, obtain
To solid sediment.Then gained solid sediment is pressed into solid sediment (butt)：HCl：H2O=1：0.08：10 weight
Than being exchanged 30 minutes at 60 DEG C, filtering washing makes sodium oxide content be less than 0.3%, obtains solid product and is designated as SA-L5, then
By obtained solid product by solid product (butt)：H2O=1：8 weight ratio is mixed with beating with water, and presses P2O5：Solid produces
Thing butt=0.016：1 weight is reacted 2 hours, filtering washing is after at 120 DEG C dry 10 than adding phosphoric acid at 60 DEG C
Hour, mesopore activity silicon phosphor-aluminum material is obtained, is designated as A-5.
Mesopore activity silicon phosphor-aluminum material A-5 has structure of similar to thin diaspore, its X-ray diffraction spectrogram and mesopore activity silicon phosphorus
Aluminum A-1 is similar.Measured using X-ray fluorescence method, mesopore activity silicon phosphor-aluminum material A-5 is with the weight ratio meter of oxide
Chemical composition be：0.12Na2O·50.2Al2O3·48.0SiO2·1.5P2O5.Mesopore activity silicon phosphor-aluminum material A-5 ratio table
Area is 289m2/ g, pore volume 0.64cm3/ g, average pore size 8.8nm.
Contrast preparation example 1
The contrast preparation example is used to illustrate mesopore silica-alumina material and preparation method thereof.
Method according to preparation example 1 prepares mesopore silica-alumina material, unlike, do not include the solid product pressing solid
Product (butt)：H2O=1：8 weight ratio be mixed with beating with water after the step of, but sodium oxide content is directly less than 0.3
Mesopore activity silica-alumina material of the product that weight % solid product obtains after being dried 10 hours at 120 DEG C as reference, note
For DA-1.
Mesopore activity silica-alumina material DA-1 has structure of similar to thin diaspore, its X-ray diffraction spectrogram and mesopore activity silicon phosphorus
Aluminum A-1 is similar.Measured using X-ray fluorescence method, mesopore activity silica-alumina material DA-1 is with the weight ratio meter of oxide
Chemical composition be：0.19Na2O·81.9Al2O3·16.7SiO2.Mesopore activity silica-alumina material DA-1 specific surface area is
514m2/ g, pore volume 1.45cm3/ g, average pore size 11.3nm.
Embodiment 1
The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.
The boehmite of 19 parts by weight in terms of butt is mixed with beating with deionized water, and added into obtained slurries
Enter hydrochloric acid peptization, sour aluminum ratio (weight) is 0.20：1, temperature is then risen to 65 DEG C and is acidified 1 hour, is then separately added into dry
The slurries (solid content is 25 weight %) of 28 parts by weight kaolin clay of base meter, 7 parts by weight in terms of butt Alumina gel and with
(solid content is 18 weights to the mesopore activity silicon phosphor-aluminum material A-1 prepared by preparation example 1 of 10 parts by weight of butt meter slurries
Measure %), stir 20 minutes, first Y type molecular sieve of 5 parts by weight added thereto again in terms of butt afterwards, with butt
Second Y type molecular sieve of 23 parts by weight of meter and the first MFI structure molecular sieve of 8 parts by weight in terms of butt it is mixed
Slurries (solid content is 35 weight %) are closed, continues spray drying after stirring and microspherical catalyst is made.Then by the microspherical catalyst
It is calcined 1 hour at 500 DEG C, then (NH is used at 60 DEG C4)2SO4Solution washs (wherein, (NH4)2SO4：Microspherical catalyst：H2O
=0.05：1：10) to Na2O content is less than 0.25 weight %, is then eluted and is filtered with deionized water, afterwards at 110 DEG C
Drying, obtains catalytic cracking catalyst C1, wherein, on the basis of the gross weight of the catalytic cracking catalyst C1, the catalysis
Mesopore activity silicon phosphor-aluminum material containing 10 weight % in Cracking catalyst C1,28 weight % Y type molecular sieve, 8 weight %
MFI structure molecular sieve, 28 weight % kaolin, 26 weight % Al2O3Binding agent.
Comparative example 1
The comparative example is used to illustrate catalytic cracking catalyst of reference and preparation method thereof.
Method according to embodiment 1 prepares catalytic cracking catalyst, unlike, the mesopore prepared by preparation example 1 is lived
Property silicon phosphor-aluminum material A-1 is replaced with the mesopore activity silica-alumina material DA-1 prepared by contrast preparation example 1 of identical weight part, is obtained
Reference catalytic cracking catalyst CB1, wherein, on the basis of the gross weight of the reference catalytic cracking catalyst CB1, the reference
The Y type molecular sieve of mesopore silica-alumina material, 28 weight % containing 10 weight % in catalytic cracking catalyst CB1,8 weight %
MFI structure molecular sieve, 28 weight % kaolin, 26 weight % Al2O3Binding agent.
Comparative example 2
The comparative example is used to illustrate catalytic cracking catalyst of reference and preparation method thereof.
Method according to embodiment 1 prepares catalytic cracking catalyst, unlike, it is added without mesopore activity silicon phosphor-aluminum material
A-1, and mesopore activity silicon phosphor-aluminum material A-1 is substituted with the kaolin of identical butt weight, obtain reference catalytic cracking catalysis
Agent CB2, wherein, on the basis of the gross weight of the reference catalytic cracking catalyst CB2, the reference catalytic cracking catalyst
The MFI structure molecular sieve of Y molecular sieve, 8 weight %, 38 weight % kaolin, 26 weight % containing 28 weight % in CB2
Al2O3Binding agent.
Embodiment 2
The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.
20 parts by weight kaolin clay in terms of butt are mixed with beating with deionized water, 20 parts by weight added in terms of butt
Boehmite, and into obtained slurries add hydrochloric acid peptization, sour aluminum ratio (weight) be 0.20：1, then temperature is risen to
65 DEG C be acidified 1 hour, the Alumina gel for 5 parts by weight being then separately added into terms of butt, 30 parts by weight in terms of butt by making
Mesopore activity silicon phosphor-aluminum material A-2 prepared by standby example 2 slurries (solid content be 20 weight %), stirring 20 minutes, afterwards again to
The 3rd Y types of first Y type molecular sieve of 5 parts by weight wherein added in terms of butt, 10 parts by weight in terms of butt
(solid content is 35 weight to the mixed serum of molecular sieve and the second MFI structure molecular sieve for 10 parts by weight counted using butt
Measure %), continue spray drying after stirring and microspherical catalyst is made.Then the microspherical catalyst is calcined 1 hour at 500 DEG C,
(NH is used at 60 DEG C again4)2SO4Solution washs (wherein, (NH4)2SO4：Microspherical catalyst：H2O=0.05：1：10) to Na2O contains
Amount is less than 0.25 weight %, is then eluted and is filtered with deionized water, dried afterwards at 110 DEG C, obtained catalytic cracking and urge
Agent C2, wherein, on the basis of the gross weight of the catalytic cracking catalyst C2, contain 30 in the catalytic cracking catalyst C2
Weight % mesopore activity silicon phosphor-aluminum material, 15 weight % Y type molecular sieve, 10 weight % MFI structure molecular sieve, 20 weights
Measure % kaolin, 25 weight % Al2O3Binding agent.
Embodiment 3
The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.
28 parts by weight kaolin clay in terms of butt are mixed with beating with deionized water, 25 parts by weight added in terms of butt
Boehmite, and into obtained slurries add hydrochloric acid peptization, sour aluminum ratio (weight) be 0.20：1, then temperature is risen to
65 DEG C are acidified 1 hour, the mesopore activity silicon phosphorus aluminium prepared by preparation example 3 for 20 parts by weight being then separately added into terms of butt
Expect A-3 slurries (solid content is 25 weight %), stir 20 minutes, 10 parts by weight added thereto again in terms of butt afterwards
Second Y type molecular sieve, the 3rd Y type molecular sieve of 9 parts by weight in terms of butt, the institute of 3 parts by weight in terms of butt
State the first MFI structure molecular sieve and the second MFI structure molecular sieve of 5 parts by weight in terms of butt mixed serum (admittedly contain
Measure as 35 weight %), continue spray drying after stirring and microspherical catalyst is made.Then the microspherical catalyst is roasted at 500 DEG C
Burn 1 hour, then (NH is used at 60 DEG C4)2SO4Solution washs (wherein, (NH4)2SO4：Microspherical catalyst：H2O=0.05：1：10)
To Na2O content is less than 0.25 weight %, is then eluted and is filtered with deionized water, dried, urged at 110 DEG C afterwards
Fluidized cracking catalysts C3, wherein, on the basis of the gross weight of the catalytic cracking catalyst C3, the catalytic cracking catalyst C3
In the mesopore activity silicon phosphor-aluminum material containing 20 weight %, 19 weight % Y type molecular sieve, 8 weight % MFI structure molecule
Sieve, 28 weight % kaolin, 25 weight % Al2O3Binding agent.
Embodiment 4
The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.
By the kaolin of 40 parts by weight in terms of butt with the Alumina gel of 15 parts by weight in terms of butt and in terms of butt
15 parts by weight the mesopore activity silicon phosphor-aluminum material A-4 prepared by preparation example 4 slurries (solid content is 20 weight %) mixing
Mashing, stir 120 minutes, the 3rd Y type molecular sieve of 15 parts by weight added thereto again in terms of butt afterwards and with dry
The mixed serum (solid content is 35 weight %) of the second MFI structure molecular sieve of 15 parts by weight of base meter, after continuing stirring
Microspherical catalyst is made in spray drying.Then the microspherical catalyst is calcined 1 hour at 500 DEG C, then (NH is used at 60 DEG C4)2SO4Solution washs (wherein, (NH4)2SO4：Microspherical catalyst：H2O=0.05：1：10) to Na2O content is less than 0.25 weight %,
Then eluted and filtered with deionized water, dried afterwards at 110 DEG C, obtain catalytic cracking catalyst C4, wherein, with described
On the basis of catalytic cracking catalyst C4 gross weight, the mesopore activity silicon containing 15 weight % in the catalytic cracking catalyst C4
Phosphor-aluminum material, 15 weight % Y type molecular sieve, 15 weight % MFI structure molecular sieve, 40 weight % kaolin, 15 weights
Measure % Al2O3Binding agent.
Embodiment 5
The embodiment is used to illustrate catalytic cracking catalyst provided by the invention and preparation method thereof.
(1) Ludox is prepared：
1.7L hydrochloric acid is diluted with 8.0kg decationized Y sieve water, by 7.7kg sodium silicates 8.0kg decationized Y sieve water
It is diluted, the sodium silicate diluted is slowly added in above-mentioned hydrochloric acid weak solution under stirring, obtains SiO2Concentration is 7.8 weights
Measure %, the Ludox that pH value is 2.8.
(2) catalytic cracking catalyst is prepared：
The kaolin of 10 parts by weight added in the above-mentioned Ludox of 20 parts by weight in terms of butt in terms of butt, stirring
The mesopore activity silicon phosphor-aluminum material A-5 prepared by preparation example 5 of 40 parts by weight added after 1h in terms of butt slurries (solid content
For 18 weight %) be mixed with beating, first Y type molecular sieve of 10 parts by weight added thereto again in terms of butt afterwards, with
Second Y type molecular sieve of 5 parts by weight of butt meter, 12 parts by weight in terms of butt the 3rd Y type molecular sieve and with
The mixed serum (solid content is 30 weight %) of the first MFI structure molecular sieve of 3 parts by weight of butt meter, after continuing stirring
Microspherical catalyst is made in spray drying.Then the microspherical catalyst is used into (NH at 60 DEG C4)2SO4(wherein, solution washs
(NH4)2SO4：Microspherical catalyst：H2O=0.05：1：10) to Na2O content is less than 0.25 weight %, is then eluted with deionized water
And filter, dried afterwards at 110 DEG C, obtain catalytic cracking catalyst C5, wherein, with the catalytic cracking catalyst C5's
On the basis of gross weight, the mesopore activity silicon phosphor-aluminum material containing 40 weight %, 27 weight % in the catalytic cracking catalyst C5
Y type molecular sieve, 3 weight % MFI structure molecular sieve, 10 weight % kaolin, 20 weight % SiO2Binding agent.
Comparative example 3
The comparative example is used to illustrate catalytic cracking catalyst of reference and preparation method thereof.
By the solid product SA-L5 that preparation example 5 obtains in 120 DEG C of dryings, then it is calcined 2 hours in 550 DEG C, obtains mesopore
Silica-alumina material is designated as SSA-5.Method according to embodiment 5 prepares catalytic cracking catalyst, unlike, it will be made by preparation example 5
Standby mesopore activity silicon phosphor-aluminum material A-5 is replaced with the mesopore activity silica-alumina material SSA-5 of identical weight part, obtains reference catalysis
Cracking catalyst CB3.Wherein, on the basis of the gross weight of the reference catalytic cracking catalyst CB3, the reference catalytic cracking
The Y type molecular sieve of mesopore silica-alumina material, 27 weight % containing 40 weight % in catalyst CB3,3 weight % MFI structure point
Sub- sieve, 10 weight % kaolin, 20 weight % SiO2Binding agent.
Embodiment 6-10
Embodiment 6-10 is used for the test for illustrating catalytic cracking catalyst performance provided by the invention.
Respectively by the catalytic cracking catalyst C1-C5 of above-mentioned preparation agings 12 under conditions of 800 DEG C, 100% water vapour
Hour, it is filled in afterwards in small fixed flowing bed ACE devices (being purchased from KTI companies of the U.S.), amount of fill is each 9g.So
Afterwards, reaction temperature be 500 DEG C, air speed 16h-1, agent weight of oil ratio be 5：The feedstock oil shown in table 2 is carried out under conditions of 1
Catalytic cracking reaction, reaction result are listed in Table 3 below.Wherein, coke selectivity refers to the ratio of coke yield and conversion ratio.
Comparative example 4-6
Comparative example 4-6 is used for the test for illustrating the catalytic cracking catalyst performance of reference.
Catalytic cracking reaction is carried out to feedstock oil according to embodiment 6-10 method, unlike, catalytic cracking is catalyzed
Agent C1-C5 is substituted with catalytic cracking catalyst CB1, CB2 and CB3 of the reference of identical weight part respectively, and reaction result is listed in table 3
In.
Table 2
Table 3
The result of table 3 illustrates, compared with catalyst that is identical with zeolite content but being free of mesopore activity silicon phosphor-aluminum material, this hair
The catalyst of bright offer can be obviously improved the selectivity of coke, while also have higher cracking activity, with each component content
The catalyst for the mesopore activity silicon phosphor-aluminum material that mesoporous active materials that are identical but using are different from the present invention is compared, and the present invention carries
The coke yield of the catalyst of confession is reduced, and coke selectivity is obviously improved.As can be seen here, catalysis provided by the invention is split
More preferable coke selectivity and higher catalytic cracking work can be shown during RFCC by changing catalyst
Property, while higher yield of liquefied gas can also be obtained.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of catalytic cracking catalyst, it is characterised in that described to urge on the basis of the gross weight of the catalytic cracking catalyst
Fluidized cracking catalysts contain 1-60 weight % cracking activity constituent element, 1-50 weight % mesopore activity silicon phosphor-aluminum material, 1-70
Weight % clay and 1-70 weight % binding agent；The mesopore activity silicon phosphor-aluminum material has boehmite crystalline phase knot
Structure, in the mesopore activity silicon phosphor-aluminum material using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.2)Na2O·
(50-86)Al2O3·(12-50)SiO2·(0.5-10)P2O5, and the specific surface area of the mesopore activity silicon phosphor-aluminum material is
200-600m2/ g, pore volume 0.5-1.8cm3/ g, average pore size 8-18nm；
On the basis of the gross weight of the cracking activity constituent element, the cracking activity constituent element contains first point of 50-95 weight %
Second molecular sieve component of sub- screen banks point and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, the 2nd Y
One or more in type molecular sieve and the 3rd Y type molecular sieve, second molecular sieve component are the first MFI structure molecular sieve
And/or the second MFI structure molecular sieve；
First Y type molecular sieve is the DASY molecular sieves containing rare earth；
Second Y type molecular sieve is REY molecular sieves；
Using the content of rare earth that rare earth oxide is counted as 12-16 weight % in 3rd Y type molecular sieve, with P2O5The phosphorus content of meter
For 0.5-7 weight %, the molecular sieve31In P MAS NMR spectras, chemical shift is -14 ± 2ppm and -23 ± 2ppm resonance letters
Number peak area account for total peak area percentage be more than 85%, the molecular sieve27In Al MAS NMR spectras, chemical shift 0
The percentage that the peak area of ± 2ppm resonance signals accounts for total peak area is more than 20%；
In the first MFI structure molecular sieve using the anhydrous chemical expression of the molar ratio computing of oxide as：(0.01-0.25)
RE2O3·(0.005-0.02)Na2O·Al2O3·(0.2-1)P2O5·(35-120)SiO2, the molecular sieve is to n-hexane and hexamethylene
The absorption weight ratio of alkane is 4-5：1；
In the second MFI structure molecular sieve using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.3)Na2O·
(0.5-5.5)Al2O3·(1.3-10)P2O5·(0.7-15)M1xOy·(0.01-5)M2mOn·(70-97)SiO2, wherein, M1
For Fe, Co or Ni, x represents M1 atomicity, and y represents the number for meeting M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or Sn, m
M2 atomicity is represented, n represents the number for meeting M2 oxidation state requisite oxygens.
2. catalytic cracking catalyst according to claim 1, wherein, using the gross weight of the catalytic cracking catalyst as base
Standard, the catalytic cracking catalyst contain 10-50 weight % cracking activity constituent element, 5-40 weight % mesopore activity silicon phosphorus aluminium
The binding agent of material, 10-60 weight % clay and 10-60 weight %.
3. catalytic cracking catalyst according to claim 1, wherein, the specific surface area of the mesopore activity silicon phosphor-aluminum material
For 250-550m2/ g, pore volume 0.6-1.6cm3/ g, average pore size 9-15nm.
4. according to the catalytic cracking catalyst described in any one in claim 1-3, wherein, the mesopore activity silicon phosphorus aluminium
Material is prepared in accordance with the following methods：
By silicon source and alkaline solution in room temperature at 85 DEG C and plastic, the pH value for controlling plastic is 7-11, according still further to SiO2：
Al2O3=1：1-7.5 weight ratio adds silicon source into plastic slurries, then then will in room temperature to ageing 1-5 hours at 90 DEG C
It is aged after obtained solid sediment contacts with ammonium salt or acid solution and filters, obtains sodium oxide content less than 0.3 weight %'s
Solid product, then the solid product is contacted with phosphorus source again, and product of contact is dried；Phosphorus source is with P2O5The use of meter
Amount and the weight ratio of the butt of the solid product are 0.005-0.1：1.
5. catalytic cracking catalyst according to claim 4, wherein, source of aluminium is selected from aluminum nitrate, aluminum sulfate and chlorination
One or more in aluminium；The alkaline solution is selected from ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution
In one or more；One or more of the silicon source in waterglass, sodium metasilicate, tetraethoxy-silicane and silica.
6. catalytic cracking catalyst according to claim 4, wherein, the method that the solid sediment is contacted with ammonium salt
Including：The solid sediment is pressed into its butt：Ammonium salt：H2O=1：0.1-1：5-30 weight ratio is in room temperature to entering at 100 DEG C
Row exchanges.
7. catalytic cracking catalyst according to claim 4, wherein, the ammonium salt is selected from ammonium chloride, ammonium sulfate, nitric acid
One or more in ammonium, ammonium carbonate and ammonium hydrogen carbonate.
8. catalytic cracking catalyst according to claim 4, wherein, the solid sediment is contacted with acid solution
Method includes：The solid sediment is pressed into its butt：Acid：H2O=1：0.03-0.3：5-30 weight ratio is in room temperature to 100
Exchanged at DEG C at least 0.2 hour.
9. catalytic cracking catalyst according to claim 4, wherein, the acid in the acid solution is selected from sulfuric acid, chlorination
One or more in hydrogen and nitric acid.
10. catalytic cracking catalyst according to claim 4, wherein, the contact between the solid product and phosphorus source exists
Carried out in the presence of water, the contact method includes：The solid product is pressed into its butt：Water=1：5-20 weight is than mixing
Mashing, add phosphorus source and in room temperature to reaction 0.2-5 hours at 90 DEG C.
11. catalytic cracking catalyst according to claim 4, wherein, phosphorus source be selected from ammonium phosphate, diammonium hydrogen phosphate,
One or more in ammonium dihydrogen phosphate and phosphoric acid.
12. according to the catalytic cracking catalyst described in any one in claim 1-3, wherein, with the cracking activity constituent element
Gross weight on the basis of, the cracking activity constituent element contains 65-86 weight % the first molecular sieve component and 14-35 weight %
Second molecular sieve component.
13. according to the catalytic cracking catalyst described in any one in claim 1-3, wherein, first molecular sieve component
For at least two mixture in first Y type molecular sieve, second Y type molecular sieve and the 3rd Y type molecular sieve,
Second molecular sieve component is the first MFI structure molecular sieve or the second MFI structure molecular sieve.
14. the preparation method of the catalytic cracking catalyst in claim 1-13 described in any one, this method is included by described in
Cracking activity constituent element, mesopore activity silicon phosphor-aluminum material, clay and binding agent are mixed with beating, be then spray-dried successively again,
Washing, filter and dry.
15. application of the catalytic cracking catalyst in claim 1-13 described in any one in RFCC.
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| US4747935A (en) * | 1986-03-26 | 1988-05-31 | Union Oil Company Of California | Process for the catalytic cracking of feedstocks containing nitrogen |
| CN102974389A (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 |
| CN103657712A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4747935A (en) * | 1986-03-26 | 1988-05-31 | Union Oil Company Of California | Process for the catalytic cracking of feedstocks containing nitrogen |
| CN102974389A (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 |
| CN103657712A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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| Title |
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| 催化裂化催化剂的配方设计及研究进展;陆红军;《炼油技术与工程》;20061130;第36卷(第11期);第31页第2.1.4部分 * |
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