CN106179475B

CN106179475B - A kind of catalytic cracking catalyst and its preparation method and application

Info

Publication number: CN106179475B
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: 2018-07-31
Anticipated expiration: 2035-04-29
Also published as: CN106179475A

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, catalytic cracking catalyst 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)M_xO_y, 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 in heavy oil catalytic cracking, and can obtain higher yield of liquefied gas and lower 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 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)M_xO_y, 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 a kind of new to have lower coke selectivity, compared with high cracking activity, higher Yield of liquefied gas, 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)M_xO_y, 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；

With the total weight benchmark of the cracking activity constituent element, the cracking activity constituent element contains the first of 50-95 weight % Second molecular sieve component of molecular sieve component and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, second One or more in Y type molecular sieve and third Y type molecular sieve, second molecular sieve component is the first MFI structure molecular sieve And/or the second MFI structure molecular sieve；

First Y type molecular sieve is the DASY molecular sieves containing rare earth；

Second Y type molecular sieve is REY molecular sieves；

Content of rare earth in the third Y type molecular sieve in terms of rare earth oxide is 12-16 weight %, with P₂O₅The phosphorus of meter Content is 0.5-7 weight %, the molecular sieve³¹In P MAS NMR spectras, chemical shift is that -14 ± 2ppm and -23 ± 2ppm are total Shake signal peak area account for total peak area percentage be more than 85%, the molecular sieve²⁷In Al MAS NMR spectras, chemical shift The percentage of total peak area is accounted for more than 20% for the peak area of 0 ± 2ppm resonance signals；

It is with the anhydrous chemical expression of the molar ratio computing of oxide in the first 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 Absorption weight ratio with hexamethylene is 4-5：1；

It is with the anhydrous chemical expression of the weight ratio meter of oxide in the second MFI structure molecular sieve：(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, In, M1 Fe, Co or Ni, x indicate the atomicity of M1, and y indicates to meet the numbers of M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or Sn, m indicate that the atomicity of M2, n indicate the number for meeting M2 oxidation state requisite oxygens.

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 Show lower coke selectivity and higher catalytic cracking activity, and can also obtain higher yield of liquefied gas and Lower content of sulfur in 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)M_xO_y, 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；

On the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains the of 50-95 weight % Second molecular sieve component of one molecular sieve component and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, the One or more in two Y type molecular sieves and third Y type molecular sieve, second molecular sieve component is the first MFI structure molecule Sieve and/or the second MFI structure molecular sieve；

Second Y type molecular sieve is REY molecular sieves；

It is with the anhydrous chemical expression of the weight ratio meter of oxide in the second MFI structure molecular sieve：(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 Fe, Co or Ni, m1 indicate the atomicity of M1, and n1 indicates to meet the numbers of M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or Sn, m2 indicate that the atomicity of M2, n2 indicate the number for meeting M2 oxidation state requisite oxygens.

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)M_xO_y。

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, in order to enable the first molecular sieve component and the second molecular sieve Component can play the role of better coordinated, it is preferable that described to split on the basis of the total weight of the cracking activity constituent element Change the second molecular sieve component of the first molecular sieve component and 14-35 weight % that active component contains 65-86 weight %.

According to above-mentioned catalytic cracking catalyst provided by the invention, it is preferable that first molecular sieve component is described the At least two mixture in one Y type molecular sieve, second Y type molecular sieve and the third Y type molecular sieve, described second Molecular sieve component is the first MFI structure molecular sieve or the second MFI structure molecular sieve.

As described above, first Y type molecular sieve is the DASY molecular sieves containing rare earth.The DASY molecular sieves containing rare earth Refer to the hydro-thermal super stable molecular sieve containing rare earth, wherein with rare earth oxide (RE in the DASY molecular sieves containing rare earth₂O₃) meter Content of rare earth can be 1.5-3 weight %.The DASY molecular sieves containing rare earth can be various commercial product, such as can be with For the DASY2.0 molecular sieves purchased from Sinopec catalyst asphalt in Shenli Refinery.

Second Y type molecular sieve is REY molecular sieves.The REY molecular sieves refer to rare earth Y type molecular sieve, can be Various commercially available REY zeolite products, such as Sinopec catalyst asphalt in Shenli Refinery can be purchased from.

Content of rare earth in the third Y type molecular sieve in terms of rare earth oxide is 12-16 weight %, with P₂O₅The phosphorus of meter Content is 0.5-7 weight %, the molecular sieve³¹In P MAS NMR spectras, chemical shift is that -14 ± 2ppm and -23 ± 2ppm are total Shake signal peak area account for total peak area percentage be more than 85%, the molecular sieve²⁷In Al MAS H NMR spectroscopies, chemical shift is The percentage that the peak area of 0 ± 2ppm resonance signals accounts for total peak area is more than 20%.Preferably, in the third Y type molecular sieve With P₂O₅The phosphorus content of meter is 1-3 weight %.It is further preferred that the third Y type molecular sieve³¹In P MAS H NMR spectroscopies, change Displacement study is -14 ± 2ppm and the peak area of -23 ± 2ppm resonance signals accounts for the percentage of total peak area more than 90%.More preferably The lattice constant on ground, the third Y type molecular sieve is 24.55-24.70In addition, the third Y type molecular sieve can be according to Well known to a person skilled in the art various methods to be prepared, for example, being referred to method system disclosed in CN101088917A It is standby to obtain.

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

Table 1

D values (× 10^-1Nanometer)	Relative intensity value (I/I₀)
		11.2±0.2	VS

10.1±0.2	M
		9.8±0.2	VW
3.85±0.04	VS
		3.81±0.04	S
3.75±0.04	W
		3.72±0.04	M
3.65±0.04	M
		3.60±0.04	W

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

In addition, in the first MFI structure molecular sieve, it is transgranular that rare earth is included in molecular sieve, wherein rare earth is from synthesis The used faujasite seeds containing rare earth when the first MFI structure molecular sieve.In the first MFI structure molecular sieve In, phosphorus is combined with the aluminum chemistry in framework of molecular sieve, which exists²⁷Have in Al H NMR spectroscopies and corresponds to Al Spectral peak that (4Si) is coordinated (i.e. Al is originated from forms tetrahedral structures by oxygen and four Si atoms), that chemical shift is 55ppm, And it is coordinated (i.e. Al atoms pass through oxygen and four P atoms form tetrahedral structures), chemical shift with Al (4P) is corresponded to For the spectral peak of 39ppm；The first MFI structure molecular sieve exists³¹In P H NMR spectroscopies then have correspond to P (4Al) coordination (i.e. there is PO₄Tetrahedron and adjacent AlO₄Tetrahedral interaction), chemical shift be -29ppm spectral peak.Preferably, described first Phosphorus in MFI structure molecular sieve is uniformly distributed in molecular sieve crystalline phase, is specifically reflected in：Transmission electron microscope-energy dispersive spectrum (TEM- EDS analysis result) shows that the phosphorus content in arbitrary single crystal grain is close with the phosphorus content in molecular sieve phase.

The first MFI structure molecular sieve is 4-5 to the absorption weight ratio of n-hexane and hexamethylene：1, be in adsorption temp 40 DEG C, adsorption time be 3 hours, absorption phase pressure P/P₀Under conditions of=0.20-0.25, the first MFI structure molecular sieve pair The adsorbance of n-hexane is 98-105 milligrams per grams, and the adsorbance to hexamethylene is 20-25 milligrams per grams.The absorption weight ratio (4-5) is apparently higher than the absorption weight ratio (2-2.5) of ZSM-5 zeolite.

In addition, the first MFI structure molecular sieve can be commercially available, it can also be according to those skilled in the art's public affairs The various methods known are prepared, for example, can be prepared according to method disclosed in CN1147420A.

According to catalytic cracking catalyst provided by the invention, it is preferable that the second MFI structure molecular sieve is with oxide The anhydrous chemical expression of weight ratio meter is (0-0.2) Na₂O·(0.9-5)Al₂O₃·(1.5-7)P₂O₅·(0.9-10) M1_m1O_n1·(0.5-2)M2_m2O_n2·(82-92)S iO₂, wherein M1 Fe, Co or Ni, m1 indicate that the atomicity of M1, n1 indicate Meet the number of M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or Sn, m2 indicates that the atomicity of M2, n2 expressions meet M2 oxidation state The number of requisite oxygen.It is particularly preferred that M1 is Fe, M2 Zn.

In addition, the second MFI structure molecular sieve can be commercially available, it can also be according to those skilled in the art's public affairs The various methods known are prepared, for example, can be prepared according to method disclosed in CN1611299A.

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, the preferably mixing of one kind in Zn, Y, Ti, Mn or metal, 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 catalytic cracking catalyst provided by the invention, it is preferable that 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.

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) second solid sediment, phosphorus source and metal M compound, according to P₂O₅：M_xO_y：Second solid is heavy The sediment butt of starch=(0.005-0.1)：(0.005-0.1)：1 weight ratio contact treatment, and product of contact is dried, Wherein metal M be selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race's elements and one kind in lanthanide series rare-earth elements or It is a variety of.

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 solid sediment and the method for ammonium salt contact treatment particularly in above-mentioned steps (3) It is fixed, for example, may include by first solid sediment by its sediment butt：Ammonium salt：H₂O=1：(0.1-1)：(5-30) Weight ratio in room temperature to swapping at 100 DEG C.Wherein, the number of the contact can be 1-3 times, each time of contact Can be with 0.5-1 hours, the content of sodium oxide molybdena is less than subject to 0.3 weight % in the solid product that should specifically make.

In addition, the type of ammonium salt described in above-mentioned steps (3) can be the conventional selection of this field, for example, can be selected from It is one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.

The present invention is not to limiting the method that the solid sediment is contacted with acid solution particularly in above-mentioned steps (3) It is fixed, for example, may include first solid sediment by its sediment butt：Acid：H₂O=1：(0.03-0.3)：(5-30) Weight ratio in room temperature to exchanging at least 0.2 hour at 100 DEG C.

In addition, the type of acid solution can be the conventional selection of this field in the above-mentioned steps (3), 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 P₂O₅：M_xO_y：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.

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.

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.

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 are mixed with beating and subsequent spray drying, washing, filtering and dry, the embodiment party of these processes Method can be used conventional method and implement, their specific implementation method for example CN1916166A, CN1098130A, There is detailed description in CN1362472A, CN1727442A, CN1132898C and CN1727445A, introduces this hair together here In bright by reference.Typically also, after the spray drying, before washing, the preparation of the catalytic cracking catalyst Method also typically includes the step of being roasted Spray dried products.The condition of the roasting generally includes calcination temperature can be with It it is 500-700 DEG C, 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 is DASY2.0 molecular sieves, is produced by Sinopec catalyst asphalt in Shenli Refinery；

Second Y type molecular sieve is REY molecular sieves, is produced by Sinopec catalyst asphalt in Shenli Refinery；

Third Y type molecular sieve is made according to the method in CN101088917A embodiments 1；

First MFI structure molecular sieve is made according to the method in CN1147420A embodiments 1；

Second MFI structure molecular sieve is made according to the method in CN1611299A embodiments 1.

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 (M_xO_y) 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

(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

(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

(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

(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 molten by drying sample and magnesium nitrate and lanthanum chloride Liquid mixes, 10 hours dry in 120 DEG C after grinding uniformly, and 2 hours are roasted then at 550 DEG C up to phosphorus provided by the invention, metal Modified mesoporous silica-alumina material.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

(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 La and Ce) solution, by the sediment butt of third solid sediment： RE₂O₃=1：5.5 weight ratio with mix, it is 10 hours dry in 120 DEG C after grinding uniformly, then at 550 DEG C of roastings 2 hours to obtain the final product 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

(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 19 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, 7 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 %), stir 20 minutes, be added thereto again later 5 parts by weight in terms of butt first Y type molecular sieve, Second Y type molecular sieve of 23 parts by weight in terms of butt and the first MFI structure molecule of 8 parts by weight in terms of butt The mixed serum (solid content is 35 weight %) of sieve, 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 of 28 weight %, 8 weight % The Al of MFI structure molecular sieve, the kaolin of 28 weight %, 26 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 the Y type molecular sieve of mesoporous silica-alumina material, 28 weight % containing 10 weight % in catalytic cracking catalyst CB1,8 weight % The Al of MFI structure molecular sieve, the kaolin of 28 weight %, 26 weight %₂O₃Binder.

Comparative example 2

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 mesoporous silica-alumina material containing 10 weight % in the reference catalytic cracking catalyst CB2,28 weight % Y type molecular sieve, The Al of the MFI structure molecular sieve of 8 weight %, the kaolin of 28 weight %, 26 weight %₂O₃Binder.

Comparative example 3

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 Y type molecules of the mesoporous silica-alumina material containing 10 weight %, 28 weight % in the reference catalytic cracking catalyst CB3 The Al of sieve, the MFI structure molecular sieve of 8 weight %, the kaolin of 28 weight %, 26 weight %₂O₃Binder.

Comparative example 4

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 MFI structure molecular sieve of Y molecular sieve, 8 weight % containing 28 weight % in fluidized cracking catalysts CB4, the kaolinite of 38 weight % The Al of soil, 26 weight %₂O₃Binder.

Embodiment 2

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 Be added thereto again afterwards first Y type molecular sieve of 5 parts by weight in terms of butt, 10 parts by weight in terms of butt described (solid content is 35 weights to the mixed serum of three Y type molecular sieves and the second MFI structure molecular sieve of 10 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 C2, wherein on the basis of the total weight of the catalytic cracking catalyst C2, contain 30 in the catalytic cracking catalyst C2 The height of the mesoporous active materials of weight %, the Y type molecular sieve of 15 weight %, the MFI structure molecular sieve of 10 weight %, 20 weight % The Al of ridge soil, 25 weight %₂O₃Binder.

Embodiment 3

28 parts by weight kaolin clay in terms of butt are mixed with beating with deionized water, add 25 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 10 in terms of butt thereto again later Second Y type molecular sieve of parts by weight, the third Y type molecular sieve of 9 parts by weight in terms of butt, 3 weights in terms of butt Measure the mixing slurry of the first MFI structure molecular sieve of part and the second MFI structure molecular sieve of 5 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 C3, wherein on the basis of the total weight of the catalytic cracking catalyst C3, the catalysis is split Change the MFI structure point of the mesoporous active materials containing 20 weight % in catalyst C3, the Y type molecular sieve of 19 weight %, 8 weight % The Al of son sieve, the kaolin of 28 weight %, 25 weight %₂O₃Binder.

Embodiment 4

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, the 3rd Y type molecules of 15 parts by weight in terms of butt is added thereto again later The mixed serum (solid content is 35 weight %) of sieve and the second MFI structure molecular sieve of 15 parts by weight in terms of butt, after Microspherical catalyst is made in spray drying after continuous stirring.Then the microspherical catalyst is roasted 1 hour at 500 DEG C, then at 60 DEG C It is lower to use (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 C4 is obtained, Wherein, on the basis of the total weight of the catalytic cracking catalyst C4,15 weight % are contained in the catalytic cracking catalyst C4 Mesoporous active materials, the Y type molecular sieve of 15 weight %, the MFI structure molecular sieve of 15 weight %, 40 weight % kaolin, The Al of 15 weight %₂O₃Binder.

Embodiment 5

(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 the first Y types point of 10 parts by weight in terms of butt are added thereto again later The 3rd Y type molecules of son sieve, second Y type molecular sieve of 5 parts by weight in terms of butt, 12 parts by weight in terms of butt The mixed serum (solid content is 30 weight %) of sieve and the first MFI structure molecular sieve of 3 parts by weight in terms of butt, continues Microspherical catalyst is made in spray drying after stirring.Then the microspherical catalyst is used to (NH at 60 DEG C₄)₂SO₄Solution washs (its In, (NH₄)₂SO₄：Microspherical catalyst：H₂O=0.05：1：10) to Na₂O content is less than 0.25 weight %, then uses deionized water It elutes and filters, dried at 110 DEG C later, obtain catalytic cracking catalyst C5, wherein with the catalytic cracking catalyst On the basis of the total weight of C5, the Y of mesoporous active materials, 27 weight % containing 40 weight % in the catalytic cracking catalyst C5 The SiO of type molecular sieve, the MFI structure molecular sieve of 3 weight %, the kaolin of 10 weight %, 20 weight %₂Binder.

Embodiment 6

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, first Y type molecular sieve of 15 parts by weight in terms of butt is added thereto again later, with dry Second Y type molecular sieve of 15 parts by weight of base meter and the second MFI structure molecular sieve of 10 parts by weight in terms of butt Mixed serum (solid content be 35 weight %), after continuing stirring spray drying microspherical catalyst is made.Then the microballoon is urged Agent roasts 1 hour at 500 DEG C, then (NH is used at 60 DEG C₄)₂SO₄Solution washs (wherein, (NH₄)₂SO₄：Microspherical catalyst： H₂O=0.05：1：10) to Na₂O content is less than 0.25 weight %, is then eluted and is filtered with deionized water, later then at 110 DEG C Lower drying, obtains catalytic cracking catalyst C6, wherein described to urge on the basis of the total weight of the catalytic cracking catalyst C6 The Y type molecular sieve of mesoporous active materials, 30 weight % containing 5 weight % in fluidized cracking catalysts C6, the MFI knots of 10 weight % The Al of structure molecular sieve, the kaolin of 30 weight %, 25 weight %₂O₃Binder.

Embodiment 7

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 of mesoporous active materials, 28 weight % containing 10 weight % in Cracking catalyst C7, the MFI structure of 8 weight % The Al of molecular sieve, the kaolin of 28 weight %, 26 weight %₂O₃Binder.

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 2 is carried out under conditions of 1 Catalytic cracking reaction, reaction result are listed 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 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 3.

Table 2

Table 3

Table 4

The result of table 3 and table 4 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 be shown more during heavy oil catalytic cracking Good coke selectivity and higher catalytic cracking activity, while higher yield of liquefied gas and lower vapour can also 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

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)M_xO_y, 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；

On the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains first point of 50-95 weight % Second molecular sieve component of sub- screen banks point and 5-50 weight %, first molecular sieve component are the first Y type molecular sieve, the 2nd Y One or more in type molecular sieve and third Y type molecular sieve, second molecular sieve component is the first MFI structure molecular sieve And/or the second MFI structure molecular sieve；

Second Y type molecular sieve is REY molecular sieves；

Content of rare earth in the third Y type molecular sieve in terms of rare earth oxide is 12-16 weight %, with P₂O₅The phosphorus content of meter For 0.5-7 weight %, the molecular sieve³¹In P MAS NMR spectras, chemical shift is -14 ± 2ppm and -23 ± 2ppm resonance letters Number peak area account for total peak area percentage be more than 85%, the molecular sieve²⁷In Al MAS NMR spectras, chemical shift 0 The percentage that the peak area of ± 2ppm resonance signals accounts for total peak area is more than 20%；

It is with the anhydrous chemical expression of the molar ratio computing of oxide in the first 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；

It is with the anhydrous chemical expression of the weight ratio meter of oxide in the second MFI structure molecular sieve：(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 indicates the atomicity of M1, and n1 indicates to meet the numbers of M1 oxidation state requisite oxygens, M2 Zn, Mn, Ga or Sn, m2 indicate that the atomicity of M2, n2 indicate the number for meeting M2 oxidation state requisite oxygens.

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 in Mg, Zn, Y, Ti, Mn, La and Ce 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：M_xO_y：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 compound contact treatment process of phosphorus source and metal M, 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) second solid sediment is directly mixed with the compound of phosphorus source and category M in proportion, 100 after grinding uniformly It is 10-20 hours dry at DEG C -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 described in step (4) The compound of dissolubility.

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 with the cracking activity constituent element Total weight on the basis of, the cracking activity constituent element contains the first molecular sieve component and 14-35 weight % of 65-86 weight % Second molecular sieve component.

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

19. the preparation method of the catalytic cracking catalyst described in any one of claim 1-18, 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.

20. application of the catalytic cracking catalyst described in any one of claim 1-18 in heavy oil catalytic cracking.