CN106179458B - 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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- CN106179458B CN106179458B CN201510214228.5A CN201510214228A CN106179458B CN 106179458 B CN106179458 B CN 106179458B CN 201510214228 A CN201510214228 A CN 201510214228A CN 106179458 B CN106179458 B CN 106179458B
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- catalytic cracking
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- cracking catalyst
- rare earth
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 85
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 102
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000011149 active material Substances 0.000 claims abstract description 38
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000000694 effects Effects 0.000 claims abstract description 33
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 24
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- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 22
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- 239000013049 sediment Substances 0.000 claims description 111
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- 239000002808 molecular sieve Substances 0.000 claims description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 82
- 239000000463 material Substances 0.000 claims description 63
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 45
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- 238000005336 cracking Methods 0.000 claims description 44
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 5
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- 238000010521 absorption reaction Methods 0.000 claims description 4
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- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052725 zinc Inorganic materials 0.000 claims description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000003483 aging Methods 0.000 claims description 3
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- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of catalytic cracking catalysts and its preparation method and application.On the basis of the total weight of catalytic cracking catalyst, which contains the mesoporous active materials of 1 50 weight %；Mesoporous active materials are with the anhydrous chemical expression of the weight ratio meter of oxide：(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, one or more in periodic table of elements IIB, IIIB, IVB, VIIB race's elements and lanthanide series rare-earth elements, and y is highest valent state when metal M forms oxide, and the numerical value of x and y makes the chemical valence of M and O balance.It has lower coke selectivity and higher catalytic cracking activity during heavy oil catalytic cracking, and can obtain lower content of sulfur in gasoline and higher yield of gasoline.
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 heavy oil catalytic cracking.
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
It answers, is converted into the high value added products such as liquefied gas, gasoline, diesel oil, 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.
It asks, especially 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, enhance heavy oil conversion performance, while reducing further turning for intermediate oil and naphtha
Change, traditional micro porous molecular sieve catalysis material shows apparent limitation diffusion since its duct is smaller, to larger raw molecule
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 needs using aperture is larger, does not spread limitation to reactant molecule and with the material compared with high cracking activity.Cause
This, mesoporous and macropore catalysis material research and development are increasingly valued by people.In addition, in catalytic cracking field, sial material
Expect to be widely applied with stronger acid centre and good cracking performance due to it.
CN1565733A discloses a kind of mesoporous silica-alumina material, which has boehmite crystalline phase knot
Structure, the anhydrous chemical expression with the weight ratio meter of oxide are：(0-0.3)Na2O·(40-90)Al2O3·(10-60)
SiO2, specific surface area 200-400m2/ g, Kong Rongwei 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-
15nm.The preparation of the mesoporous silica-alumina material is without the use of organic formwork agent, and synthesis cost is low, and obtained mesoporous 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, which contains the warp of 3-20 weight %
The mesoporous silica-alumina materials of acid processing, which has 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, Kong Rongwei 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 with 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 is 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 rate can be not only improved, but also can effectively reduce FCC vapour
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, binder and mesoporous silica-alumina materials composition, the mesoporous silica-alumina materials have boehmite crystalline phase
Structure, the anhydrous chemical expression with the weight ratio meter of oxide are：(0-0.3)Na2O·(40-90)Al2O3·(10-60)
SiO2, specific surface area 200-400m2/ g, Kong Rongwei 0.5-2.0mL/g, average pore size 8-20nm, most probable pore size 5-
15nm, the binder are Ludox and/or Aluminum sol.Although the Cracking catalyst and the Conventional catalytic for using boehmite
Agent is compared, low, the better advantage of converting crude oil ability with production cost, but its coke selectivity is poor.
Invention content
The purpose of the invention is to provide it is a kind of it is new have lower coke selectivity, higher cracking activity, compared with
High yield of gasoline, and can also effectively reduce the catalytic cracking catalyst of FCC (catalytic cracking) content of sulfur in gasoline, described urge
The application of the preparation method of fluidized cracking catalysts and the catalytic cracking catalyst in heavy oil catalytic cracking.
For this purpose, according to an aspect of the invention, there is provided a kind of catalytic cracking catalyst, wherein split with the catalysis
On the basis of the total weight for changing catalyst, the catalytic cracking catalyst contains the cracking activity constituent element of 1-60 weight %, 1-50 weights
Measure the binder of the mesoporous active materials of %, the clay and 1-70 weight % of 1-70 weight %；The mesoporous active materials have
Boehmite crystal phase structure is with the anhydrous chemical expression of the weight ratio meter of oxide in the mesoporous active materials：(0-
0.2)Na2O·(40-85)Al2O3·(10-55)SiO2·(0.5-10)P2O5·(0.5-10)MxOy, wherein metal M be selected from Mg,
One or more in periodic table of elements IIB, IIIB, IVB, VIIB race's elements and lanthanide series rare-earth elements, y is that metal M is formed
Highest valent state when oxide, and the numerical value of x and y makes the chemical valence of M and O balance, and the mesoporous active materials
Specific surface area is 200-500m2/ g, Kong Rongwei 0.5-1.5cm3/ g, average pore size 8-18nm；
The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y types containing rare earth point
Son is screened from the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth
It is one or more；
Wherein, the preparation method of the described first Y type molecular sieve containing rare earth includes：Under stiring, by the Y types containing rare earth point
Son sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, the Y types containing rare earth
The weight ratio of molecular sieve and silicon tetrachloride is 1：0.05-0.5；
The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30：1, initial lattice constant is 2.430-
2.460nm, the content of rare earth on the basis of the total weight of the described second Y type molecular sieve containing rare earth and in terms of oxide is 10-
20 weight %, balance lattice constant and the ratio of initial lattice constant are at least 0.985, wherein the X-ray diffraction analysis molecule
Sieve two diffraction peak intensity ratio I for being 12.43 ± 0.06 ° and 11.87 ± 0.06 ° in 2 θ1/I2More than 1；
The preparation method of Y type molecular sieve of the third containing rare earth includes：By super-stable Y molecular sieves and a concentration of 0.01-
The acid solution of 2N is with liquid-solid ratio 4-20：1 ratio is sufficiently mixed at 20-100 DEG C, washing, filtering after processing 10-300 minutes,
It adds rare-earth salt solution and carries out rare earth ion exchanged, washed, filtered and dried successively after exchange.
According to another aspect of the present invention, the preparation method of the catalytic cracking catalyst, this method packet are additionally provided
It includes and is mixed with beating the cracking activity constituent element, mesoporous active materials, clay and binder, it is dry then to carry out spraying successively again
Dry, washing, filtering and drying.
In addition, according to a further aspect of the invention, additionally providing the catalytic cracking catalyst in heavy oil catalytic cracking
In application.
Catalytic cracking catalyst provided by the invention is by by specific cracking activity constituent element, specific mesoporous active materials
It is used cooperatively with clay and binder, increases the content of catalytic cracking catalyst mesoporous, be conducive to the diffusion of heavy oil macromolecular
And cracking, the catalytic cracking catalyst, can not only during heavy oil catalytic cracking especially suitable for heavy oil catalytic cracking
Lower coke selectivity and higher catalytic cracking activity are shown, but also lower content of sulfur in gasoline can be obtained, and
Higher yield of gasoline.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and 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 mesoporous active materials obtained by preparation example 1.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalytic cracking catalysts, wherein using the total weight of the catalytic cracking catalyst as base
Standard, the catalytic cracking catalyst contain mesoporous active materials, the 1- of the cracking activity constituent element of 1-60 weight %, 1-50 weight %
The binder of the clay and 1-70 weight % of 70 weight %；The mesoporous active materials have boehmite crystal phase structure, institute
The anhydrous chemical expression for stating the weight ratio meter in mesoporous active materials with oxide is：(0-0.2)Na2O·(40-85)
Al2O3·(10-55)SiO2·(0.5-10)P2O5·(0.5-10)MxOy, wherein metal M be selected from Mg, periodic table of elements IIB,
One or more in IIIB, IVB, VIIB race element and lanthanide series rare-earth elements, y is highest when metal M forms oxide
Valent state, and the numerical value of x and y makes the chemical valence of M and O balance, and the specific surface area of the mesoporous active materials is 200-
500m2/ g, Kong Rongwei 0.5-1.5cm3/ g, average pore size 8-18nm；
The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y types containing rare earth point
Son is screened from the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth
It is one or more；
Wherein, the preparation method of the described first Y type molecular sieve containing rare earth includes：Under stiring, by the Y types containing rare earth point
Son sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, the Y types containing rare earth
The weight ratio of molecular sieve and silicon tetrachloride is 1：0.05-0.5；
The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30：1, initial lattice constant is 2.430-
2.460nm, the content of rare earth on the basis of the total weight of the described second Y type molecular sieve containing rare earth and in terms of oxide is 10-
20 weight %, balance lattice constant and the ratio of initial lattice constant are at least 0.985, wherein the X-ray diffraction analysis molecule
Sieve two diffraction peak intensity ratio I for being 12.43 ± 0.06 ° and 11.87 ± 0.06 ° in 2 θ1/I2More than 1；
The preparation method of Y type molecular sieve of the third containing rare earth includes：By super-stable Y molecular sieves and a concentration of 0.01-
The acid solution of 2N is with liquid-solid ratio 4-20：1 ratio is sufficiently mixed at 20-100 DEG C, washing, filtering after processing 10-300 minutes,
It adds rare-earth salt solution and carries out rare earth ion exchanged, washed, filtered and dried successively after exchange.
In the present invention, the specific surface area, Kong Rong and average pore size are all made of nitrogen absorption under low temperature-desorption method and are surveyed
Fixed, used instrument is the physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S..
According to above-mentioned catalytic cracking catalyst provided by the invention, it is preferable that with oxide in the mesoporous active materials
The anhydrous chemical expression of weight ratio meter be：(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。
According to above-mentioned catalytic cracking catalyst provided by the invention, it is preferable that with the gross weight of the catalytic cracking catalyst
On the basis of amount, the catalytic cracking catalyst contains the mesopore activity of the cracking activity constituent element of 10-50 weight %, 5-40 weight %
The binder of material, the clay of 10-60 weight % and 10-60 weight %, the content control of above-mentioned each component is preferred at this
The catalytic cracking catalyst enabled in range has better comprehensive performance.
According to above-mentioned catalytic cracking catalyst provided by the invention, it is preferable that the specific surface area of the mesoporous active materials
For 300-450m2/ g, Kong Rongwei 0.7-1.2cm3/ g, average pore size 10-15nm.
According to above-mentioned catalytic cracking catalyst provided by the invention, it is preferable that the metal M be selected from IIB, IIIB, IVB,
When VIIB races metal, one or more mixing preferably in Zn, Y, Ti, Mn, the mixing such as Ti of the various metals
The mixing of mixing, Mn and Zn with Mn.When the metal M is selected from lanthanide series rare-earth elements, preferably lanthanum, cerium or containing lanthanum and cerium
Mischmetal.According to above-mentioned catalytic cracking catalyst provided by the invention, preferably metal M is in Mg, Zn, Y, Ti, Mn, La and Ce
One or more mixing.
According to above-mentioned catalytic cracking catalyst provided by the invention, wherein mesoporous active materials be referred to prior art into
Prepared by row, it is preferable that the mesoporous active materials are to be prepared by the method comprising the following steps in the present invention：
(1) silicon source and aqueous slkali are obtained into rubber cement room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11
Liquid；
(2) according to SiO2：Al2O3=1：Silicon source is added into the plastic slurries in the weight ratio of (0.6-9), room temperature extremely
It is aged 1-5 hours at 90 DEG C, obtains the first solid sediment；
(3) by first solid sediment and ammonium salt or acid solution contact treatment, sodium oxide content is obtained by filtration and is less than
0.3% the second solid sediment；
(4) by the second solid sediment, phosphorus source and metal M compounds, according to P2O5：MxOy：Second solid sediment
Sediment butt=(0.005-0.1)：(0-0.05)：(0.005-0.1)：1 weight ratio contact treatment, and by product of contact
It is dry, wherein the metal M is in Mg, periodic table of elements IIB, IIIB, IVB, VIIB race's elements and lanthanide series rare-earth elements
It is one or more.
Specifically, the silicon source described in above-mentioned steps (1) can be the existing various substances that can be converted into aluminium oxide,
For example, can be selected from one or more in aluminum nitrate, aluminum sulfate and aluminium chloride.
The alkaline solution described in above-mentioned steps (1) can be the existing various substances that alkalinity is presented, for example, can select
From one or more in ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution.Wherein, the alkalinity is molten
The concentration of liquid can be the conventional selection of this field, and therefore not to repeat here.
The silicon source described in above-mentioned steps (2) can be the existing various substances that can be converted into silica, for example, can
With one in waterglass, sodium metasilicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon and silica
Kind is a variety of.
The present invention is not to limiting the method that first solid sediment is contacted with ammonium salt particularly in above-mentioned steps (3)
It is fixed, for example, may include by the first solid sediment by its sediment butt：Ammonium salt：H2O=1：(0.1-1)：The weight of (5-30)
Amount than in room temperature to swapping at 100 DEG C.Wherein, the number of the contact can be 1-3 times, and each time of contact can be with
0.5-1 hours, the content of sodium oxide molybdena was less than subject to 0.3 weight % in the solid product that should specifically make.
In addition, the type of the ammonium salt described in above-mentioned steps (3) can be the conventional selection of this field, for example, can select
From one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.
The present invention is not special to the method for contacting first solid sediment with acid solution in above-mentioned steps (3)
Ground limits, for example, may include by first solid sediment by its sediment butt：Acid：H2O=1：(0.03-0.3)：(5-
30) weight ratio is in room temperature to exchanging at least 0.2 hour at 100 DEG C.
In addition, the type of the acid solution described in above-mentioned steps (3) can be the conventional selection of this field, it is usually inorganic
Acid, for example, the acid in the acid solution can be selected from one or more in sulfuric acid, hydrogen chloride and nitric acid.
It can be with by the contact treatment process of the compound of the second solid sediment, phosphorus source and metal M in above-mentioned steps (4)
There are many mode, for example, it is following a), b), c), d) any one of process：
A) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with water beats
Slurry, then the compound of phosphorus source and metal M is added sequentially in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2
Hour, preferably contact treatment 0.2-5 hours, more preferable contact treatment 0.5-3 hours, after filtering washing at 100 DEG C -150 DEG C
It is 10-20 hours dry；
B) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with water beats
Slurry, then phosphorus source is added in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour, preferably contact treatment
It 0.2-5 hours, more preferable contact treatment 0.5-3 hours, is directly mixed in proportion with the compound of metal M after filtering, grinding is equal
It is 10-20 hours dry at 100 DEG C -150 DEG C after even；
C) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with water beats
Slurry, then the compound of phosphorus source and the first metal M is added in above-mentioned slurries, room temperature to contact treatment at 90 DEG C at least
0.2 hour, preferably contact treatment 0.2-5 hours more preferable contact treatment 0.5-3 hours, obtain third solid precipitation after filtering
Object, then third solid sediment is directly mixed with second of metal M, 10-20 is dried after grinding uniformly at 100 DEG C -150 DEG C
Hour, wherein the compound and the compound of second of metal M of the first metal M is identical or different；
D) second solid sediment is directly mixed with phosphorus source and metal M compounds in proportion, grinding uniformly after
It is 10-20 hours dry at 100 DEG C -150 DEG C.
In aforesaid way c), compound for the first metal M and included in the compound of second of metal M
There is no particular/special requirements for the dosage of specific material and material, as long as enabling to second solid sediment and phosphorus source and gold
The compound for belonging to M, is finally according to P2O5MxOy：The sediment butt of second solid sediment=(0.005-0.1)：
(0.005-0.1)：1 weight ratio mixing.
Further, optionally, the preparation method of the mesoporous active materials can also include roasting desciccate, institute
State roasting condition generally include calcination temperature can be 500-700 DEG C, roasting time can be 1-4 hours.
The type of phosphorus source described in above-mentioned steps (4) can be the conventional selection of this field, for example, phosphoric acid can be selected from
It is one or more in ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid.
The compound of metal M described in above-mentioned steps (4) can be any one water-soluble compound.
The compound of metal M described in above-mentioned steps (4) is nitrate, sulfate or the chloride of metal M.For example,
It magnesium source can be selected from one or more in magnesium nitrate, magnesium chloride and magnesium sulfate.
According to catalytic cracking catalyst provided by the invention, the Y type molecular sieve containing rare earth is selected from the first Y containing rare earth
It is one or more in the Y type molecular sieve of Y type molecular sieve and third containing rare earth of type molecular sieve, second containing rare earth, it is preferably selected from
The described first Y type molecules of Y type molecular sieve, the described second Y type molecular sieve and the third containing rare earth containing rare earth containing rare earth
At least two in sieve.
The specific preparation method of described first Y type molecular sieve containing rare earth is referred to CN1683244A, especially wherein
Embodiment 5,6 and 8.
In the present invention, the specific descriptions of the described second Y type molecular sieve containing rare earth are referred to CN101081369A.Institute
That states that the second Y type molecular sieve containing rare earth can be prepared according to the conventional method obtains, and specific preparation method can also reference
CN101081369A, embodiment 1-5 especially therein.
The specific preparation method of Y type molecular sieve of the third containing rare earth is referred to CN1958452A, especially wherein
Embodiment 1-6.
According to catalytic cracking catalyst provided by the invention, the cracking activity constituent element can also contain MFI structure molecule
It sieves, is with the anhydrous chemical composition expression formula of the molar ratio computing of oxide in the MFI structure molecular sieve：(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.Preferably, on the basis of the total weight of the cracking activity constituent element, the cracking activity group
The MFI structure molecular sieve of Y type molecular sieve and 0.1-10 weight % containing rare earth of the member containing 90-99.9 weight %；It is highly preferred that
The cracking activity constituent element contains the MFI structure molecular sieve of the Y type molecular sieve and 1-6 weight % containing rare earth of 94-99 weight %.
The specific descriptions of the MFI structure molecular sieve are referred to CN1147420A.The MFI structure molecular sieve can root
It is obtained according to prepared by conventional method, specific preparation method can also be with reference to CN1147420A, embodiment especially therein
1-6。
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
Moisten one or more of soil.
The binder can be the existing various binders that can be used in catalytic cracking catalyst, for example, can be with
Selected from one or more of Ludox, Aluminum sol and boehmite.
In addition, the catalytic cracking catalyst can also contain additional rare earth.The additional rare earth is urged described in preparation
It is formed by rare earth chloride additionally is added during fluidized cracking catalysts.It is described in the catalytic cracking catalyst
Additional rare earth is usually with rare earth oxide (RE2O3) form exist.Using the dry weight of the catalytic cracking catalyst as base
The content of standard, the additional rare earth in terms of rare earth oxide can be 0-3 weight %, preferably 0.5-2 weight %.Wherein,
Rare earth element in the additional rare earth refers to the various conventional rare earth elements involved in catalytic cracking catalyst field, such as
Can be lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium etc..
The preparation method of catalytic cracking catalyst provided by the invention includes by above-mentioned cracking activity constituent element, mesopore activity material
Material, clay and binder are mixed with beating, and are then spray-dried, washed, filtered and dried successively again.In addition, being urged when described
When fluidized cracking catalysts also contain additional rare earth, the preparation method of catalytic cracking catalyst provided by the invention further includes will be described
Rare earth chloride and the cracking activity constituent element, mesoporous active materials, clay and binder are mixed together mashing, then again successively into
Row spray drying, washing, filtering and drying.
According to the preparation method of catalytic cracking catalyst provided by the invention, by the cracking activity constituent element, mesopore activity
Material, clay and binder and the rare earth chloride selectively contained are mixed with beating and subsequent spray drying, washing, mistake
Filter and drying, the implementation of these processes can be used conventional method and implement, their specific implementation method for example exists
Have in CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A detailed
Description, be introduced into together in the present invention here by reference.Typically also, after the spray drying, before washing,
The preparation method of the catalytic cracking catalyst also typically includes the step of being roasted Spray dried products.The roasting
It can be 500-700 DEG C that condition, which generally includes calcination temperature, and roasting time can be 1-4 hours.
In addition, the application the present invention also provides above-mentioned catalytic cracking catalyst in heavy oil catalytic cracking.
The present invention will be described in detail by way of examples below.
The raw material used in following preparation example, comparison preparation example, embodiment and comparative example is as follows：
Hydrochloric acid is produced by Beijing Chemical Plant, pure, a concentration of 36 weight % of chemistry；
Sodium silicate is commercially available, SiO2A concentration of 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 %；
Aluminum sol is Sinopec catalyst asphalt in Shenli Refinery product, Al2O3Content is 21.5 weight %；
First Y type molecular sieve containing rare earth is made according to the method in CN1683244A embodiments 5；
Second Y type molecular sieve containing rare earth is made according to the method in CN101081369A embodiments 1；
Y type molecular sieve of the third containing rare earth is made according to the method in CN1958452A embodiments 1；
MFI structure molecular sieve is made according to the method in CN1147420A embodiments 1；
Rare earth chloride is purchased from Xitu Hi-Tech skill limited liability company of Baogang, and rare earth element therein is La and Ce.
In following embodiment and comparative example：
Specific surface area, Kong Rong and average pore size are all made of nitrogen absorption under low temperature-desorption method and are measured, and used instrument is
The physical and chemical adsorption instrument ASAP2400 of Micro meritics companies of the U.S..Na in mesoporous active materials2O、Al2O3、SiO2、
P2O5, MgO and metal oxide (MxOy) content with x-ray fluorescence method measure (referring to《(RIPP is real for petrochemical analysis method
Proved recipe method)》, Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes).
Preparation example 1
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) first by a concentration of 90gAl2O3The Al of/L2(SO4)3Solution is placed in beaker, by a concentration of 25wt.% under stirring
Ammonium hydroxide is added, until system pH=10.0, it is 40 DEG C to keep gelling temperature, collects metering plastic slurries；(2) under agitation
According to SiO2：Al2O3=1：A concentration of 60gSiO is added into plastic slurries for 3 weight ratio2The waterglass of/L is warming up to 80 DEG C
Ageing 1 hour, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt：HCl：H2O=
1：0.08：12 weight ratio exchanges 30 minutes at 50 DEG C, and filtering washing obtains the second solid that sodium oxide content is less than 0.3%
Sediment；(4) the second solid sediment is pressed into its sediment butt：H2O=1：10 weight ratio is mixed with beating with water, and is pressed
P2O5：MgO：TiO2：Sediment butt=0.075 of second solid sediment：0.017：0.012：1 weight ratio sequentially adds
Ammonium phosphate, magnesium nitrate and titanium sulfate react 2 hours at 60 DEG C, after filtering washing at 120 DEG C dry 10 hours up to this
The phosphorus provided, metal-modified mesoporous silica-alumina material are provided.It is denoted as A-1.
A-1 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry forms
For 0.08Na2O·74.2Al2O3·15.3SiO2·7.3P2O5·1.5MgO·1.0TiO2；Specific surface area 455m2/ g, Kong Rong
1.24cm3/ g, average pore size 10.9nm.
Preparation example 2
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) with a concentration of 90gAl2O3The Al of/L2(SO4)3Solution and a concentration of 102gAl2O3/ L, Crater corrosion are 2.5
NaAlO2Solution is reaction raw materials, using cocurrent plastic mode, mixing plastic is carried out under being vigorously stirred, control system temperature is 40
DEG C, system pH=10.5 collects metering plastic slurries；(2) under stiring according to SiO2：Al2O3=1：1.2 weight ratio at
A concentration of 100gSiO is added in rubber cement liquid2The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the first solid sediment；
(3) first solid sediment is pressed into its sediment butt：HCl：H2O=1：0.08：15 weight ratio exchanges at 60 DEG C
30 minutes, filtering washing obtained the second solid sediment that sodium oxide content is less than 0.3%；(4) P is pressed2O5：TiO2：MnO2：The
Sediment butt=0.015 of two solid sediments：0.035：0.049：1 weight ratio is by the second solid sediment and di(2-ethylhexyl)phosphate
Hydrogen ammonium, titanium sulfate and manganese chloride are mixed, 15 hours dry at 120 DEG C after grinding uniformly, are roasted 4 hours then at 600 DEG C
Up to phosphorus provided by the invention, metal-modified mesoporous silica-alumina material.It is denoted as A-2.
A-2 has boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry
Group becomes 0.17Na2O·55.1Al2O3·34.4SiO2·1.5P2O5·3.5TiO2·4.9MnO2；Specific surface area 312m2/ g,
Hole holds 0.87cm3/ g, average pore size 11.1nm.
Preparation example 3
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) with a concentration of 90gAl2O3The Al of/L2(SO4)3The ammonium hydroxide of solution and a concentration of 24wt.% are reaction raw materials, are adopted
With cocurrent plastic mode, it is vigorously stirred lower by Al2(SO4)3Solution and ammonium hydroxide carry out mixing plastic, and control system temperature is 50 DEG C,
System pH=9.5 collects metering plastic slurries；(2) and under agitation according to SiO2：Al2O3=1：1.8 weight ratio to
A concentration of 60gSiO is added in plastic slurries2The waterglass of/L is warming up to 60 DEG C and is aged 3 hours, obtains the first solid sediment；
(3) first solid sediment is pressed into its sediment butt：Ammonium salt：H2O=1：1：It is small that 12 weight ratio exchanges 1 at 60 DEG C
When, filtering washing obtains the second solid sediment that sodium oxide content is less than 0.3%；(4) precipitation of the second solid sediment is pressed
Object butt：H2O=1：The second solid sediment of gained is mixed with beating by 10 weight ratio with water, and presses P2O5：Y2O3：Second solid
Sediment butt=0.038 of sediment：0.032：Phosphoric acid is added in 1 weight ratio and yttrium nitrate solution is mixed, then at 70
It is reacted 2 hours at DEG C, 15 hours is dried at 120 DEG C up to phosphorus provided by the invention, metal-modified mesoporous after filtering washing
Silica-alumina material.It is denoted as A-3.
A-3 has boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry
Group becomes 0.12Na2O·65.4Al2O3·27.2SiO2·3.7P2O5·3.1Y2O3；Specific surface area 418m2/ g, Kong Rong
1.09cm3/ g, average pore size 10.4nm.
Preparation example 4
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) by a concentration of 102gAl2O3/ L, Crater corrosion 2.5NaAlO2Solution is placed in beaker, will be a concentration of under stirring
90gAl2O3The Al of/L2(SO4)3It is added, until system pH=8.5, it is 40 DEG C to keep gelling temperature, collects metering plastic slurries；
(2) according to SiO under stirring2：Al2O3=1：A concentration of 100gSiO is added into plastic slurries for 2.1 weight ratio2The water glass of/L
Glass is warming up to 70 DEG C and is aged 2 hours, obtains the first solid sediment；(3) the first solid sediment is pressed into its sediment butt：
NH4Cl：H2O=1：1：10 weight ratio exchanges 1 hour at 60 DEG C, and filtering washing obtains the of sodium oxide content less than 0.3%
Two solid sediments；(4) the second solid sediment is pressed into its sediment butt：H2O=1：8 weight ratio is mixed with beating with water,
And press P2O5：MgO：TiO2：MnO2：ZnO：Sediment butt=0.012 of second solid sediment：0.01：0.012：0.012：
0.01：Phosphoric acid, magnesium nitrate, titanium sulfate, manganese chloride and zinc nitrate is added in 1 weight ratio, is reacted 2 hours at 70 DEG C, filters
10 hours are dried up to phosphorus provided by the invention, metal-modified mesoporous silica-alumina material at 120 DEG C after washing.It is denoted as A-4.
A-4 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry forms
For 0.06Na2O·68.2Al2O3·26.1SiO2·1.1P2O5·0.9MgO·1.1TiO2·1.2MnO2·0.8ZnO；Compare table
Area 408m2/ g, hole hold 1.03cm3/ g, average pore size 10.1nm.
Preparation example 5
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) a concentration of 90gAl is used2O3The Al of/L2(SO4)3Solution and a concentration of 102gAl2O3/ L, Crater corrosion are 2.5
NaAlO2Solution is reaction raw materials, using cocurrent plastic mode, mixing plastic is carried out under being vigorously stirred, control system temperature is 35
DEG C, system pH=9.5 collects metering plastic slurries, and (2) are under stiring according to SiO2：Al2O3=1：1 weight ratio is at rubber cement
A concentration of 60gSiO is added in liquid2The waterglass of/L is warming up to 70 DEG C and is aged 1 hour, obtains the first solid sediment；(3) mistake
After drainage is washed, by the sediment butt of the first solid sediment：Ammonium salt：H2O=1:1:10 weight ratio and NH4Cl and deionization
Water mixes, and ion exchange is carried out at 55 DEG C and obtains the second solid sediment that sodium oxide content is less than 0.3%；(4) by second
Solid sediment reslurry, and press MgO：Sediment butt=0.025 of second solid sediment：Nitre is added in 1 weight ratio
Sour magnesium reacts 1 hour at 65 DEG C, filters simultaneously 10 hours dry in 120 DEG C, obtains third solid sediment；It is heavy by third solid
The sediment butt of starch：P2O5：La2O3=1：0.007：0.010 weight ratio is by drying sample and phosphoric acid and lanthanum chloride solution
Mixing, it is 10 hours dry in 120 DEG C after grinding uniformly, change up to phosphorus provided by the invention, metal within 2 hours then at 550 DEG C of roastings
The mesoporous silica-alumina material of property.It is denoted as A-5.
A-5 has boehmite phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry
Group becomes 0.13Na2O·49.8Al2O3·45.6SiO2·0.7P2O5·2.5MgO·1.0La2O3；Specific surface area 360m2/ g,
Hole holds 0.93cm3/ g, average pore size 10.3nm.
Preparation example 6
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) by a concentration of 90gAl2O3The Al of/L2(SO4)3Solution is placed in beaker, is added with stirring a concentration of 25wt.%
Ammonium hydroxide, until system pH=9.0, it is 40 DEG C to keep gelling temperature, collects metering plastic slurries；(2) it presses under agitation
According to SiO2：Al2O3=1：A concentration of 60gSiO is added into plastic slurries for 3 weight ratio2The waterglass of/L, be warming up to 60 DEG C it is old
Change 2 hours, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt：HCl：H2O=1：
0.08：10 weight ratio exchanges 1 hour at 50 DEG C, and filtering washing obtains Na2Second solid of the O content less than 0.3% precipitates
Object；(4) by the second solid sediment reslurry and by the sediment butt of the second solid sediment：P2O5=1：0.6 weight
It than being mixed with phosphoric acid, is stirred 1 hour at 70 DEG C, filters and 10 hours dry in 120 DEG C, obtain third solid sediment；It will
Obtained third solid sediment and rare earth chloride (containing lanthanide-indueed shift) solution, by the precipitation of third solid sediment
Object butt：RE2O3=1：5.5 weight ratio with mix, it is 10 hours dry in 120 DEG C after grinding uniformly, it is small then at 550 DEG C of roastings 2
When up to phosphorus provided by the invention, metal-modified mesoporous silica-alumina material.It is denoted as A-6.
A-6 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its element point
Analysis chemical composition is 0.11Na2O·72.4Al2O3·21.2SiO2·0.6P2O5·5.3RE2O3；Specific surface area 396m2/ g, hole
Hold 0.96cm3/ g, average pore size 9.7nm.
Preparation example 7
The preparation example is for illustrating phosphorus provided by the invention, metal-modified mesoporous silica-alumina material and preparation method thereof.
(1) a concentration of 90gAl is used2O3The Al of/L2(SO4)3Solution and a concentration of 102gAl2O3/ L, Crater corrosion 2.5
NaAlO2Solution is reaction raw materials, using cocurrent plastic mode, mixing plastic is carried out under being vigorously stirred, control system temperature is
35 DEG C, system pH=9.5, metering plastic slurries are collected, (2) are under stiring according to SiO2：Al2O3=1：1.3 weight ratio at
A concentration of 60gSiO is added in rubber cement liquid2The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the first solid sediment；
(3) after filtering washing, by the sediment butt of the first solid sediment：Ammonium salt：H2O=1:1:15 weight ratio and NH4It Cl and goes
Ionized water mixes, and ion exchange is carried out at 65 DEG C and obtains the second solid sediment that sodium oxide content is less than 0.3%；(4) it presses
P2O5：MgO：Sediment butt=0.015 of second solid sediment：0.035：1 weight ratio is by the second solid sediment and phosphorus
Sour and magnesium nitrate is mixed, 10 hours dry at 120 DEG C after grinding uniformly, and 2 hours are roasted then at 600 DEG C up to the present invention
The phosphorus of offer, metal-modified mesoporous silica-alumina material.It is denoted as A-7.
A-7 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its elementary analytical chemistry forms
For 0.16Na2O·55.4Al2O3·38.1SiO2·1.5P2O5·3.5MgO；Specific surface area 329m2/ g, hole hold 0.88cm3/ g,
Average pore size 10.7nm.
Compare preparation example 1
The comparison preparation example is for illustrating mesoporous silica-alumina material and preparation method thereof.
Mesoporous silica-alumina material is prepared according to the method for preparation example 1, unlike, do not include step (4), but directly by the
Mesoporous silica-alumina material of the product obtained after two solid sediments are 10 hours dry at 120 DEG C as reference, is denoted as DA-1.
DA-1 has structure of similar to thin diaspore, X-ray diffraction spectrogram similar to A-1；Its elementary analytical chemistry group becomes
0.19Na2O·81.9Al2O3·16.7SiO2；Specific surface area 514m2/ g, hole hold 1.45cm3/ g, average pore size 11.3nm.
Compare preparation example 2
The comparison preparation example is for illustrating mesoporous silica-alumina material of P Modification and preparation method thereof.
Prepare mesoporous silica-alumina material according to the method for preparation example 1, unlike, be added without in step (4) magnesium nitrate and
Titanium sulfate；The second solid sediment is pressed into its sediment butt：H2O=1：10 weight ratio is mixed with beating with water, and is pressed
P2O5：Sediment butt=0.075 of second solid sediment：Ammonium phosphate is added in 1 weight ratio, and it is small that 2 are reacted at 60 DEG C
When, the mesoporous silica-alumina material of the product that is obtained after dry 10 hours at 120 DEG C after filtering washing as the P Modification of reference is remembered
For DA-2.
DA-2 has structure of similar to thin diaspore, X-ray diffraction spectrogram similar to A-1；Its elementary analytical chemistry group becomes
0.08Na2O·76.6Al2O3·15.8SiO2·7.3P2O5；Specific surface area 469m2/ g, hole hold 1.31cm3/ g, average pore size
11.0nm。
Compare preparation example 3
The comparison preparation example is for illustrating metal-modified mesoporous silica-alumina material and preparation method thereof.
Mesoporous silica-alumina material is prepared according to the method for preparation example 1, unlike, it is added without ammonium phosphate in step (4)；I.e.
The second solid sediment of gained is pressed into its sediment butt：H2O=1：10 weight ratio is mixed with beating with water, and presses MgO：TiO2：
Sediment butt=0.017 of second solid sediment：0.012：Magnesium nitrate and titanium sulfate is added in 1 weight ratio, then at 60 DEG C
Lower reaction 2 hours, metal-modified mesoporous of the product obtained after 10 hours dry at 120 DEG C after filtering washing as reference
Silica-alumina material is denoted as DA-3.
DA-3 has structure of similar to thin diaspore, X-ray diffraction spectrogram similar to A-1；Its elementary analytical chemistry group becomes
0.08Na2O·77.2Al2O3·15.9SiO2·1.5MgO·1.0TiO2；Specific surface area 496m2/ g, hole hold 1.38cm3/ g is put down
Equal aperture 11.2nm.
Embodiment 1
The embodiment is for illustrating catalytic cracking catalyst provided by the invention and preparation method thereof.
The boehmite of 20 parts by weight in terms of butt is mixed with beating with deionized water, and is added into obtained slurries
Enter hydrochloric acid peptization, acid-aluminum ratio (weight ratio) is 0.20：1, then by temperature rise to 65 DEG C be acidified 1 hour, be then separately added into
The slurries (solid content be 25 weight %) of 28 parts by weight kaolin clay of butt meter, 13 parts by weight in terms of butt Aluminum sol and
Slurries (the solid content of the phosphorus of 10 parts by weight in terms of butt prepared by preparation example 1, metal-modified mesoporous silica-alumina material A-1
For 18 weight %), it stirs 20 minutes, the described second Y containing rare earth of 29 parts by weight in terms of butt is added thereto again later
Type molecular sieve pulp (solid content is 35 weight %) continues spray drying after stirring and microspherical catalyst is made.Then by the microballoon
Catalyst roasts 1 hour at 500 DEG C, then (NH is used at 60 DEG C4)2SO4Solution washs (wherein, (NH4)2SO4：Microballoon is catalyzed
Agent：H2O=0.05：1：10) to Na2O content be less than 0.25 weight %, then eluted and filtered with deionized water, later then at
It is dried at 110 DEG C, obtains catalytic cracking catalyst C1, wherein on the basis of the total weight of the catalytic cracking catalyst C1, institute
State mesoporous active materials containing 10 weight % in catalytic cracking catalyst C1, the Y type molecular sieve containing rare earth of 29 weight %, 28
The Al of the kaolin of weight %, 33 weight %2O3Binder.
Comparative example 1
The comparative example is for illustrating catalytic cracking catalyst of reference and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, phosphorus, the metal that will be prepared by preparation example 1
Modified mesoporous silica-alumina material A-1 is replaced with the mesoporous silica-alumina material DA-1 prepared by comparison preparation example 1 of identical weight part, is obtained
To reference catalytic cracking catalyst CB1, wherein on the basis of the total weight of the reference catalytic cracking catalyst CB1, the ginseng
Than mesoporous silica-alumina material, 29 weight % containing 10 weight % in catalytic cracking catalyst CB1 the Y type molecular sieve containing rare earth,
The Al of the kaolin of 28 weight %, 33 weight %2O3Binder.
Comparative example 2
The comparative example is for illustrating catalytic cracking catalyst of reference and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, phosphorus, the metal that will be prepared by preparation example 1
The mesoporous silica-alumina material DA- of the P Modification prepared by comparison preparation example 2 of modified mesoporous silica-alumina material A-1 identical weight parts
2 replace, and obtain reference catalytic cracking catalyst CB2, wherein using the total weight of the reference catalytic cracking catalyst CB2 as base
Standard, the Y containing rare earth of the mesoporous silica-alumina material containing 10 weight %, 29 weight % in the reference catalytic cracking catalyst CB2
The Al of type molecular sieve, the kaolin of 28 weight %, 33 weight %2O3Binder.
Comparative example 3
The comparative example is for illustrating catalytic cracking catalyst of reference and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, phosphorus, the metal that will be prepared by preparation example 1
The metal-modified mesoporous silica-alumina material prepared by comparison preparation example 3 of modified mesoporous silica-alumina material A-1 identical weight parts
DA-3 is replaced, and obtains reference catalytic cracking catalyst CB3, wherein the total weight with the reference catalytic cracking catalyst CB3 is
Benchmark, the mesoporous silica-alumina material containing 10 weight % in the reference catalytic cracking catalyst CB3,29 weight % containing rare earth
The Al of Y type molecular sieve, the kaolin of 28 weight %, 33 weight %2O3Binder.
Comparative example 4
The comparative example is for illustrating catalytic cracking catalyst of reference and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, it is added without phosphorus, metal-modified mesoporous
Silica-alumina material A-1, and the kaolin of phosphorus, the identical dry weights of metal-modified mesoporous silica-alumina material A-1 is substituted, joined
Than catalytic cracking catalyst CB4, wherein on the basis of the total weight of the reference catalytic cracking catalyst CB4, the reference is urged
The kaolin of the Y type molecular sieve containing rare earth, 38 weight % containing 29 weight % in fluidized cracking catalysts CB4,33 weight %
Al2O3Binder.
Embodiment 2
The embodiment is for illustrating 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, add 20 parts by weight in terms of butt
Boehmite, and into obtained slurries be added hydrochloric acid peptization, acid-aluminum ratio (weight) be 0.20：1, then temperature is risen to
65 DEG C are acidified 1 hour, be then separately added into the Aluminum sol of 5 parts by weight in terms of butt, 30 parts by weight in terms of butt by making
The slurries (solid content is 20 weight %) of phosphorus, metal-modified mesoporous silica-alumina material A-2 prepared by standby example 2, are stirred 20 minutes, it
The described first Y type molecular sieve containing rare earth that 13 parts by weight in terms of butt are added thereto again afterwards, 10 weight in terms of butt
The mixing slurry of the Y type molecular sieve of the third containing rare earth of part and the MFI structure molecular sieve of 2 parts by weight in terms of butt
Liquid (solid content is 35 weight %) continues spray drying after stirring and microspherical catalyst is made.Then by the microspherical catalyst 500
It is roasted 1 hour at DEG C, then uses (NH 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 at 110 DEG C later
It is dry, obtain catalytic cracking catalyst C2, wherein on the basis of the total weight of the catalytic cracking catalyst C2, the catalysis is split
Change mesoporous active materials containing 30 weight % in catalyst C2, the Y type molecular sieve containing rare earth of 23 weight %, 2 weight %
The Al of MFI structure molecular sieve, the kaolin of 20 weight %, 25 weight %2O3Binder.
Embodiment 3
The embodiment is for illustrating 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, add 30 parts by weight in terms of butt
Boehmite, and into obtained slurries be added hydrochloric acid peptization, acid-aluminum ratio (weight) be 0.20：1, then temperature is risen to
65 DEG C be acidified 1 hour, be then separately added into 20 parts by weight in terms of butt the phosphorus prepared by preparation example 3, it is metal-modified in
The slurries (solid content is 25 weight %) of hole silica-alumina material A-3, stir 20 minutes, are added 15 in terms of butt thereto again later
The described second Y type molecules containing rare earth of the described first Y type molecular sieve containing rare earth of parts by weight and 5 parts by weight in terms of butt
The mixed serum (solid content is 35 weight %) of sieve and the re chloride of 2 parts by weight in terms of rare earth oxide, continue
Microspherical catalyst is made in spray drying after stirring.Then the microspherical catalyst is roasted 1 hour at 500 DEG C, then at 60 DEG C
With (NH4)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, is dried at 110 DEG C later, and catalytic cracking catalyst C3 is obtained,
In, contain 20 weight %'s on the basis of the total weight of the catalytic cracking catalyst C3, in the catalytic cracking catalyst C3
The Al of mesoporous active materials, the Y type molecular sieve containing rare earth of 20 weight %, the kaolin of 28 weight %, 30 weight %2O3It bonds
Agent, 2 weight % rare earth oxide.
Embodiment 4
The embodiment is for illustrating 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 Aluminum sol of 15 parts by weight in terms of butt and in terms of butt
The phosphorus prepared by preparation example 4 of 15 parts by weight, metal-modified mesoporous silica-alumina material A-4 slurries (solid content is 20 weights
Amount %) it is mixed with beating, it stirs 120 minutes, described second that 15 parts by weight in terms of butt are added thereto again later contains rare earth
Y type molecular sieve and the mixed serums of Y type molecular sieve of the third containing rare earth of 15 parts by weight in terms of butt (solid content is
35 weight %), continue spray drying after stirring and microspherical catalyst is made.Then the microspherical catalyst is roasted to 1 at 500 DEG C small
When, 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 at 110 DEG C later, obtain catalytic cracking
Catalyst C4, wherein on the basis of the total weight of the catalytic cracking catalyst C4, contain in the catalytic cracking catalyst C4
The mesoporous active materials of 15 weight %, the Y type molecular sieve containing rare earth of 30 weight %, the kaolin of 40 weight %, 15 weight %
Al2O3Binder.
Embodiment 5
The embodiment is for illustrating 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 SiO2A concentration of 7.8 weight
Measure %, the Ludox that pH value is 2.8.
(2) catalytic cracking catalyst is prepared：
The kaolin of 10 parts by weight in terms of butt, stirring are added in the above-mentioned Ludox of 20 parts by weight in terms of butt
The phosphorus of 40 parts by weight in terms of butt prepared by preparation example 5, the slurries of metal-modified mesoporous silica-alumina material A-5 are added after 1h
(solid content is 18 weight %) is mixed with beating, and described first that 10 parts by weight in terms of butt are added thereto again later contains rare earth
Y type molecular sieve, 10 parts by weight in terms of butt the described second Y type molecular sieve containing rare earth and 10 parts by weight in terms of butt
Y type molecular sieve slurries (solid content be 30 weight %s) of the third containing rare earth, after continuing stirring spray drying microballoon is made
Catalyst.Then the microspherical catalyst is used to (NH 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, later then at 110 DEG C
Lower drying, obtains catalytic cracking catalyst C5, wherein described to urge on the basis of the total weight of the catalytic cracking catalyst C5
The Y type molecular sieve containing rare earth, 10 weights of mesoporous active materials, 30 weight % containing 40 weight % in fluidized cracking catalysts C5
Measure the kaolin of %, the SiO of 20 weight %2Binder.
Embodiment 6
The embodiment is for illustrating catalytic cracking catalyst provided by the invention and preparation method thereof.
The boehmite of 18 parts by weight in terms of butt is mixed with beating with deionized water, and is added into obtained slurries
Enter hydrochloric acid peptization, acid-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 be 25 weight %) of 30 parts by weight kaolin clay of base meter, 7 parts by weight in terms of butt Aluminum sol and with
Slurries (the solid content 18 of the phosphorus of 5 parts by weight of butt meter prepared by preparation example 6, metal-modified mesoporous silica-alumina material A-6
Weight %), it stirs 20 minutes, the described first Y types containing rare earth point of 18 parts by weight in terms of butt is added thereto again later
(solid content is 35 weights to the mixed serum of son sieve and the described second Y type molecular sieve containing rare earth of 22 parts by weight in terms of butt
Measure %), continue spray drying after stirring and microspherical catalyst is made.Then the microspherical catalyst is roasted 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 at 110 DEG C later, obtained catalytic cracking and urge
Agent C6, wherein on the basis of the total weight of the catalytic cracking catalyst C6, contain 5 in the catalytic cracking catalyst C6
The mesoporous active materials of weight %, the Y type molecular sieve containing rare earth of 40 weight %, the kaolin of 30 weight %, 25 weight %
Al2O3Binder.
Embodiment 7
The embodiment is for illustrating catalytic cracking catalyst provided by the invention and preparation method thereof.
Catalytic cracking catalyst is prepared according to the method for embodiment 1, unlike, phosphorus, the metal that will be prepared by preparation example 1
The phosphorus prepared by preparation example 7, metal-modified mesoporous silica-alumina material A- of modified mesoporous silica-alumina material A-1 identical weight parts
7 replace, and obtain catalytic cracking catalyst C7, wherein on the basis of the total weight of the catalytic cracking catalyst C7, the catalysis
The Y type molecular sieve containing rare earth, the 28 weight % of mesoporous active materials, 29 weight % containing 10 weight % in Cracking catalyst C7
Kaolin, 33 weight % Al2O3Binder.
Embodiment 8-14
Embodiment 8-14 is used to illustrate the test of catalytic cracking catalyst performance provided by the invention.
Respectively by the catalytic cracking catalyst C1-C7 of above-mentioned preparation agings 17 under conditions of 800 DEG C, 100% water vapour
Hour, it is filled in later in small fixed flowing bed ACE devices (being purchased from KTI companies of the U.S.), amount of fill is respectively 9g.So
Afterwards, reaction temperature be 500 DEG C, air speed 16h-1, agent weight of oil ratio be 6：Feedstock oil shown in table 1 is carried out under conditions of 1
Catalytic cracking reaction, reaction result are listed 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 used to illustrate the test of the catalytic cracking catalyst performance of reference.
Catalytic cracking reaction is carried out to feedstock oil according to the method for embodiment 8-14, unlike, catalytic cracking is catalyzed
Agent C1-C7 uses catalytic cracking catalyst CB1, CB2, CB3 and CB4 of the reference of identical weight part to substitute respectively, reaction result row
In table 2.
Table 1
Table 2
Table 3
The result of table 2 and table 3 illustrates, compared with identical with zeolite content but catalyst CB4 without mesoporous active materials, this
The catalyst that invention provides can be obviously improved the selectivity of coke, and content of sulfur in gasoline is greatly lowered, while also have higher
Cracking activity；But use catalyst CB1 phase without phosphorus and metal-modified mesoporous active materials identical as each component content
Than the coke yield of catalyst provided by the invention reduces, and coke selectivity is obviously improved, and content of sulfur in gasoline is big
Amplitude reduction；Compared with the catalyst CB2 of mesoporous active materials that are identical with each component content but using P Modification, the present invention provides
The content of sulfur in gasoline of catalyst be greatly lowered；It is identical as each component content but using metal-modified mesoporous active materials
Catalyst CB3 is compared, and the coke yield of catalyst provided by the invention reduces, and coke selectivity is obviously improved, and
Also have the effect of preferably reducing content of sulfur in gasoline.
It can be seen that catalytic cracking catalyst provided by the invention can not only show during heavy oil catalytic cracking
Go out better coke selectivity and higher catalytic cracking activity, but also higher yield of gasoline and lower vapour can be obtained
Oily sulfur content.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, 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 also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of catalytic cracking catalyst, which is characterized in that described to urge on the basis of the total weight of the catalytic cracking catalyst
Fluidized cracking catalysts contain the cracking activity constituent element of 1-60 weight %, the mesoporous active materials of 1-50 weight %, 1-70 weight %
Clay and 1-70 weight % binder；There is the mesoporous active materials boehmite crystal phase structure, the mesoporous to live
It is with the anhydrous chemical expression of the weight ratio meter of oxide in property material：(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, the periodic table of elements IIB, IIIB, IVB, VIIB
It is one or more in race's element and lanthanide series rare-earth elements, highest valent state when y is metal M formation oxides, and x
With the numerical value of y the chemical valence of M and O is balanced, and the specific surface area of the mesoporous active materials is 200-500m2/ g, Kong Rong
For 0.5-1.5cm3/ g, average pore size 8-18nm；
The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y type molecular sieve containing rare earth
One in the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth
Kind is a variety of；
Wherein, the preparation method of the described first Y type molecular sieve containing rare earth includes：Under stiring, by the Y type molecular sieve containing rare earth
It is contacted with silicon tetrachloride, the temperature of contact is 100-500 DEG C, and the time of contact is 1-10 hours, the Y type molecules containing rare earth
The weight ratio of sieve and silicon tetrachloride is 1：0.05-0.5；
The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30：1, initial lattice constant is 2.430-2.460nm, with
Content of rare earth on the basis of the total weight of described second Y type molecular sieve containing rare earth and in terms of oxide is 10-20 weight %, is put down
The ratio of weighing apparatus lattice constant and initial lattice constant is at least 0.985, wherein the X-ray diffraction analysis molecular sieve is in 2 θ
12.43 ± 0.06 ° and 11.87 ± 0.06 ° of two diffraction peak intensity ratio I1/I2More than 1；
The preparation method of Y type molecular sieve of the third containing rare earth includes：By super-stable Y molecular sieves and a concentration of 0.01-2N
Acid solution is with liquid-solid ratio 4-20：1 ratio is sufficiently mixed at 20-100 DEG C, washing, filtering after processing 10-300 minutes, then is added
Enter rare-earth salt solution and carry out rare earth ion exchanged, is washed, filtered and dried successively after exchange.
2. catalytic cracking catalyst according to claim 1, wherein using the total weight of the catalytic cracking catalyst as base
Standard, the catalytic cracking catalyst contain the cracking activity constituent element of 10-50 weight %, 5-40 weight % mesoporous active materials,
The binder of the clay and 10-60 weight % of 10-60 weight %.
3. catalytic cracking catalyst according to claim 1, wherein the specific surface area of the mesoporous active materials is 300-
450m2/ g, Kong Rongwei 0.7-1.2cm3/ g, average pore size 10-15nm.
4. catalytic cracking catalyst according to claim 1, wherein the metal M is Mg, Zn, Y, Ti, Mn, La and Ce
In one or more mixing.
5. according to the catalytic cracking catalyst described in any one of claim 1-4, wherein the mesoporous active materials according to
Following methods are prepared：
(1) silicon source and aqueous slkali are obtained into plastic slurries room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11；
(2) according to SiO2：Al2O3=1：Silicon source is added into the plastic slurries in the weight ratio of (0.6-9), in room temperature to 90 DEG C
Lower ageing 1-5 hours, obtains the first solid sediment；
(3) by first solid sediment and ammonium salt or acid solution contact treatment, sodium oxide content is obtained by filtration and is less than 0.3 weight
Measure the second solid sediment of %；
(4) by second solid sediment, the compound of phosphorus source and metal M, according to P2O5：MxOy：The second solid precipitation
The sediment butt of object=(0.005-0.1)：(0.005-0.1)：1 weight ratio contact treatment, and product of contact is dried.
6. catalytic cracking catalyst according to claim 5, wherein silicon source described in step (1) is selected from aluminum nitrate, sulfuric acid
It is one or more in aluminium and aluminium chloride；The alkaline solution is selected from ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution and inclined aluminium
It is one or more in acid sodium solution.
7. catalytic cracking catalyst according to claim 5, wherein silicon source described in step (2) is selected from waterglass, silicic acid
It is one or more in sodium, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon and silica.
8. catalytic cracking catalyst according to claim 5, wherein in step (3) will first solid sediment and
The process of ammonium salt contact treatment is by the first solid sediment obtained by step (2) by its sediment butt：Ammonium salt：H2O=1：
(0.1-1)：The weight ratio of (5-30) in room temperature to exchanging at 100 DEG C, until sodium oxide content is less than 0.3 weight in solid sediment
Measure %.
9. catalytic cracking catalyst according to claim 5, wherein ammonium salt described in step (3) is selected from ammonium chloride, sulfuric acid
It is one or more in ammonium, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.
10. catalytic cracking catalyst according to claim 5, wherein in step (3) will first solid sediment and
The process of acid solution contact treatment is by the first solid sediment obtained by step (2) by its sediment butt：Acid：H2O=1：
(0.03-0.30)：The weight ratio of (5-30) is in room temperature at least exchanging 0.2 hour at 100 DEG C.
11. catalytic cracking catalyst according to claim 5, wherein the acid in acid solution described in step (3) is selected from sulphur
It is one or more in acid, hydrochloric acid and nitric acid.
12. catalytic cracking catalyst according to claim 5, wherein in step (4) by second solid sediment,
The contact treatment process of phosphorus source and the compound of metal, selected from it is following a), b), c), d) during one kind：
A) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with beating with water, then
The compound of phosphorus source and metal M is added sequentially in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour,
It is 10-20 hours dry at 100 DEG C -150 DEG C after filtering washing；
B) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with beating with water, then
Phosphorus source is added in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour, directly with metal M's after filtering
Compound mixes in proportion, 10-20 hours dry at 100 DEG C -150 DEG C after grinding uniformly；
C) second solid sediment is pressed into its sediment butt：H2O=1：The weight ratio of (5-20) is mixed with beating with water, then
The compound of phosphorus source and the first metal M is added in above-mentioned slurries, it is small to contact treatment at 90 DEG C at least 0.2 in room temperature
When, third solid sediment is obtained after filtering, then third solid sediment is directly mixed with the compound of second of metal M,
It is 10-20 hours dry at 100 DEG C -150 DEG C after grinding uniformly, wherein the compound of the first metal M and second of gold medal
The compound for belonging to M is identical or different；
D) the second solid sediment is directly mixed with phosphorus source and the compound of metal M in proportion, grinding uniformly after 100 DEG C-
It is 10-20 hours dry at 150 DEG C.
13. catalytic cracking catalyst according to claim 5, wherein after the drying steps described in step (4), also wrap
It includes and roasts gained desciccate 1-4 hours at 500 DEG C -700 DEG C.
14. catalytic cracking catalyst according to claim 5, wherein phosphorus source described in step (4) is selected from ammonium phosphate, phosphorus
It is one or more in sour hydrogen diammonium, ammonium dihydrogen phosphate and phosphoric acid.
15. catalytic cracking catalyst according to claim 5, wherein the compound of metal M is water-soluble in step (4)
Compound.
16. catalytic cracking catalyst according to claim 5, wherein the compound of the metal M described in step (4) is
Nitrate, sulfate or the chloride of metal M.
17. according to the catalytic cracking catalyst described in any one of claim 1-4, wherein the cracking activity constituent element is also
Containing MFI structure molecular sieve, with the anhydrous chemical composition expression formula of the molar ratio computing of oxide in the MFI structure molecular sieve
For：(0.01-0.25)RE2O3·(0.005-0.02)Na2O·Al2O3·(0.2-1)P2O5·(35-120)SiO2, the molecular sieve
Absorption weight ratio to n-hexane and hexamethylene is 4-5：1.
18. the preparation method of the catalytic cracking catalyst described in any one of claim 1-17, this method includes will be described
Cracking activity constituent element, mesoporous active materials, clay and binder are mixed with beating, and are then spray-dried, are washed successively again, mistake
Filter and drying.
19. application of the catalytic cracking catalyst described in any one of claim 1-17 in heavy oil catalytic cracking.
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| 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
| 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 |
| 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 |
| 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 |
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