CN106179475A

CN106179475A - A kind of catalytic cracking catalyst and its preparation method and application

Info

Publication number: CN106179475A
Application number: CN201510212725.1A
Authority: CN
Inventors: 任飞; 朱玉霞; 罗斌; 罗一斌; 郑金玉; 田辉平; 陈振宇; 杨雪
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-04-29
Filing date: 2015-04-29
Publication date: 2016-12-07
Anticipated expiration: 2035-04-29
Also published as: CN106179475B

Abstract

The invention provides a kind of catalytic cracking catalyst and its preparation method and application.On the basis of the gross weight of catalytic cracking catalyst, catalytic cracking catalyst contains the mesoporous active materials of 1-50 weight %；Mesoporous active materials with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, and y is that metal M maximum when forming oxide closes valence state, and the numerical value of x and y makes the quantivalence of M and O balance.It has relatively low coke selectivity and higher catalytic cracking activity in RFCC, and can obtain higher yield of liquefied gas and relatively low content of sulfur in gasoline.

Description

A kind of catalytic cracking catalyst and its preparation method and application

Technical field

The present invention relates to a kind of catalytic cracking catalyst, the preparation method of described catalytic cracking catalyst and The application in RFCC of the described catalytic cracking catalyst.

Background technology

Catalytic cracking (FCC) is important crude oil secondary processing process, occupies act foot in petroleum refining industry The status of weight.In catalytic cracking process, heavy end is (such as vacuum distillate or the slag of more heavy constituent Oil) react in the presence of a catalyst, it is converted into the high value added products such as liquefied gas, gasoline, diesel oil, Typically require in this process and use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material Owing to having excellent shape selective catalysis performance and the highest cracking reaction activity, it is widely used in oil refining In system and processing industry.Along with the requirement of the aspects such as the day by day exhausted of petroleum resources and environmental conservation, special It not that crude oil becomes heavy growth trend and the market wilderness demand to light-end products, increasingly in PETROLEUM PROCESSING work Industry is increasingly paid attention to the deep processing to heavy oil and residual oil.

For improving conversion ratio, strengthen heavy oil conversion performance, reduce intermediate oil and Petroleum simultaneously Converting further, traditional micro porous molecular sieve catalysis material is less due to its duct, to bigger raw molecule Demonstrate and significantly limit diffusion so that simple micro porous molecular sieve catalysis material be less suitable for for The catalytic cracking of the heavy distillate such as heavy oil and residual oil, so that use that aperture is relatively big, divide reactant Son does not has diffusion-restricted and has the material of higher cracking activity.Therefore, mesoporous and macropore catalysis material Research and development are increasingly subject to people's attention.Additionally, in catalytic cracking field, silica-alumina material has due to it Stronger acid centre and good cracking performance is had to be widely applied.

CN1565733A discloses a kind of mesoporous silicon aluminum, and this mesoporous silicon aluminum has the thin water aluminum of plan Stone crystal phase structure, with the anhydrous chemical expression of the mass ratio range of oxide be: (0-0.3)Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, its specific surface area is 200-400m²/ g, pore volume is 0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.This mesoporous silicon aluminum Preparation be not required to use organic formwork agent, synthesis low cost, and the mesoporous silicon aluminum obtained have high Cracking activity and hydrothermal stability, show good macromole cracking performance in catalytic cracking reaction.

CN1854258A discloses a kind of fluid cracking catalyst, and this fluid cracking catalyst contains 3-20 The mesoporous silica-alumina materials through acid treatment of weight %, this mesoporous silica-alumina materials has boehmite crystalline phase knot Structure, with the anhydrous chemical expression of the mass ratio range of oxide be: (0-0.3)Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, specific surface area is 200-400m²/ g, pore volume is 0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.

CN1978593A discloses a kind of Cracking catalyst, containing a kind of mesoporous material in this Cracking catalyst Material, the anhydrous compound composition of described mesoporous material with the mass ratio range of oxide is (0-0.3)Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(1-20)M_xO_y, wherein, metal M is selected from element week In phase Table II A, IB, IIB, IVB, VB, VIB, VIIB, VIIIB or lanthanide series rare-earth elements one Kind, this mesoporous material has boehmite crystal phase structure, and specific surface area is 200-400m²/ g, pore volume For 0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm.This catalyst is permissible It is directly used in catalytic cracking reaction, under conventional FCC operating condition, both can improve crude oil and weight Oil conversion ratio, can effectively reduce again FCC gasoline sulfur content.

CN102078821A discloses a kind of Cracking catalyst containing mesoporous silica-alumina materials, and wherein, this splits Change catalyst to be made up of cracking activity constituent element, clay, binding agent and mesoporous silica-alumina materials, described mesoporous silicon Aluminum has boehmite crystal phase structure, with the anhydrous chemical expression of the mass ratio range of oxide For: (0-0.3) Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, specific surface area is 200-400m²/ g, pore volume is 0.5-2.0mL/g, average pore size is 8-20nm, and most probable pore size is 5-15nm, and described binding agent is silicon Colloidal sol and/or Alumina gel.Although this Cracking catalyst is compared with the conventional catalyst using boehmite, Have that production cost is low, the more preferable advantage of converting crude oil ability, but its coke selectivity is poor.

Summary of the invention

The invention aims to provide a kind of new there is relatively low coke selectivity, higher cracking is lived Property, higher yield of liquefied gas, and also can effectively reduce FCC (catalytic cracking) content of sulfur in gasoline Catalytic cracking catalyst, the preparation method of described catalytic cracking catalyst and described catalytic cracking catalysis Agent application in RFCC.

To this end, according to an aspect of the invention, it is provided a kind of catalytic cracking catalyst, wherein, with On the basis of the gross weight of described catalytic cracking catalyst, described catalytic cracking catalyst contains 1-60 weight % Cracking activity constituent element, the mesoporous active materials of 1-50 weight %, the clay of 1-70 weight % and 1-70 weight The binding agent of amount %；Described mesoporous active materials has boehmite crystal phase structure, described mesopore activity In material, the anhydrous chemical expression of mass ratio range with oxide is: (0-0.2) Na₂O·(40-85) Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and in lanthanide series rare-earth elements Planting or multiple, y is that maximum during metal M formation oxide closes valence state, and the numerical value of x and y makes The quantivalence of M and O balances, and the specific surface area of described mesoporous active materials is 200-500m²/ g, hole Hold for 0.5-1.5cm³/ g, average pore size is 8-18nm；

With the gross weight benchmark of described cracking activity constituent element, described cracking activity constituent element contains 50-95 weight First molecular sieve component of amount % and the second molecular sieve component of 5-50 weight %, described first molecule screen banks It is divided into one or more in the first Y type molecular sieve, the second Y type molecular sieve and the 3rd Y type molecular sieve, Described second molecular sieve component is the first MFI structure molecular sieve and/or the second MFI structure molecular sieve；

Described first Y type molecular sieve is the DASY molecular sieve containing rare earth；

Described second Y type molecular sieve is REY molecular sieve；

The content of rare earth counted with rare earth oxide in described 3rd Y type molecular sieve for 12-16 weight %, with P₂O₅The phosphorus content of meter is 0.5-7 weight %, this molecular sieve³¹In P MAS NMR spectra, chemical potential The peak area that shifting is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for the percent of total peak area and is more than 85%, this molecular sieve²⁷In Al MAS NMR spectra, chemical shift is 0 ± 2ppm resonance signal Peak area accounts for the percent of total peak area more than 20%；

Described first MFI structure molecular sieve with the anhydrous chemical expression of the molar ratio computing of oxide is: (0.01-0.25)RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1)P₂O₅·(35-120)SiO₂, this molecular sieve Absorption weight ratio to normal hexane Yu hexamethylene is 4-5:1；

Described second MFI structure molecular sieve with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.3)Na₂O·(0.5-5.5)Al₂O₃·(1.3-10)P₂O₅·(0.7-15)M1_xO_y·(0.01-5)M2_mO_n·(70-97) SiO₂, wherein, M1 is Fe, Co or Ni, and x represents the atomic number of M1, and y represents and meets M1 oxygen Changing the number of state requisite oxygen, M2 is Zn, Mn, Ga or Sn, and m represents the atomic number of M2, n table Show the number meeting M2 oxidation state requisite oxygen.

According to another aspect of the present invention, additionally provide the preparation method of described catalytic cracking catalyst, The method includes the mixing making beating of described cracking activity constituent element, mesoporous active materials, clay and binding agent, Carry out the most successively being spray-dried, wash, filter and being dried.

Additionally, according to a further aspect of the invention, described catalytic cracking catalyst is additionally provided at heavy oil Application in catalytic cracking.

The catalytic cracking catalyst that the present invention provides is by by specific cracking activity constituent element, specific mesopore Active material and clay and binding agent with the use of, add the content of catalytic cracking catalyst mesopore, have Being beneficial to diffusion and the cracking of heavy oil macromole, this catalytic cracking catalyst is particularly well-suited to heavy-oil catalytic and splits Change, relatively low coke selectivity and higher can not only be shown during RFCC Catalytic cracking activity, and also it is obtained in that higher yield of liquefied gas and relatively low content of sulfur in gasoline.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Accompanying drawing explanation

Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.? In accompanying drawing:

Fig. 1 is the X-ray diffraction spectrogram of the mesoporous active materials obtained by preparation example 1.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of catalytic cracking catalyst, wherein, total with described catalytic cracking catalyst On the basis of weight, described catalytic cracking catalyst contains the cracking activity constituent element of 1-60 weight %, 1-50 The mesoporous active materials of weight %, the clay of 1-70 weight % and the binding agent of 1-70 weight %；In described Hole active material has boehmite crystal phase structure, with the weight of oxide in described mesoporous active materials Than the anhydrous chemical expression of meter it is: (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂· (0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, y is metal M Maximum when forming oxide closes valence state, and the numerical value of x and y makes the quantivalence of M and O balance, And the specific surface area of described mesoporous active materials is 200-500m²/ g, pore volume is 0.5-1.5cm³/ g, averagely Aperture is 8-18nm；

On the basis of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains 50-95 weight First molecular sieve component of amount % and the second molecular sieve component of 5-50 weight %, described first molecule screen banks It is divided into one or more in the first Y type molecular sieve, the second Y type molecular sieve and the 3rd Y type molecular sieve, Described second molecular sieve component is the first MFI structure molecular sieve and/or the second MFI structure molecular sieve；

Described second Y type molecular sieve is REY molecular sieve；

Described second MFI structure molecular sieve with the anhydrous chemical expression of the mass ratio range of oxide is: (0-0.3)Na₂O·(0.5-5.5)Al₂O₃·(1.3-10)P₂O₅·(0.7-15)M1_m1O_n1·(0.01-5)M2_m2O_n2·(70- 97)SiO₂, wherein, M1 is Fe, Co or Ni, and m1 represents the atomic number of M1, and n1 represents satisfied The number of M1 oxidation state requisite oxygen, M2 is Zn, Mn, Ga or Sn, and m2 represents the atomic number of M2, N2 represents the number meeting M2 oxidation state requisite oxygen.

In the present invention, described specific surface area, pore volume and average pore size all use nitrogen absorption under low temperature-desorption Method is measured, and the instrument used is the physical and chemical adsorption instrument of Micro meritics company of the U.S. ASAP2400。

The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that in described mesoporous active materials With the anhydrous chemical expression of the mass ratio range of oxide it is: (0.06-0.17) Na₂O·(49.5-74.5) Al₂O₃·(15.3-45.6)SiO₂·(0.6-7.5)P₂O₅·(2.5-8.5)M_xO_y。

The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that be catalyzed with described catalytic cracking On the basis of the gross weight of agent, described catalytic cracking catalyst contain 10-50 weight % cracking activity constituent element, The mesoporous active materials of 5-40 weight %, the clay of 10-60 weight % and the binding agent of 10-60 weight %, The content of above-mentioned each component is controlled the catalytic cracking catalyst enabled in the range of this is preferred There is more preferable combination property.

The above-mentioned catalytic cracking catalyst provided according to the present invention, so that the first molecular sieve component and the Two molecular sieve component can play more preferable coordinated effect, it is preferable that with described cracking activity constituent element Gross weight on the basis of, described cracking activity constituent element contain 65-86 weight % the first molecular sieve component and Second molecular sieve component of 14-35 weight %.

The above-mentioned catalytic cracking catalyst provided according to the present invention, it is preferable that described first molecular sieve component For in described first Y type molecular sieve, described second Y type molecular sieve and described 3rd Y type molecular sieve The mixture of at least two, described second molecular sieve component is described first MFI structure molecular sieve or described Second MFI structure molecular sieve.

As it has been described above, described first Y type molecular sieve is the DASY molecular sieve containing rare earth.Described containing dilute The DASY molecular sieve of soil refers to the hydro-thermal super stable molecular sieve containing rare earth, wherein, described containing rare earth With rare earth oxide (RE in DASY molecular sieve₂O₃) content of rare earth counted can be 1.5-3 weight %. The described DASY molecular sieve containing rare earth can be various commercially available prod, such as, can be purchased from Sinopec The DASY2.0 molecular sieve of catalyst asphalt in Shenli Refinery.

Described second Y type molecular sieve is REY molecular sieve.Described REY molecular sieve refers to Y-type rare earth Molecular sieve, it can be various commercially available REY zeolite products, such as, can be catalyzed purchased from Sinopec Agent asphalt in Shenli Refinery.

The content of rare earth counted with rare earth oxide in described 3rd Y type molecular sieve for 12-16 weight %, with P₂O₅The phosphorus content of meter is 0.5-7 weight %, this molecular sieve³¹In P MAS NMR spectra, chemical potential The peak area that shifting is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for the percent of total peak area and is more than 85%, this molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is the peak of 0 ± 2ppm resonance signal Area accounts for the percent of total peak area more than 20%.Preferably, with P in described 3rd Y type molecular sieve₂O₅ The phosphorus content of meter is 1-3 weight %.It is further preferred that described 3rd Y type molecular sieve³¹P MAS In H NMR spectroscopy, chemical shift is-14 ± 2ppm and the peak area of-23 ± 2ppm resonance signal accounts for face, total peak Long-pending percent is more than 90%.It is highly preferred that the lattice constant of described 3rd Y type molecular sieve is 24.55-24.70Additionally, described 3rd Y type molecular sieve can be according to well known to a person skilled in the art Various methods prepare, for example, it is possible to prepare with reference to the method disclosed in CN101088917A.

The x-ray diffraction spectra data of described first MFI structure molecular sieve are as shown in table 1 below:

Table 1

D value (× 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

In table 1, the relative intensity value represented by each symbol is as follows: VS:80-100%；S:60-80%； M:40-60%；W:20-40%；VW: < 20%.

Additionally, in described first MFI structure molecular sieve, rare earth is included in molecular sieve intracrystalline, wherein, Rare earth is from the faujasite seeds containing rare earth used when synthesizing described first MFI structure molecular sieve. In described first MFI structure molecular sieve, phosphorus aluminum chemistry in framework of molecular sieve is combined, and this is first years old MFI structure molecular sieve exists²⁷Al H NMR spectroscopy has corresponding to Al (4Si) coordination (i.e. Al is derived from and passes through Oxygen and four Si atoms form tetrahedral structures), chemical shift is the spectral peak of 55ppm, and has Have corresponding to Al (4P) coordination (i.e. Al atom is by oxygen and four P atoms formation tetrahedral structures), Chemical shift is the spectral peak of 39ppm；This first MFI structure molecular sieve exists³¹P H NMR spectroscopy then has (PO is i.e. there is corresponding to P (4Al) coordination₄Tetrahedron and adjacent AlO₄Tetrahedral interaction) , chemical shift be the spectral peak of-29ppm.Preferably, the phosphorus in described first MFI structure molecular sieve It is uniformly distributed in molecular sieve crystalline phase, is specifically reflected in: transmission electron microscope-energy dispersion spectrum (TEM-EDS) Analysis result show the phosphorus content during phosphorus content in any single crystal grain and molecular sieve are mutually Close.

Described first MFI structure molecular sieve is 4-5:1 to the absorption weight ratio of normal hexane Yu hexamethylene, Adsorption temp be 40 DEG C, adsorption time be 3 hours, absorption phase pressure P/P₀The condition of=0.20-0.25 Under, this first MFI structure molecular sieve is 98-105 milligrams per gram to the adsorbance of normal hexane, to hexamethylene Adsorbance be 20-25 milligrams per gram.This absorption weight ratio (4-5) is apparently higher than ZSM-5 zeolite Absorption weight ratio (2-2.5).

Additionally, described first MFI structure molecular sieve can be commercially available, it is also possible to according to this area Known to technical staff, various methods prepare, for example, it is possible to disclosed according to CN1147420A Method prepares.

The catalytic cracking catalyst provided according to the present invention, it is preferable that described second MFI structure molecule Sieve with the anhydrous chemical expression of the mass ratio range of oxide is (0-0.2)Na₂O·(0.9-5)Al₂O₃·(1.5-7)P₂O₅·(0.9-10)M1_m1O_n1·(0.5-2)M2_m2O_n2·(82-92)S iO₂, wherein, M1 is Fe, Co or Ni, and m1 represents the atomic number of M1, and n1 represents and meets M1 The number of oxidation state requisite oxygen, M2 is Zn, Mn, Ga or Sn, and m2 represents the atomic number of M2, N2 represents the number meeting M2 oxidation state requisite oxygen.It is particularly preferred that M1 is Fe, M2 is Zn.

Additionally, described second MFI structure molecular sieve can be commercially available, it is also possible to according to this area Known to technical staff, various methods prepare, for example, it is possible to disclosed according to CN1611299A Method prepares.

According to the present invention provide above-mentioned catalytic cracking catalyst, it is preferable that described metal M selected from IIB, During IIIB, IVB, VIIB race metal, the preferably mixing of a kind of or metal in Zn, Y, Ti, Mn, The mixing of the mixing of described various metals such as Ti and Mn, the mixing of Mn and Zn.Described metal M when lanthanide series rare-earth elements, preferably lanthanum, cerium or containing lanthanum and the mischmetal of cerium.According to this The above-mentioned catalytic cracking catalyst of bright offer, preferably metal M are Mg, Zn, Y, Ti, Mn, La Mixing with one or more in Ce.

The catalytic cracking catalyst provided according to the present invention, it is preferable that the ratio table of described mesoporous active materials Area is 300-450m²/ g, pore volume is 0.7-1.2cm³/ g, average pore size is 10-15nm.

The above-mentioned catalytic cracking catalyst provided according to the present invention, wherein mesoporous active materials is referred to existing Technique is had to be prepared, it is preferable that the most described mesoporous active materials is according to including following step Rapid method prepares:

(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11, Obtain plastic serosity；

(2) according to SiO₂: Al₂O₃=1:(0.6-9) weight ratio in described plastic serosity, add silicon Source, is aged 1-5 hour at room temperature to 90 DEG C, obtains the first solid sediment；

(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get oxidation The sodium content the second solid sediment less than 0.3%；

(4) described second solid sediment, phosphorus source and the compound of metal M, according to P₂O₅: M_xO_y: The precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): the weight ratio of 1 Contact processes, and product of contact is dried, wherein metal M selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements.

Specifically, described in above-mentioned steps (1), aluminum source can be existing various can be converted into oxygen Change the material of aluminum, for example, it is possible to one or more in aluminum nitrate, aluminum sulfate and aluminum chloride.

Described in above-mentioned steps (1), alkaline solution can be the existing various material presenting alkalescence, For example, it is possible to be selected from ammonia, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution one Plant or multiple.Wherein, the concentration of described alkaline solution can be the conventional selection of this area, does not makees at this Repeat.

Described in above-mentioned steps (2), silicon source can be the existing various thing that can be converted into silicon oxide Matter, for example, it is possible to selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, four propoxyl group One or more in silicon, four butoxy silicon and silicon oxide.

The present invention does not has described solid sediment contacts in above-mentioned steps (3) method processed with ammonium salt Have and limit especially, for example, it is possible to include described first solid sediment by its precipitate butt: ammonium Salt: H₂O=1:(0.1-1): the weight ratio of (5-30) swaps at room temperature to 100 DEG C.Wherein, The number of times of described contact can be 1-3 time, and each time of contact can specifically should with 0.5-1 hour The content of sodium oxide in the solid product obtained is made to be as the criterion less than 0.3 weight %.

Additionally, the kind of ammonium salt described in above-mentioned steps (3) can be the conventional selection of this area, example As, one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate can be selected from.

The method that described solid sediment contacts with acid solution is not had by the present invention in above-mentioned steps (3) Have and limit especially, for example, it is possible to include that described first solid sediment is by its precipitate butt: acid: H₂O=1:(0.03-0.3): the weight ratio of (5-30) exchanges at least 0.2 hour at room temperature to 100 DEG C.

Additionally, the kind of acid solution can be the conventional selection of this area in described above-mentioned steps (3), Usually mineral acid, such as, the acid in described acid solution can be selected from sulphuric acid, hydrogen chloride and nitric acid One or more.

By the contact of the compound of the second solid sediment, phosphorus source and metal M in above-mentioned steps (4) Processing procedure can have a various ways, such as following a), b), c), d) during any one:

A) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mix making beating with water, then the compound of phosphorus source and metal M is added sequentially in above-mentioned serosity, in room At warm to 90 DEG C, contact processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, more preferably contacts Process 0.5-3 hour, be dried 10-20 hour at 100 DEG C-150 DEG C after filtering washing；

B) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mixing making beating with water, then phosphorus source joined in above-mentioned serosity, at room temperature to 90 DEG C, contact processes at least 0.2 hour, preferably contact processed 0.2-5 hour, and more preferably contact processes 0.5-3 hour, straight after filtration Connect the compound with metal M to be mixed in proportion, at 100 DEG C-150 DEG C, after grinding uniformly, be dried 10-20 Hour；

C) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mix making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity, Room temperature to contact at 90 DEG C processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, more preferably connects Synapsis is managed 0.5-3 hour, obtains the 3rd solid sediment after filtration, then by direct for the 3rd solid sediment Mix with the second metal M, at 100 DEG C-150 DEG C, after grinding uniformly, be dried 10-20 hour, wherein, The compound of described the first metal M is identical or different with the compound of the second metal M；

D) described second solid sediment is directly mixed in proportion with phosphorus source and metal M compound, grinds It is dried 10-20 hour at 100 DEG C-150 DEG C after mill is uniform.

In aforesaid way c), for compound and the change of the second metal M of the first metal M Concrete material and the consumption of material included in compound do not have particular/special requirement, as long as enabling to institute State the second solid sediment and phosphorus source and the compound of metal M, be finally according to P₂O₅: M_xO_y: institute State precipitate butt=(0.005-0.1): (0.005-0.1) of the second solid sediment: the weight ratio of 1 is mixed Close.

Further, optionally, the preparation method of described mesoporous active materials can also include entering desciccate Row roasting, the condition of described roasting generally includes sintering temperature can be 500-700 DEG C, and roasting time can Think 1-4 hour.

Described in above-mentioned steps (4), the kind of phosphorus source can be the conventional selection of this area, such as, One or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid can be selected from.

Described in above-mentioned steps (4), the compound of metal M can be any one water miscible chemical combination Thing.

Described in above-mentioned steps (4), the compound of metal M is the nitrate of metal M, sulfate Or chloride.Such as, magnesium source can be selected from one or more in magnesium nitrate, magnesium chloride and magnesium sulfate.

Described clay can be the existing various clay that can be used in catalytic cracking catalyst, such as, Can be selected from Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, One or more in meerschaum, attapulgite, brucite and bentonite.

Described binding agent can be the existing various binding agent that can be used in catalytic cracking catalyst, example As, one or more in Ludox, Alumina gel and boehmite can be selected from.

The preparation method of catalytic cracking catalyst that the present invention provides include by above-mentioned cracking activity constituent element, in Hole active material, clay and binding agent mixing making beating, carry out the most successively being spray-dried, wash, mistake Filter and be dried.

The preparation method of catalytic cracking catalyst provided according to the present invention, by described cracking activity constituent element, Mesoporous active materials, clay and binding agent mixing making beating, and follow-up spray drying, wash, filter With dry, the implementation of these operations all can use the method for routine to implement, their specific embodiment party Rule as CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A have detailed description, introduce the most in the lump in the present invention with Make reference.Typically also, after described spray drying, before washing, described catalytic cracking is urged The preparation method of agent the most also includes the step that Spray dried products carries out roasting.The bar of described roasting Part generally includes sintering temperature can be 500-700 DEG C, and roasting time can be 1-4 hour.

Additionally, present invention also offers the application in RFCC of the above-mentioned catalytic cracking catalyst.

Hereinafter will be described the present invention by embodiment.

The raw material used in following preparation example, contrast preparation example, embodiment and comparative example is as follows:

Hydrochloric acid is produced by Beijing Chemical Plant, chemical pure, and concentration is 36 weight %；

Sodium silicate is commercially available, SiO₂Concentration is 26.0 weight %, and modulus is 3.2；

Kaolin is Kaolin of Suzhou Products, and solid content is 74.0 weight %；

Boehmite is Shandong Aluminum Plant's industrial products, and solid content is 62.0 weight %；

Alumina gel is Sinopec catalyst asphalt in Shenli Refinery product, Al₂O₃Content is 21.5 weight %；

First Y type molecular sieve is DASY2.0 molecular sieve, raw by Sinopec catalyst asphalt in Shenli Refinery Produce；

Second Y type molecular sieve is REY molecular sieve, Sinopec catalyst asphalt in Shenli Refinery produce；

3rd Y type molecular sieve prepares according to the method in CN101088917A embodiment 1；

First MFI structure molecular sieve prepares according to the method in CN1147420A embodiment 1；

Second MFI structure molecular sieve prepares according to the method in CN1611299A embodiment 1.

In following example and comparative example:

Specific surface area, pore volume and average pore size all use nitrogen absorption under low temperature-desorption method to be measured, and are adopted The physical and chemical adsorption instrument ASAP2400 that instrument is Micro meritics company of the U.S..Mesopore activity Na in material₂O、Al₂O₃、SiO₂、P₂O₅, MgO and metal-oxide (M_xO_y) content X (seeing " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui is fixed for ray fluorescence mensuration Compiling, Science Press, nineteen ninety publishes).

Preparation example 1

This preparation example is for illustrating phosphorus, metal-modified mesoporous silicon aluminum and the preparation thereof that the present invention provides Method.

(1) it is first 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, by dense under stirring Spending and add for 25wt.% ammonia, until system pH=10.0, keeping gelling temperature is 40 DEG C, collects meter Amount plastic serosity；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:3 is to becoming rubber cement Adding concentration in liquid is 60gSiO₂The waterglass of/L, is warming up to 80 DEG C and is aged 1 hour, obtain first solid Body precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H₂O=1:0.08: The weight ratio of 12 exchanges 30 minutes at 50 DEG C, and filtration washing obtains sodium oxide content and is less than 0.3% Second solid sediment；(4) by the second solid sediment by its precipitate butt: H₂O=1:10's Weight ratio mixes making beating with water, and presses P₂O₅: MgO:TiO₂: the precipitate of the second solid sediment The weight ratio of butt=0.075:0.017:0.012:1 is sequentially added into ammonium phosphate, magnesium nitrate and titanium sulfate, React 2 hours at 60 DEG C, be dried at 120 DEG C after filtering washing and within 10 hours, i.e. obtain the present invention and carry The phosphorus of confession, metal-modified mesoporous silicon aluminum.It is designated as A-1.

A-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element Analytical chemistry consists of 0.08Na₂O·74.2Al₂O₃·15.3SiO₂·7.3P₂O₅·1.5MgO·1.0TiO₂；Ratio Surface area 455m²/ g, pore volume 1.24cm³/ g, average pore size 10.9nm.

Preparation example 2

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, severe Property than be 2.5 NaAlO₂Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down Row mixing plastic, controlling system temperature is 40 DEG C, system pH=10.5, collects metering plastic serosity；(2) Under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.2 adds concentration in plastic serosity 100gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: HCl:H₂The weight ratio of O=1:0.08:15 Exchange 30 minutes at 60 DEG C, filter washing and obtain the sodium oxide content the second solid precipitation less than 0.3% Thing；(4) P is pressed₂O₅: TiO₂: MnO₂: the precipitate butt=0.015:0.035 of the second solid sediment: Second solid sediment is mixed by the weight ratio of 0.049:1 with ammonium dihydrogen phosphate, titanium sulfate and manganese chloride Close, be dried 15 hours at 120 DEG C after grinding uniformly, within 4 hours, i.e. obtain the present invention then at 600 DEG C of roastings The phosphorus provided, metal-modified mesoporous silicon aluminum.It is designated as A-2.

A-2 has boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its Elementary analytical chemistry consists of 0.17Na₂O·55.1Al₂O₃·34.4SiO₂·1.5P₂O₅ ·3.5TiO₂·4.9MnO₂；Specific surface area 312m²/ g, pore volume 0.87cm³/ g, average pore size 11.1nm.

Preparation example 3

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and the ammonia that concentration is 24wt.% are Reaction raw materials, uses and flows plastic mode, is stirred vigorously lower by Al₂(SO₄)₃Solution and ammonia mix Rubber polymer, controlling system temperature is 50 DEG C, system pH=9.5, collects metering plastic serosity；(2) and Under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.8 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: ammonium salt: H₂The weight ratio of O=1:1:12 exists Exchange 1 hour at 60 DEG C, filter washing and obtain the sodium oxide content the second solid sediment less than 0.3%； (4) by the precipitate butt of the second solid sediment: H₂The weight ratio of O=1:10 is by solid for gained second Body precipitate mixes making beating with water, and presses P₂O₅: Y₂O₃: the precipitate butt of the second solid sediment= The weight ratio of 0.038:0.032:1 adds phosphoric acid and yttrium nitrate solution mixes, anti-at 70 DEG C Answering 2 hours, filtration is dried at 120 DEG C after washing and within 15 hours, i.e. obtains the phosphorus of present invention offer, metal changes The mesoporous silicon aluminum of property.It is designated as A-3.

A-3 has boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its Elementary analytical chemistry consists of 0.12Na₂O·65.4Al₂O₃·27.2SiO₂·3.7P₂O₅·3.1Y₂O₃；Compare table Area 418m²/ g, pore volume 1.09cm³/ g, average pore size 10.4nm.

Preparation example 4

(1) it is 102gAl by concentration₂O₃/ L, Crater corrosion are 2.5NaAlO₂Solution is placed in beaker, stirs Mixing lower is 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Add, until system pH=8.5, keep plastic temperature Degree is 40 DEG C, collects metering plastic serosity；(2) according to SiO under stirring₂: Al₂O₃The weight of=1:2.1 It is 100gSiO that amount adds concentration than in plastic serosity₂The waterglass of/L, is warming up to 70 DEG C of ageings 2 little Time, obtain the first solid sediment；(3) by the first solid sediment by its precipitate butt: NH₄Cl: H₂The weight ratio of O=1:1:10 exchanges 1 hour at 60 DEG C, and it is low that filtration washing obtains sodium oxide content In second solid sediment of 0.3%；(4) by the second solid sediment by its precipitate butt: H₂O= The weight ratio of 1:8 mixes making beating with water, and presses P₂O₅: MgO:TiO₂: MnO₂: ZnO: the second The weight ratio of the precipitate butt=0.012:0.01:0.012:0.012:0.01:1 of solid sediment adds Enter phosphoric acid, magnesium nitrate, titanium sulfate, manganese chloride and zinc nitrate, react 2 hours at 70 DEG C, filter The phosphorus i.e. obtaining the present invention for 10 hours and providing, metal-modified mesoporous silicon aluminium are provided after washing at 120 DEG C Material.It is designated as A-4.

A-4 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its yuan Element analytical chemistry consists of 0.06Na₂O·68.2Al₂O₃·26.1SiO₂·1.1P₂O₅·0.9MgO·1.1TiO₂ ·1.2MnO₂·0.8ZnO；Specific surface area 408m²/ g, pore volume 1.03cm³/ g, average pore size 10.1nm.

Preparation example 5

(1) using concentration is 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/L、 Crater corrosion is the NaAlO of 2.5₂Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down Carrying out mixing plastic, controlling system temperature is 35 DEG C, system pH=9.5, collects metering plastic serosity, (2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 1 hour, obtain the first solid sediment；(3) After filtering washing, by the precipitate butt of the first solid sediment: ammonium salt: H₂The weight of O=1:1:10 Ratio and NH₄Cl and deionized water mixing, carry out ion exchange at 55 DEG C and obtain sodium oxide content and be less than Second solid sediment of 0.3%；(4) by the second solid sediment reslurry, and MgO is pressed: the The weight ratio of the precipitate butt=0.025:1 of two solid sediments adds magnesium nitrate, reacts 1 at 65 DEG C Hour, filter and be dried 10 hours in 120 DEG C, obtain the 3rd solid sediment；By the 3rd solid precipitation The precipitate butt of thing: P₂O₅: La₂O₃The weight ratio of=1:0.007:0.010 is by drying sample and nitre Acid magnesium and lanthanum chloride solution mixing, be dried 10 hours in 120 DEG C after grinding uniformly, then at 550 DEG C of roastings Within 2 hours, i.e. obtain phosphorus, metal-modified mesoporous silicon aluminum that the present invention provides.It is designated as A-5.

A-5 has boehmite phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its Elementary analytical chemistry consists of 0.13Na₂O·49.8Al₂O₃·45.6SiO₂·0.7P₂O₅·2.5MgO·1.0 La₂O₃；Specific surface area 360m²/ g, pore volume 0.93cm³/ g, average pore size 10.3nm.

Preparation example 6

(1) it is 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, and the lower addition of stirring is dense Degree is the ammonia of 25wt.%, until system pH=9.0, keeping gelling temperature is 40 DEG C, collects metering Plastic serosity；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:3 is to plastic serosity Middle addition concentration is 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 2 hours, obtain the first solid Precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H₂O=1:0.08: The weight ratio of 10 exchanges 1 hour at 50 DEG C, filters washing and obtains Na₂O content less than 0.3% the Two solid sediments；(4) by the second solid sediment reslurry and by the precipitation of the second solid sediment Thing butt: P₂O₅The weight ratio of=1:0.6 mixes with phosphoric acid, stirs 1 hour at 70 DEG C, filters also It is dried 10 hours in 120 DEG C, obtains the 3rd solid sediment；The 3rd solid sediment and the chlorine that will obtain Change rare earth (containing La and Ce) solution, by the precipitate butt of the 3rd solid sediment: RE₂O₃=1: The weight ratio of 5.5 with mix, be dried 10 hours in 120 DEG C after grinding uniformly, then at 550 DEG C of roastings 2 Hour i.e. obtain phosphorus, metal-modified mesoporous silicon aluminum that the present invention provides.It is designated as A-6.

A-6 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with special shown in Fig. 1 Levy；Its elementary analytical chemistry consists of 0.11Na₂O·72.4Al₂O₃·21.2SiO₂·0.6P₂O₅ ·5.3RE₂O₃；Specific surface area 396m²/ g, pore volume 0.96cm³/ g, average pore size 9.7nm.

Preparation example 7

(1) using concentration is 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, Crater corrosion is the NaAlO of 2.5₂Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down Carrying out mixing plastic, controlling system temperature is 35 DEG C, system pH=9.5, collects metering plastic serosity, (2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.3 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3) After filtering washing, by the precipitate butt of the first solid sediment: ammonium salt: H₂The weight of O=1:1:15 Ratio and NH₄Cl and deionized water mixing, carry out ion exchange at 65 DEG C and obtain sodium oxide content and be less than Second solid sediment of 0.3%；(4) P is pressed₂O₅: the precipitate of the MgO: the second solid sediment is done Second solid sediment is mixed by the weight ratio of base=0.015:0.035:1 with phosphoric acid and magnesium nitrate, Being dried 10 hours at 120 DEG C after grinding uniformly, within 2 hours, i.e. obtaining the present invention then at 600 DEG C of roastings provides Phosphorus, metal-modified mesoporous silicon aluminum.It is designated as A-7.

A-7 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element Analytical chemistry consists of 0.16Na₂O·55.4Al₂O₃·38.1SiO₂·1.5P₂O₅·3.5MgO；Specific surface area 329m2/g, pore volume 0.88cm3/g, average pore size 10.7nm.

Contrast preparation example 1

This contrast preparation example is used for mesoporous silicon aluminum and preparation method thereof is described.

Prepare mesoporous silicon aluminum according to the method for preparation example 1, except for the difference that, do not include step (4), But the product obtained after being directly dried 10 hours at 120 DEG C by the second solid sediment is as reference Mesoporous silicon aluminum, be designated as DA-1.

DA-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides Analysis chemical composition is 0.19Na₂O·81.9Al₂O₃·16.7SiO₂；Specific surface area 514m²/ g, pore volume 1.45 cm³/ g, average pore size 11.3nm.

Contrast preparation example 2

This contrast preparation example is for mesoporous silicon aluminum that P Modification is described and preparation method thereof.

Mesoporous silicon aluminum is prepared, except for the difference that, in step (4) not according to the method for preparation example 1 Add magnesium nitrate and titanium sulfate；Its precipitate butt: H will be pressed by second solid sediment₂O=1:10 Weight ratio mix making beating with water, and press P₂O₅: precipitate butt=0.075 of the second solid sediment: The weight ratio of 1 adds ammonium phosphate, reacts 2 hours at 60 DEG C, dry at 120 DEG C after filtering washing The product obtained after dry 10 hours, as the mesoporous silicon aluminum of the P Modification of reference, is designated as DA-2.

DA-2 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides Analysis chemical composition is 0.08Na₂O·76.6Al₂O₃·15.8SiO₂·7.3P₂O₅；Specific surface area 469m²/ g, Pore volume 1.31cm³/ g, average pore size 11.0nm.

Contrast preparation example 3

This contrast preparation example is used for metal-modified mesoporous silicon aluminum and preparation method thereof is described.

Mesoporous silicon aluminum is prepared, except for the difference that, in step (4) not according to the method for preparation example 1 Add ammonium phosphate；Its precipitate butt: H will be pressed by gained the second solid sediment₂The weight of O=1:10 Amount mixes making beating than with water, and presses MgO:TiO₂: precipitate butt=0.017 of the second solid sediment: The weight ratio of 0.012:1 adds magnesium nitrate and titanium sulfate, reacts 2 hours at 60 DEG C, filters washing After at 120 DEG C, be dried the product that obtains after the 10 hours metal-modified mesoporous silicon aluminium as reference Material, is designated as DA-3.

DA-3 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is similar to A-1；Its element divides Analysis chemical composition is 0.08Na₂O·77.2Al₂O₃·15.9SiO₂·1.5MgO·1.0TiO₂；Specific surface area 496 m²/ g, pore volume 1.38cm³/ g, average pore size 11.2nm.

Embodiment 1

Catalytic cracking catalyst that this embodiment provides for the present invention is described and preparation method thereof.

The boehmite of 19 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining Serosity in add hydrochloric acid peptization, acid aluminum ratio (weight ratio) be 0.20:1, then temperature is risen to 65 DEG C Being acidified 1 hour, (solid content is then to be separately added into the serosity of 28 parts by weight kaolin clay in terms of butt 25 weight %), the Alumina gel of 7 weight portions in terms of butt and 10 weight portions in terms of butt by making The phosphorus of standby example 1 preparation, the serosity (solid content is 18 weight %) of metal-modified mesoporous silicon aluminum A-1, Stir 20 minutes, be added thereto to a described Y type molecule of 5 weight portions in terms of butt the most again Sieve, described second Y type molecular sieve of 23 weight portions in terms of butt and 8 weight portions in terms of butt The mixed serum (solid content is 35 weight %) of described first MFI structure molecular sieve, sprays after continuing stirring Mist is dried makes microspherical catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then With (NH at 60 DEG C₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05: 1:10) to Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, the most again Dry at 110 DEG C, obtain catalytic cracking catalyst C1, wherein, with described catalytic cracking catalyst On the basis of the gross weight of C1, described catalytic cracking catalyst C1 contains the mesopore activity of 10 weight % Material, the Y type molecular sieve of 28 weight %, the MFI structure molecular sieve of 8 weight %, the height of 28 weight % Ridge soil, the Al of 26 weight %₂O₃Binding agent.

Comparative example 1

This comparative example is for catalytic cracking catalyst that reference is described and preparation method thereof.

Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1 Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 1 prepare Mesoporous silicon aluminum DA-1 replace, obtain reference catalytic cracking catalyst CB1, wherein, with described On the basis of the gross weight of reference catalytic cracking catalyst CB1, described reference catalytic cracking catalyst CB1 In containing the mesoporous silicon aluminum of 10 weight %, the Y type molecular sieve of 28 weight %, the MFI of 8 weight % Structure molecular screen, the Kaolin of 28 weight %, the Al of 26 weight %₂O₃Binding agent.

Comparative example 2

Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1 Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 2 prepare The mesoporous silicon aluminum DA-2 of P Modification replace, obtain reference catalytic cracking catalyst CB2, wherein, On the basis of the gross weight of described reference catalytic cracking catalyst CB2, described reference catalytic cracking is catalyzed Containing the mesoporous silicon aluminum of 10 weight %, the Y type molecular sieve of 28 weight %, 8 weight % in agent CB2 MFI structure molecular sieve, the Kaolin of 28 weight %, the Al of 26 weight %₂O₃Binding agent.

Comparative example 3

Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1 Standby phosphorus, metal-modified mesoporous silicon aluminum A-1 identical weight part by contrast preparation example 3 prepare Metal-modified mesoporous silicon aluminum DA-3 replace, obtain reference catalytic cracking catalyst CB3, its In, on the basis of the gross weight of described reference catalytic cracking catalyst CB3, described reference catalytic cracking In catalyst CB3 containing the mesoporous silicon aluminum of 10 weight %, the Y type molecular sieve of 28 weight %, 8 The MFI structure molecular sieve of weight %, the Kaolin of 28 weight %, the Al of 26 weight %₂O₃Binding agent.

Comparative example 4

Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, be added without phosphorus, metal Modified mesoporous silicon aluminum A-1, and by phosphorus, metal-modified mesoporous silicon aluminum A-1 with identical dry The Kaolin of basic weight amount substitutes, and obtains reference catalytic cracking catalyst CB4, wherein, urges with described reference On the basis of the gross weight of fluidized cracking catalysts CB4, described reference catalytic cracking catalyst CB4 contains The Y molecular sieve of 28 weight %, the MFI structure molecular sieve of 8 weight %, the Kaolin of 38 weight %, 26 The Al of weight %₂O₃Binding agent.

Embodiment 2

20 parts by weight kaolin clay in terms of butt are mixed making beating with deionized water, adds in terms of butt The boehmite of 20 weight portions, and in the serosity obtained, add hydrochloric acid peptization, acid aluminum ratio (weight Amount) it is 0.20:1, then temperature is risen to 65 DEG C and is acidified 1 hour, be then separately added in terms of butt The Alumina gel of 5 weight portions, the phosphorus prepared by preparation example 2 of 30 weight portions in terms of butt, metal The serosity (solid content is 20 weight %) of modified mesoporous silicon aluminum A-2, stirs 20 minutes, it After be added thereto to described first Y type molecular sieve of 5 weight portions in terms of butt again, in terms of butt Described 3rd Y type molecular sieve of 10 weight portions and described 2nd MFI of 10 weight portions in terms of butt The mixed serum (solid content is 35 weight %) of structure molecular screen, after continuing stirring, spray drying is made micro- Sphere catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then use at 60 DEG C (NH₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05:1:10) To Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, afterwards then at 110 DEG C Lower drying, obtains catalytic cracking catalyst C2, wherein, with the gross weight of described catalytic cracking catalyst C2 On the basis of amount, in described catalytic cracking catalyst C2 containing the mesoporous active materials of 30 weight %, 15 The Y type molecular sieve of weight %, the MFI structure molecular sieve of 10 weight %, the Kaolin of 20 weight %, The Al of 25 weight %₂O₃Binding agent.

Embodiment 3

28 parts by weight kaolin clay in terms of butt are mixed making beating with deionized water, adds in terms of butt The boehmite of 25 weight portions, and in the serosity obtained, add hydrochloric acid peptization, acid aluminum ratio (weight Amount) it is 0.20:1, then temperature is risen to 65 DEG C and is acidified 1 hour, be then separately added in terms of butt The phosphorus prepared by preparation example 3 of 20 weight portions, the serosity of metal-modified mesoporous silicon aluminum A-3 (solid content is 25 weight %), stirs 20 minutes, is added thereto to 10 weights in terms of butt the most again Described second Y type molecular sieve of amount part, described 3rd Y type molecular sieve of 9 weight portions in terms of butt, The described first MFI structure molecular sieve of 3 weight portions in terms of butt and the institute of 5 weight portions in terms of butt State the mixed serum (solid content is 35 weight %) of the second MFI structure molecular sieve, spray after continuing stirring It is dried and makes microspherical catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then at 60 DEG C Lower with (NH₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05:1: 10) to Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, afterwards then at Dry at 110 DEG C, obtain catalytic cracking catalyst C3, wherein, with described catalytic cracking catalyst C3 Gross weight on the basis of, in described catalytic cracking catalyst C3 containing 20 weight % mesoporous active materials, The Y type molecular sieve of 19 weight %, the MFI structure molecular sieve of 8 weight %, the Kaolin of 28 weight %, The Al of 25 weight %₂O₃Binding agent.

Embodiment 4

By the Alumina gel of the Kaolin of 40 weight portions in terms of butt and 15 weight portions in terms of butt and The phosphorus prepared by preparation example 4 of 15 weight portions in terms of butt, metal-modified mesoporous silicon aluminum A-4 Serosity (solid content is 20 weight %) mixing making beating, stir 120 minutes, add the most wherein Enter described 3rd Y type molecular sieve and the institute of 15 weight portions in terms of butt of 15 weight portions in terms of butt State the mixed serum (solid content is 35 weight %) of the second MFI structure molecular sieve, spray after continuing stirring It is dried and makes microspherical catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then at 60 DEG C Lower with (NH₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05:1: 10) to Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, afterwards then at Dry at 110 DEG C, obtain catalytic cracking catalyst C4, wherein, with described catalytic cracking catalyst C4 Gross weight on the basis of, in described catalytic cracking catalyst C4 containing 15 weight % mesoporous active materials, The Y type molecular sieve of 15 weight %, the MFI structure molecular sieve of 15 weight %, the Kaolin of 40 weight %, The Al of 15 weight %₂O₃Binding agent.

Embodiment 5

(1) Ludox is prepared:

1.7L hydrochloric acid 8.0kg decationized Y sieve water is diluted, by 7.7kg sodium silicate 8.0kg Decationized Y sieve water is diluted, and the sodium silicate diluted is slowly added under stirring above-mentioned hydrochloric acid weak solution In, obtain SiO₂Concentration be 7.8 weight %, pH value be the Ludox of 2.8.

(2) catalytic cracking catalyst is prepared:

The height of 10 weight portions in terms of butt is added in the above-mentioned Ludox of 20 weight portions in terms of butt Ridge soil, phosphorus, the metal prepared by preparation example 5 that add 40 weight portions in terms of butt after stirring 1h change Property mesoporous silicon aluminum A-5 serosity (solid content is 18 weight %) mixing making beating, the most again to Wherein add described first Y type molecular sieve of 10 weight portions in terms of butt, 5 weight in terms of butt Part described second Y type molecular sieve, described 3rd Y type molecular sieve of 12 weight portions in terms of butt and (solid content is 30 to the mixed serum of the described first MFI structure molecular sieve of 3 weight portions in terms of butt Weight %), it is spray-dried after continuing stirring and makes microspherical catalyst.Then by this microspherical catalyst at 60 DEG C Lower with (NH₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05:1: 10) to Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, afterwards then at Dry at 110 DEG C, obtain catalytic cracking catalyst C5, wherein, with described catalytic cracking catalyst C5 Gross weight on the basis of, in described catalytic cracking catalyst C5 containing 40 weight % mesoporous active materials, The Y type molecular sieve of 27 weight %, the MFI structure molecular sieve of 3 weight %, the Kaolin of 10 weight %, The SiO of 20 weight %₂Binding agent.

Embodiment 6

The boehmite of 18 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining Serosity in add hydrochloric acid peptization, acid aluminum ratio (weight) be 0.20:1, then temperature is risen to 65 DEG C Being acidified 1 hour, (solid content is then to be separately added into the serosity of 30 parts by weight kaolin clay in terms of butt 25 weight %), the Alumina gel of 7 weight portions in terms of butt and 5 weight portions in terms of butt by making The phosphorus of standby example 6 preparation, the serosity (solid content is 18 weight %) of metal-modified mesoporous silicon aluminum A-6, Stir 20 minutes, be added thereto to a described Y type molecule of 15 weight portions in terms of butt the most again Sieve, described second Y type molecular sieve of 15 weight portions in terms of butt and 10 weight portions in terms of butt The mixed serum (solid content is 35 weight %) of described second MFI structure molecular sieve, sprays after continuing stirring Mist is dried makes microspherical catalyst.Then by this microspherical catalyst roasting 1 hour at 500 DEG C, then With (NH at 60 DEG C₄)₂SO₄Solution washing (wherein, (NH₄)₂SO₄: microspherical catalyst: H₂O=0.05: 1:10) to Na₂O content is less than 0.25 weight %, then with deionized water drip washing and filter, the most again Dry at 110 DEG C, obtain catalytic cracking catalyst C6, wherein, with described catalytic cracking catalyst On the basis of the gross weight of C6, described catalytic cracking catalyst C6 contains the mesopore activity material of 5 weight % Material, the MFI structure molecular sieve of the Y type molecular sieve of 30 weight %, 10 weight %, the height of 30 weight % Ridge soil, the Al of 25 weight %₂O₃Binding agent.

Embodiment 7

Prepare catalytic cracking catalyst according to the method for embodiment 1, except for the difference that, will be made by preparation example 1 Standby phosphorus, the phosphorus prepared by preparation example 7 of metal-modified mesoporous silicon aluminum A-1 identical weight part, Metal-modified mesoporous silicon aluminum A-7 replaces, and obtains catalytic cracking catalyst C7, wherein, with institute On the basis of stating the gross weight of catalytic cracking catalyst C7, containing 10 in described catalytic cracking catalyst C7 The mesoporous active materials of weight %, the Y type molecular sieve of 28 weight %, the MFI structure molecule of 8 weight % Sieve, the Kaolin of 28 weight %, the Al of 26 weight %₂O₃Binding agent.

Embodiment 8-14

The test of the catalytic cracking catalyst performance that embodiment 8-14 provides for the present invention is described.

Respectively by the catalytic cracking catalyst C1-C7 of above-mentioned preparation 800 DEG C, the condition of 100% water vapour Under aging 17 hours, be filled in small fixed flowing bed ACE device (purchased from KTI company of the U.S.) afterwards In, amount of fill is each 9g.Then, reaction temperature be 500 DEG C, air speed be 16h^-1, agent oil weight Amount ratio for carrying out catalytic cracking reaction to the raw oil shown in table 2 under conditions of 6:1, reaction result arranges In table 3 and table 4.Wherein, coke selectivity refers to the ratio of coke yield and conversion ratio.

Comparative example 5-8

Comparative example 5-8 is for illustrating the test of the catalytic cracking catalyst performance of reference.

According to the method for embodiment 8-14, raw oil is carried out catalytic cracking reaction, except for the difference that, will urge Fluidized cracking catalysts C1-C7 respectively with the catalytic cracking catalyst CB1 of reference of identical weight part, CB2, CB3 and CB4 substitutes, and reaction result is shown in Table 3.

Table 2

Table 3

Table 4

The result explanation of table 3 and table 4, identical with zeolite content but without the catalyst of mesoporous active materials CB4 compares, and the catalyst that the present invention provides can be obviously improved the selectivity of coke, and vapour is greatly lowered Oil sulfur content, the most also has higher cracking activity；Identical with each constituent content but use without phosphorus and The catalyst CB1 of metal-modified mesoporous active materials compares, the coke of the catalyst that the present invention provides Productivity reduces, and coke selectivity is obviously improved, and content of sulfur in gasoline is greatly lowered；With respectively Constituent content is identical but uses the catalyst CB2 of the mesoporous active materials of P Modification to compare, and the present invention carries The content of sulfur in gasoline of the catalyst of confession is greatly lowered；Identical with each constituent content but use metal-modified The catalyst CB3 of mesoporous active materials compares, and the coke yield of the catalyst that the present invention provides reduces, Coke selectivity is obviously improved, and also has the effect preferably reducing content of sulfur in gasoline.

As can be seen here, the catalytic cracking catalyst that the present invention provides can during RFCC Show more preferable coke selectivity and higher catalytic cracking activity, can also obtain higher simultaneously Yield of liquefied gas and relatively low content of sulfur in gasoline.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims

1. a catalytic cracking catalyst, it is characterised in that with the gross weight of described catalytic cracking catalyst On the basis of amount, described catalytic cracking catalyst contains the cracking activity constituent element of 1-60 weight %, 1-50 weight % Mesoporous active materials, the clay of 1-70 weight % and the binding agent of 1-70 weight %；Described mesopore activity Material has boehmite crystal phase structure, with the mass ratio range of oxide in described mesoporous active materials Anhydrous chemical expression is: (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10) P₂O₅·(0.5-10)M_xO_y, wherein metal M selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, y is that metal M forms oxide Time maximum close valence state, and the numerical value of x and y makes the quantivalence of M and O balance, and described in The specific surface area of hole active material is 200-500m²/ g, pore volume is 0.5-1.5cm³/ g, average pore size is 8-18nm；

Described second Y type molecular sieve is REY molecular sieve；

Catalytic cracking catalyst the most according to claim 1, wherein, urges with described catalytic cracking On the basis of the gross weight of agent, described catalytic cracking catalyst contains the cracking activity group of 10-50 weight % Unit, the mesoporous active materials of 5-40 weight %, the clay of 10-60 weight % and the bonding of 10-60 weight % Agent.

Catalytic cracking catalyst the most according to claim 1, wherein, described mesoporous active materials Specific surface area be 300-450m²/ g, pore volume is 0.7-1.2cm³/ g, average pore size is 10-15nm.

Catalytic cracking catalyst the most according to claim 1, wherein said metal M be Mg, The mixing of one or more in Zn, Y, Ti, Mn, La and Ce.

5. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, described Mesoporous active materials prepares in accordance with the following methods:

(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get oxidation Sodium content is less than the second solid sediment of 0.3 weight %；

(4) by described second solid sediment, phosphorus source and the compound of metal M, according to P₂O₅: M_xO_y: the precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): 1 Weight ratio contact processes, and product of contact is dried.

Catalytic cracking catalyst the most according to claim 5, wherein, aluminum described in step (1) One or more in aluminum nitrate, aluminum sulfate and aluminum chloride of source；Described alkaline solution selected from ammonia, One or more in sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution.

Catalytic cracking catalyst the most according to claim 5, wherein, silicon described in step (2) Source is selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy One or more in silicon and silicon oxide.

Catalytic cracking catalyst the most according to claim 5, wherein, by described in step (3) It is by the first solid precipitation of step (2) gained that first solid sediment contacts the process processed with ammonium salt Thing is by its precipitate butt: ammonium salt: H₂O=1:(0.1-1): the weight ratio of (5-30) is in room temperature to 100 DEG C Lower exchange, until sodium oxide content is less than 0.3 weight % in solid sediment.

Catalytic cracking catalyst the most according to claim 5, wherein, ammonium described in step (3) One or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate of salt.

Catalytic cracking catalyst the most according to claim 5, wherein, by institute in step (3) State the first solid sediment and contact the process processed with acid solution, be solid by the first of step (2) gained Body precipitate presses its precipitate butt: acid: H₂O=1:(0.03-0.30): the weight ratio of (5-30) exists Room temperature at least exchanges 0.2 hour at 100 DEG C.

11. catalytic cracking catalysts according to claim 5, wherein, described in step (3) One or more in sulphuric acid, hydrogen chloride and nitric acid of acid in acid solution.

12. catalytic cracking catalysts according to claim 5, wherein, by institute in step (4) State the second solid sediment, phosphorus source contacts processing procedure with the compound of metal M, selected from following a), b), C), d) during one:

A) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mix making beating with water, then the compound of phosphorus source and metal M is added sequentially in above-mentioned serosity, in room At warm to 90 DEG C, contact processes at least 0.2 hour, is dried 10-20 after filtering washing at 100 DEG C-150 DEG C Hour；

B) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mixing making beating with water, then phosphorus source joined in above-mentioned serosity, at room temperature to 90 DEG C, contact processes at least 0.2 hour, after filtration, the direct compound with metal M was mixed in proportion, at 100 DEG C after grinding uniformly It is dried 10-20 hour at-150 DEG C；

C) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight ratio Mix making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity, Room temperature processes at least 0.2 hour to contact at 90 DEG C, obtains the 3rd solid sediment after filtration, then by the Three solid sediments directly mix with the compound of the second metal M, at 100 DEG C after grinding uniformly 10-20 hour, wherein, the compound of described the first metal M and the second metal it is dried at-150 DEG C The compound of M is identical or different；

D) direct for described second solid sediment and phosphorus source and genus M compound is mixed in proportion, grinds It is dried 10-20 hour at 100 DEG C-150 DEG C after mill is uniform.

13. catalytic cracking catalysts according to claim 5, wherein, described in step (4) Drying steps after, also include gained desciccate roasting 1-4 hour at 500 DEG C-700 DEG C.

14. catalytic cracking catalysts according to claim 5, wherein, described in step (4) One or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid of phosphorus source.

15. catalytic cracking catalysts according to claim 5, wherein, described in step (4) The compound of metal M is water miscible compound.

16. catalytic cracking catalysts according to claim 5, wherein, described in step (4) The compound of metal M be the nitrate of metal M, sulfate or chloride.

17. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, with institute On the basis of stating the gross weight of cracking activity constituent element, described cracking activity constituent element contains the of 65-86 weight % A part screen banks divides the second molecular sieve component with 14-35 weight %.

18. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, described First molecular sieve component is described first Y type molecular sieve, described second Y type molecular sieve and described 3rd Y The mixture of at least two in type molecular sieve, described second molecular sieve component is described first MFI structure Molecular sieve or described second MFI structure molecular sieve.

The preparation method of catalytic cracking catalyst described in any one in 19. claim 1-18, should Method includes the mixing making beating of described cracking activity constituent element, mesoporous active materials, clay and binding agent, so After carry out the most successively being spray-dried, wash, filter and being dried.

In 20. claim 1-18, the catalytic cracking catalyst described in any one is at RFCC In application.