CN107970995B

CN107970995B - Catalytic cracking catalyst and preparation method thereof

Info

Publication number: CN107970995B
Application number: CN201610919784.7A
Authority: CN
Inventors: 王丽霞; 田辉平; 刘宇键; 周翔; 袁帅; 刘俊; 张杰潇
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: 2016-10-21
Filing date: 2016-10-21
Publication date: 2020-03-24
Anticipated expiration: 2036-10-21
Also published as: CN107970995A

Abstract

一种催化裂解催化剂及其制备方法，该催化剂包括5～65％的天然矿物质、10～60％的氧化物粘结剂、24～75％的IMF结构分子筛、0.1％～15％的磷添加剂；该催化剂的介孔质子酸量占总酸量的比例为20～70％。所述催化剂的制备方法包括形成包括IMF结构分子筛、天然矿物质、无机氧化物粘结剂的浆液，喷雾干燥，用碱和复合酸处理和引入磷添加剂的步骤。所述催化裂解催化剂用于石油烃催化裂解具有更高的丙烯产率和BTX产率。A catalytic cracking catalyst and a preparation method thereof, the catalyst comprises 5-65% of natural minerals, 10-60% of oxide binder, 24-75% of IMF structure molecular sieve, and 0.1-15% of phosphorus additive ; The ratio of the mesoporous proton acid amount of the catalyst to the total acid amount is 20-70%. The preparation method of the catalyst includes the steps of forming a slurry including IMF structure molecular sieve, natural minerals, inorganic oxide binder, spray drying, treating with alkali and complex acid and introducing phosphorus additive. The catalytic cracking catalyst used in the catalytic cracking of petroleum hydrocarbons has higher propylene yield and BTX yield.

Description

Catalytic cracking catalyst and preparation method thereof

Technical Field

The invention relates to a catalytic cracking catalyst, a preparation method and application thereof.

Background

The low-carbon olefin such as ethylene, propylene, butylene and the like is an essential chemical raw material and can be used for synthesizing resin, fiber, rubber and the like. Propylene is an important raw material for manufacturing petrochemical products, which is second only to ethylene, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide and the like. At present, propylene is mainly derived from the by-product of ethylene production by thermal cracking at home and abroad, and the second largest source of propylene is the FCC unit, which provides about 30% of the demand, and in the united states, the FCC unit provides half of the demand of propylene for petrochemical products.

In recent years, the demand for propylene has increased rapidly, and by the prediction of HIS, the global propylene consumption has increased by 2016 at an average rate of about 5% which is greater than the rate of ethylene increase by 3.4%. However, the steam cracking propylene/ethylene ratio cannot be flexibly adjusted. And the reaction temperature is up to 840-860 ℃, and the energy consumption accounts for about 40% of the energy consumption of the petrochemical industry. Thus, the large production of propylene by FCC is an effective and efficient way to meet the growing demand.

The IM-5 molecular sieve is a shape-selective molecular sieve with an IMF structure, the structure of the molecular sieve is composed of a two-dimensional ten-membered ring channel and a plurality of three-dimensional characteristic cavities, and the diameter of the channel is similar to that of ZSM-5. The catalyst has a pore channel structure similar to that of a ZSM-5 molecular sieve, and has higher acid content and better hydrothermal stability, so that the catalyst is excellent in a plurality of catalytic reactions.

The CN104117385A modifies the IM-5 molecular sieve by noble metal, phosphorus and silicon, and then is used for toluene methylation reaction, and has better activity stability, xylene selectivity and p-xylene selectivity.

CN105018128A describes a catalyst for preparing the high octane gasoline component. The catalyst consists of a phosphorus-containing IM-5 molecular sieve and an optional binder, wherein P is used in the phosphorus-containing IM-5 molecular sieve₂O₅The calculated phosphorus content is 1-10%. The catalyst can be used for producing gasoline high-octane value components by reacting benzene and methanol.

CN104117384A proposes a toluene methylation catalyst and a preparation method thereof, and the catalyst composed of P and rare earth element modified IM-5 molecular sieve and a binder has high activity stability and P-xylene selectivity when used in toluene methanol alkylation reaction.

However, in the existing catalytic cracking catalyst containing the molecular sieve with the IMF structure, in the catalytic cracking reaction of larger hydrocarbon molecules such as heavy oil, the activity of the catalyst and the selectivity of the target product are poor, such as the yield of propylene is not high, and the prior art does not disclose how to further improve the yield of propylene of the catalyst containing the molecular sieve with the IMF structure.

Disclosure of Invention

One of the technical problems to be solved by the invention is to provide a fluidized bed catalytic cracking catalyst, which contains an IMF structure molecular sieve, has excellent hydrothermal stability, and has higher propylene yield when being used for hydrocarbon oil conversion.

The invention provides a catalytic cracking catalyst, which comprises (a) 5-65% of natural mineral substances in dry basis by taking the weight of the catalyst as a reference; (b) 10% -60% of oxide; and (c) 24% to 75% on a dry basis of a first molecular sieve, the first molecular sieve being an IMF structure molecular sieve; and D) with P₂O₅0.1 to 15 percent of phosphorus additive; the proportion of the mesoporous protonic acid amount of the catalytic cracking catalyst in the total acid amount is 20-70%, for example 25-65%. The total specific surface area of the catalyst is preferably greater than 240m²/g。

Preferably, the proportion of the mesopore volume of the catalytic cracking catalyst in the total pore volume is 35-60%, for example 40-60%, or 45-58%, or 35-45%. The mesoporous volume of the catalyst is 0.14-0.35 ml/g, such as 0.15-0.30 ml/g. The mesoporous is a pore with the pore diameter of 2-100 nm.

Preferably, the total specific surface area (also called specific surface area) of the catalytic cracking catalyst is 240-350 m²A/g, for example, of 250 to 320m²/g。

The catalytic cracking catalyst provided by the invention has more mesoporous protonic acid, and the proportion of the mesoporous protonic acid in the total acid amount is 20-70%, such as 25-65%, preferably, such as 25-50% or 30-55%.

The mesoporous pore volume and the total pore volume of the catalytic cracking catalyst are measured by adopting a nitrogen adsorption BET specific surface area method; the total specific surface area of the catalyst is measured by adopting a nitrogen adsorption BET specific surface area method; the mesoporous protonic acid of the catalyst has a kinetic diameter of

The 2, 6-di-tert-butylpyridine molecule can contact with protonic acid. MediumMeasuring the amount of the pore protonic acid by adopting a 2, 6-di-tert-butylpyridine adsorption infrared acidity method; total acid content adopts NH₃The TPD method is used for the measurement.

Preferably, the phosphorus additive content in the catalytic cracking catalyst is P₂O₅From 0.1 to 15% by weight, for example from 1 to 13% by weight or from 1.5 to 8% by weight or from 0.5 to 6.5% by weight or from 2 to 5% by weight.

The catalytic cracking catalyst provided by the invention contains natural minerals, wherein the natural minerals are one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; the oxide binder is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silica-alumina binder.

The catalytic cracking catalyst provided by the invention contains a molecular sieve with an IMF structure, wherein the molecular sieve with the IMF structure can be a sodium-type IMF structure molecular sieve, and can also be a modified IMF structure molecular sieve obtained by modifying the sodium-type IMF structure molecular sieve, such as a hydrogen-type IMF structure molecular sieve, an ammonium-type IMF structure molecular sieve, and an IMF structure molecular sieve containing phosphorus and/or transition metals, wherein the transition metals are one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with IMF structure, such as IM-5, can be NaIM-5, or a molecular sieve obtained by modifying NaIM-5 molecular sieve, such as HIM-5, ammonium type IM-5, and IM-5 containing phosphorus and/or transition metal, wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.

The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the steps of preparing a microspherical composition comprising a first molecular sieve, natural minerals and an oxide binder, namely a first composition microsphere, and modifying the first composition microsphere; the first composition microsphere modification treatment comprises the following steps:

a. putting the first composition microspheres into an alkaline solution for treatment, filtering and washing to obtain alkali-treated first composition microspheres;

b. and c, treating the alkali-treated first composition microspheres obtained in the step a in a composite acid solution consisting of fluosilicic acid, organic acid and inorganic acid, filtering and washing, optionally carrying out ammonium exchange sodium washing treatment, optionally filtering and optionally washing, and optionally drying to obtain the composition microspheres rich in mesopores.

c. Introducing a phosphorus additive and a metal additive into the composition microspheres rich in mesopores;

d. roasting at 400-800 deg.c for at least 0.5 hr.

In the preparation method of the catalytic cracking catalyst provided by the invention, the alkaline solution in step a comprises an alkaline compound, preferably, the alkaline compound is a strongly alkaline inorganic compound, for example, the alkaline compound is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide and high-alkali sodium metaaluminate. The alkaline solution used in step a is at least one selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonium hydroxide solution and high-alkali sodium metaaluminate solution. The alkaline solution is an aqueous solution of an alkaline compound.

According to the method for preparing the catalytic cracking catalyst provided by the invention, in one embodiment, the alkaline solution used in the step a preferably comprises high-alkali sodium metaaluminate, preferably high-alkali sodium metaaluminate solution. Preferably, in the high-alkali sodium metaaluminate solution, Na₂O content of 270-310 g/L, Al₂O₃The content is 30-50 g/L, and the solution density is 1.25-1.45 g/mL.

According to the preparation method of the catalytic cracking catalyst provided by the invention, the treatment in the step a comprises the following steps: comprises contacting the microspheres of the first composition with an alkaline solution, wherein the alkaline solution comprises an alkaline compound, and the microspheres of the first composition are mixed with an alkali metal oxide (ammonium hydroxide as NH) based on the weight of the alkali metal oxide₃The weight ratio of the basic compound is 1 (0.01-0.35). Preferably, the microspheres of the first composition are mixed with the alkali metal oxide (ammonium hydroxide as NH) on a dry weight basis₃In terms of the weight ratio of the basic compounds) is 1: (0.050.25) or 1: (0.01-0.15).

The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: the weight ratio of the first composition microspheres to water on a dry basis is 1: (5-20).

The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: the temperature of the treatment is 25 ℃ to 100 ℃, preferably 40 ℃ to 75 ℃ or 45 ℃ to 65 ℃, and the treatment time is 10 minutes or more, for example, 0.2 to 6 hours, or 0.2 to 4 hours, or 0.3 to 3 hours.

In the preparation method of the catalytic cracking catalyst, in the step b, the alkali-treated first composition microspheres obtained in the step a are treated in a solution of a composite acid consisting of fluosilicic acid, organic acid and inorganic acid, wherein the treatment is to contact the alkali-treated first composition microspheres with a composite acid aqueous solution consisting of fluosilicic acid, organic acid and inorganic acid for 10 minutes or more, such as 0.2-10 hours or 0.5-6 hours, filter and optionally wash. The filter cake obtained by filtration or the filter cake after washing can also be contacted with an ammonium salt solution to carry out an ammonium exchange sodium washing treatment so that the sodium oxide in the obtained catalyst is not more than 0.2 wt%, preferably not more than 0.15 wt%. The ammonium salt may be a commonly used ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate, and ammonium nitrate.

In the step b, the treatment temperature is 25-100 ℃, for example, 30-75 ℃ or 45-65 ℃.

According to the preparation method of the catalytic cracking catalyst, at least one of the organic acid selected from ethylenediamine tetraacetic acid, oxalic acid, acetic acid, citric acid and sulfosalicylic acid in the step b is preferably oxalic acid, and at least one of the inorganic acid selected from hydrochloric acid, sulfuric acid and nitric acid is preferably hydrochloric acid. Preferably, the organic acid in step b is oxalic acid, and the inorganic acid is hydrochloric acid.

In the preparation method of the catalytic cracking catalyst provided by the invention, the treatment conditions in the step b are as follows: the weight ratio of the first composition microspheres, the fluosilicic acid, the inorganic acid and the organic acid is 1 (0.003-0.3) to 0.01-0.45 to 0.01-0.55 on a dry basis.

Preferably, in the preparation method of the catalytic cracking catalyst provided by the invention, the treatment conditions in the step b are as follows: the weight ratio of the first composition microspheres, the fluosilicic acid, the organic acid and the inorganic acid is 1 (0.005-0.3): (0.02-0.3): or 1 (0.005-0.17): 0.015-0.15): 0.02-0.15): or 1 (0.005-0.1): 0.02-0.2): 0.02-0.15. The weight ratio of the fluosilicic acid to the first composition microspheres is preferably (0.005-0.3): 1 or (0.005-02): 1 or (0.005-0.17): 1 or (0.005-0.1): 1; the weight ratio of the organic acid to the first composition microspheres is preferably (0.02-0.3): 1 or (0.015 to 0.15): 1 or (0.02-0.2): 1; the weight ratio of the inorganic acid to the first composition microspheres is preferably (0.01-0.2): 1 (or 0.02-0.3): 1, or (0.02-0.15): 1 or (0.02-0.15): 1.

in the preparation method of the catalytic cracking catalyst provided by the invention, in the step b, the weight ratio of water to the first composition microspheres calculated on a dry basis is 3-20: 1 is, for example, 4 to 15: 1 or 5-10: 1.

the preparation method of the catalytic cracking catalyst according to the present invention, wherein the ammonium exchange sodium wash exchange process of step b contacts the composition obtained by the complex acid treatment with an ammonium salt solution, wherein the ammonium salt may be a commonly used ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, sodium acetate and ammonium nitrate. Ammonium salt exchange sodium wash treatment followed by filtration, optionally washing, to wash out exchanged sodium and non-exchanged ammonium salts in the catalyst. For example, in ammonium exchange sodium washing, the weight ratio of an ammonium salt solution to the composition obtained by the complex acid treatment is 5-20: 1, the concentration of the ammonium salt solution is 1-10 wt%, the contact temperature is 30-80 ℃, and the contact time is 0.5-2 hours.

In the preparation method of the catalytic cracking catalyst provided by the invention, the washing in the step b is a conventional method, for example, according to a weight ratio of the first composition microspheres to water of 1: and leaching with water in a weight ratio of 5-10. In the washing, the washing liquid after washing is generally neutral, for example, the pH value is 6 to 8.

In the preparation method of the catalytic cracking catalyst provided by the invention, the step c of introducing the phosphorus additive comprises the step of contacting the composition microspheres rich in mesopores with a phosphorus-containing compound. The phosphorus additive is introduced into the catalyst by performing said contacting to effect impregnation and/or ion exchange. The phosphorus additive may be introduced into the mesopore-rich composition microspheres by one or more contacts with the composition.

In the preparation method of the catalytic cracking catalyst, the method for introducing the phosphorus additive in the step c comprises the step of impregnating and/or ion exchanging the composition microspheres rich in mesopores with a phosphorus-containing compound, wherein the phosphorus-containing compound can be one or more of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

According to the preparation method of the catalytic cracking catalyst, the roasting treatment conditions in the step d comprise the following steps: the atmosphere of the roasting treatment is air atmosphere, nitrogen atmosphere or water vapor atmosphere or the mixture atmosphere of the above atmospheres; the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours. Preferably, the roasting treatment is carried out at 500-600 ℃ for 0.5-8 hours.

According to the method of the present invention, the baking process in step d may be wet baking, and the wet baking is performed in an atmosphere of 1 to 100 vol% of water vapor (i.e., an atmosphere containing 1 to 100 vol% of water vapor), more preferably 100 vol% of water vapor.

The catalytic cracking catalyst provided by the invention can be used for producing low-carbon olefin by catalytic cracking of hydrocarbon oil, and the method for producing low-carbon olefin by catalytic cracking of hydrocarbon oil comprises the step of contact reaction of hydrocarbon oil and the catalytic cracking catalyst provided by the invention. The reaction conditions can refer to the existing conditions for producing the low-carbon olefin by catalytic cracking. The hydrocarbon oil is petroleum hydrocarbon, and can be partial fraction petroleum hydrocarbon or full fraction petroleum hydrocarbon. The catalytic cracking catalyst is suitable for producing low-carbon olefin by cracking heavy oil, such as one or more of vacuum residue, atmospheric residue, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, solvent deasphalted oil, lubricating oil refined oil and hydrotreated oil obtained by hydrotreating the above oil products.

The catalytic cracking catalyst provided by the invention has rich mesoporous structure, proper mesoporous acidity and higher hydrothermal stability, is used for heavy oil catalytic cracking reaction, and has the advantages of higher conversion rate, high propylene yield, high BTX yield and particularly good propylene selectivity. Compared with the existing cracking catalyst, the catalytic cracking catalyst provided by the invention has higher hydrocarbon oil cracking activity, higher conversion rate and higher propylene yield and BTX yield. According to the preparation method of the catalytic cracking catalyst, the IMF structure molecular sieve, the natural mineral substances and the binder component are prepared into the microsphere composition, then the pore structure and the acidity of the catalyst are further modulated by an alkali and acid coupling treatment method, and phosphorus and metal modification is carried out after the catalyst is prepared, so that the performance of the whole catalyst can be improved, the stability of the catalyst is improved, the selectivity of propylene and BTX is improved, and the phosphorus and catalyst modification efficiency can be improved.

Detailed Description

The catalytic cracking catalyst provided by the invention contains natural minerals, wherein the natural minerals comprise one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, rectorite and the like. The content of the natural mineral in the catalyst provided by the invention is 5-65 wt%, preferably 8-60 wt%, for example 15-60 wt%, or 8-45 wt%, or 20-55 wt%, calculated by weight percentage based on the total amount of the catalyst, on a dry basis.

The catalytic cracking catalyst provided by the invention contains an oxide binder component, wherein the oxide is one or a mixture of more than two of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, amorphous silica-alumina and aluminum phosphate material, and the oxide binder is derived from sol-state substances of corresponding oxide precursors such as oxides, such as one or more of silica sol, alumina sol, pepto-pseudo-boehmite, silicon-alumina sol and phosphorus-containing alumina sol. The oxide binder is present in an amount of 10 to 60 wt.%, preferably 15 to 55 wt.%, for example 10 to 30 wt.%, or 20 to 50 wt.%, or 25 to 50 wt.%, or 12 to 28 wt.%, in terms of the weight percent of oxides, based on the total amount of catalyst.

The catalytic cracking catalyst provided by the invention contains a first molecular sieve, and the first molecular sieve is a molecular sieve with an IMF structure. The molecular sieve with the IMF structure can be a sodium type IMF structure molecular sieve, or an IMF structure molecular sieve obtained by carrying out various modification methods on the molecular sieve with the sodium type IMF structure, such as an ammonium type IMF structure molecular sieve obtained by ammonium exchange, a hydrogen type IMF structure molecular sieve, and a modified IMF structure molecular sieve containing one or more of phosphorus and transition metals; the molecular sieve with the IMF structure, such as IM-5, can be NaIM-5, or a molecular sieve obtained by modifying NaIM-5 molecular sieve, such as HIM-5, ammonium type IM-5, phosphorus and/or transition metal-containing IM-5; wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The content of the first molecular sieve is 24 to 75 wt%, preferably 30 to 65 wt%, for example 30 to 55 wt% or 35 to 50 wt%.

The sodium-type IMF structure molecular sieve is well known to those skilled in the art and is commercially available and can be prepared by itself, for example, the sodium-type IMF structure molecular sieve is prepared by the steps comprising: filtering and washing the slurry of the IMF structure molecular sieve obtained by amine crystallization to obtain a washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 3.0 wt.% based on the total dry basis weight of the washed molecular sieve based on sodium oxide; and drying and air roasting the washed molecular sieve to obtain the sodium type IMF structure molecular sieve. The molecular sieve with the IMF structure is preferably a molecular sieve obtained by amine crystallization, wherein the amine crystallization refers to the preparation of the molecular sieve by hydrothermal crystallization by adopting a template agent, and specific documents refer to Chinese patents CN102452667A, CN103708491A, CN102452666A and CN103723740A by taking the preparation of the IMF molecular sieve as an example. The air roasting is used for removing the template agent in the washed molecular sieve, and the temperature of the air roasting can be 400-700 ℃, and the time can be 0.5-10 hours.

The cracking catalyst provided by the invention can also contain an auxiliary component. The content of the auxiliary component is not more than 30% by weight, for example 0 to 30% by weight or 0.5 to 25% by weight, based on the dry basis. The additive component is at least one of a desulfurization additive component, a denitration additive component and a combustion improver component.

The cracking catalyst provided by the invention also can contain a second molecular sieve, wherein the second molecular sieve is other molecular sieves except the first molecular sieve, the molecular sieves are usually associated with the active component of the catalytic cracking catalyst, the content of the second molecular sieve is 0-25 wt%, such as 0.5-20 wt%, the other molecular sieves are one or more of MFI structure molecular sieves, SAPO molecular sieves, MCM molecular sieves, BEA structure molecular sieves and ferrierite, the BEA structure molecular sieves can be sodium type BEA structure molecular sieves, and can also be modified BEA structure molecular sieves obtained by modifying sodium type BEA structure molecular sieves, such as hydrogen type BEA structure molecular sieves, ammonium type BEA structure molecular sieves, phosphorus and transition metal BEA structure molecular sieves, wherein the transition metal is one or more of hydrogen type BEA structure molecular sieves, ammonium type BEA structure molecular sieves, phosphorus and transition metals, such as β molecular sieves, such as 365 β, such as 3632 modified sodium type molecular sieves, such as β H molecular sieves obtained by modifying sodium type BEA structure molecular sieves, such as Na type BEA structure molecular sieves, and Na type molecular sieves₄β molecular sieve, β molecular sieve modified by one or more of phosphorus and transition metals, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga, ferrierite such as Fer molecular sieve, sodium Fer molecular sieve or modified Fer molecular sieve obtained by modifying sodium Fer molecular sieve such as HFer, NH₄A Fer molecular sieve modified with one or more of a Fer molecular sieve, phosphorus and a transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The MFI structure molecular sieve can be a sodium type MFI structure molecular sieve, and can also be an MFI structure molecular sieve obtained by carrying out various modification methods on a sodium type MFI structure molecular sieveFor example, an ammonium MFI structure molecular sieve obtained by ammonium exchange, a hydrogen MFI structure molecular sieve, a modified MFI structure molecular sieve containing one or more of phosphorus and a transition metal; MFI structure molecular sieves such as ZSM-5, which may be NaZSM-5, or molecular sieves modified from NaZSM-5 molecular sieves such as HZSM-5, ZSM-5 containing phosphorus and transition metals; wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.

In the preparation method of the catalytic cracking catalyst provided by the invention, a microspherical composition comprising an IMF structure molecular sieve, natural minerals and an oxide binder is prepared, and then modified. Microspheroidal compositions comprising an IMF structure molecular sieve, a natural mineral, an oxide binder may be prepared by: the microsphere composition is prepared by pulping, spray drying and optionally roasting the IMF structure molecular sieve, natural minerals, oxide binder component precursors, optional second molecular sieve, optional auxiliary components and water, and is called as a first composition microsphere. The spray drying and roasting are the prior art, and the invention has no special requirements. For example, the temperature of the calcination may be 300 to 650 ℃ or 350 to 500 ℃, and the calcination time may be 0.5 to 10 hours. The firing may be carried out in an air atmosphere, a nitrogen atmosphere, or an atmosphere containing water vapor.

The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of mixing and pulping the natural minerals, the first molecular sieve, the oxide binder such as oxide sol and/or oxide gel and water. The components are used in such amounts that the final catalyst contains, based on the total weight of the catalyst, 5 to 65 wt% of natural minerals, 10 to 60 wt% of oxides and 24 to 75 wt% of a first molecular sieve. More preferably, the components are used in amounts such that the composition of the final catalyst comprises: the natural mineral content is 5 to 50 wt% on a dry basis, for example 8 to 45 wt%, the first molecular sieve content is 30 to 65 wt% on a dry basis, for example 30 to 55 wt%, and the oxide binder content is 15 to 55 wt% on an oxide basis, for example 25 to 50 wt%.

According to the preparation method of the catalytic cracking catalyst provided by the invention, the natural mineral substances comprise one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, rectorite and the like. The natural mineral is used in an amount of 5 wt% to 65 wt%, preferably 5 wt% to 50 wt%, more preferably 8 wt% to 45 wt%, based on the total amount of the catalyst.

The invention provides a preparation method of the catalytic cracking catalyst, wherein the oxide binder precursor is selected from one or more of silica, alumina, zirconia, titania, amorphous silica-alumina and aluminum phosphate material sol or gel, and the oxide binder precursor is selected from one or more of silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol and phosphorus-containing alumina sol. The oxide binder precursor is used in an amount such that the oxide binder content in the resulting catalytic cracking catalyst is from 10 wt% to 60 wt%, for example from 15 wt% to 55 wt%, preferably from 20 wt% to 50 wt%, for example from 25 wt% to 50 wt%, in terms of the weight percent of oxide based on the total catalyst.

According to the preparation method of the catalytic cracking catalyst, the molecular sieve with the IMF structure can be a sodium type IMF structure molecular sieve, and can also be an IMF structure molecular sieve obtained by subjecting the molecular sieve with the sodium type IMF structure to various modification methods, such as an ammonium type IMF structure molecular sieve obtained by ammonium exchange, a hydrogen type IMF structure molecular sieve, and a modified IMF structure molecular sieve containing one or more of phosphorus and transition metals. The IMF structure molecular sieve such as IM-5 can be Na type IM-5, and can also be modified IM-5 molecular sieve obtained by modifying NaIM-5, such as IM-5 in hydrogen type, IM-5 in ammonium type, and IM-5 molecular sieve modified by one or more of phosphorus and transition metal, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The amount of the first molecular sieve is such that the catalyst obtained has a content of the first molecular sieve of 24 to 75 wt.%, preferably 30 to 65 wt.%, for example 30 to 55 wt.%, or 30 to 50 wt.%, or 35 to 50 wt.%, based on the total amount of the catalyst, on a dry basis.

According to the preparation method of the catalyst provided by the invention, preferably, the weight ratio of the natural mineral substance in terms of dry basis, the first molecular sieve in terms of dry basis and the oxide binder in terms of oxide in the first composition microspheres is 5-65: 24-75: 10-60, preferably 5-55: 25-55: 15-55, more preferably 8-45: 30-50: 20 to 50. Preferably, the first composition microspheres comprise, on a dry basis, 5 wt% to 65 wt% of the natural mineral, 10 wt% to 60 wt% of the oxide binder, and 24 wt% to 75 wt% of the first molecular sieve, on a dry basis, based on the dry basis weight of the first composition microspheres, and preferably, the first composition microspheres comprise, on a dry basis, 5 wt% to 55 wt% of the natural mineral, 15 wt% to 55 wt% of the oxide binder, and 25 wt% to 55 wt% of the first molecular sieve, on a dry basis. More preferably, the first composition microspheres contain 8 wt% to 45 wt% of a natural mineral on a dry basis, 20 wt% to 50 wt% of an oxide binder on an oxide basis, and 30 wt% to 50 wt% of a first molecular sieve on a dry basis.

The preparation method of the catalyst provided by the invention comprises the following steps of mixing a precursor of an inorganic oxide binder, such as pseudo-boehmite, alumina sol, silica-alumina gel or a mixture of two or more of the pseudo-boehmite, the alumina sol, the silica-alumina sol and the silica-alumina gel, with a natural mineral substance, such as kaolin, and water (such as decationized water and/or deionized water) to prepare a slurry with a solid content of 10-50 wt%, uniformly stirring, optionally adjusting the pH of the slurry to 1-4, such as 2-3, by using an inorganic acid, such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, uniformly stirring, optionally standing at 20-80 ℃ for 0-2 hours, such as 0.3-2 hours, then adding a first molecular sieve, wherein the first molecular sieve is an IMF structure molecular sieve, uniformly stirring to form a first composition slurry, and the solid content of the first composition is 20-45 wt%, spray drying to obtain microspherical composition. And then roasting the microspherical composition for 0.5 to 6 hours at 300 to 650, preferably 350 to 550 ℃, for example, to obtain the first composition microsphere. If the catalytic cracking catalyst includes a promoter component and/or a second molecular sieve, the first composition slurry also contains the promoter component and the second molecular sieve, which are introduced into the first composition slurry at any step prior to spray drying.

The washing according to the present invention is well known to those skilled in the art and, without particular reference thereto, generally refers to water washing, for example, the molecular sieve may be rinsed with 5 to 10 times the weight of the molecular sieve.

In the preparation method of the catalytic cracking catalyst provided by the invention, in the step c, a phosphorus additive is introduced into the mesoporous-rich composition microspheres obtained in the step b. Preferably, the introduction is such that the phosphorus additive content in the resulting catalytic cracking catalyst is as P₂O₅From 0.1 to 15% by weight, for example from 1 to 13% by weight or from 1.5 to 8% by weight or from 0.5 to 6.5% by weight or from 2 to 5% by weight.

The catalytic cracking catalyst prepared by the preparation method provided by the invention has more mesoporous protonic acid, and the proportion of the mesoporous protonic acid in the total acid amount is 20-70%, such as 25-65%, preferably, such as 25-50% or 30-55%.

The total specific surface area of the catalytic cracking catalyst prepared by the method is more than 240m²A total specific surface area (also referred to as specific surface area) of 240 to 350m²A/g, for example, of 250 to 320m²/g。

According to the preparation method of the catalytic cracking catalyst provided by the invention, the proportion of the mesoporous volume of the prepared catalytic cracking catalyst in the total pore volume is 35-60%, such as 40-60%, 45-58% or 35-45%. The mesoporous volume of the catalytic cracking catalyst is 0.14-0.35 ml/g, such as 0.15-0.30 ml/g.

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.

The influence of the catalytic cracking catalyst on the propylene yield and the BTX yield in the catalytic cracking of petroleum hydrocarbon is evaluated by using raw oil ACE. The catalyst is aged for 14 hours at 800 ℃ under 100 percent water vapor, and is evaluated on fixed fluidized bed micro-reaction ACE, wherein the raw oil is hydrotreated oil (the composition and physical properties are shown in Table 3), the evaluation conditions are that the reaction temperature is 535 ℃, the regeneration temperature is 620 ℃, and the agent-oil ratio (weight ratio) is 5.

The specific surface area of the present invention was measured by the standard method of GBT 5816-1995.

The pore volume of the present invention was determined using standard methods of GB/T5816-1995.

The total acid content of the invention adopts NH₃TPD method see research methods for solid catalysts, petrochemical, 30(12), 2001: 952.

the mesoporous protonic acid of the method is determined by adopting a 2, 6-di-tert-butylpyridine adsorption infrared acidity method. The specific method comprises the following steps: the catalyst was pressed to 10mg/cm²Into a band of CaF₂In the infrared bath of the window. Vacuumizing at 400 ℃, then reducing the temperature to 150 ℃, adsorbing the 2, 6-di-tert-butylpyridine for 15 minutes, and then vacuumizing for 1 hour. And cooling to room temperature to collect a spectrogram, and calculating the amount of the protonic acid. See Applied Catalysis A, General, 294, 2005: 92.

na of the invention₂O、P₂O₅The content is determined by a GB/T30905-2014 standard method.

The RIPP standard method can be found in petrochemical analysis, Yangcui and other editions, 1990 edition.

The following examples illustrate the catalysts and the process for their preparation according to the invention, in which the raw materials used have the following properties: kaolin (china kaolin, suzhou, with a solid content of 75 wt%), montmorillonite (red rock bentonite, koro, yang, louing, inc., with a solid content of 75 wt%), alumina sol (qilu division, a limited chinese petrochemical catalyst, with an alumina content of 22.5 wt%), silica sol (limited Qingdao ocean chemical, with a silica content of 25.5 wt%, pH 3.0), IM-5 molecular sieve (long ridge division, a limited chinese petrochemical catalyst, with an amine synthesis, hydrogen form, Si/Al (mass ratio) ═ 15).

The solid content is the weight ratio of the solid product obtained by roasting the material at 800 ℃ for 1 hour to the material.

Example 1

346.7g of alumina sol and 148g of kaolin are mixed, and are prepared into slurry with the solid content of 28 weight percent by using decationized water, after 2 hours of stirring, slurry containing 111g (calculated by dry basis) of IM-5 molecular sieve is added and evenly stirred to form composition slurry (the solid content is 30 weight percent), spray drying is carried out to prepare composition microspheres, and then the composition microspheres are roasted for 1 hour at 500 ℃ to prepare the first composition microspheres A1.

200g of the first composition microspheres A1 (dry basis weight, the same applies hereinafter) prepared above were taken, water was added and slurried to obtain a slurry having a solid content of 10% by weight, and 15.1g of a high-alkali sodium metaaluminate solution (Na) was added₂O is 290g/L, Al₂O₃40g/L, the solution density is 1.353g/mL), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering, and washing to neutrality (the washing to neutrality means that the washing liquid after washing is neutral, and the pH is 6-8); adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 6.2g of oxalic acid while stirring, then adding 54g of hydrochloric acid (HCl with the mass fraction of 10%) and 97g of fluorosilicic acid solution (the concentration of fluosilicic acid is 3 wt%), heating to 50 ℃, stirring for 1h at constant temperature, filtering, and washing to be neutral to obtain a filter cake; adding water into the filter cake and pulping to obtain composite microsphere slurry which has the solid content of 40 weight percent and is rich in mesopores; at 19.5gH₃PO₄Adding 60g of water (with the concentration of 85 weight percent), mixing and soaking the mixture with the composition microsphere slurry rich in mesopores, and drying; and roasting the obtained sample at 550 ℃ for 2 hours to obtain the catalytic cracking catalyst A provided by the invention. The physicochemical properties of catalyst sample A are shown in Table 1, and the results of ACE evaluation of the feedstock after aging at 800 ℃ and 100% steam for 14 hours are shown in Table 2, and the properties of the feedstock for evaluation are shown in Table 3.

Example 2

529.4g of silica sol and 36g of montmorillonite are mixed and prepared into slurry by using decationized water, the solid content of the slurry is 22.5 percent by weight, 138 g (calculated by dry basis) of IM-5 molecular sieve is added after stirring for 0.5 hour, the mixture is uniformly stirred to form first composition slurry (the solid content is 35 percent by weight), the first composition slurry is prepared into composition microspheres by spray drying, and then the composition microspheres are roasted for 1 to 2 hours at 350 ℃ to obtain first composition microspheres B1.

Taking 200g of the prepared first composition microspheres B1 (dry basis weight), adding water to prepare first composition microsphere slurry with the solid content of 10 weight percent, adding 20.5g of NaOH (with the purity of 96 percent), heating to 70 ℃, stirring at constant temperature for 0.3h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 10 weight percent, adding 25.1g of oxalic acid while stirring, then adding 247g of hydrochloric acid (the mass fraction of HCl is 10 percent) and 124.7g of fluorosilicic acid solution (the concentration of fluosilicic acid is 3 weight percent), heating to 80 ℃, stirring for 0.8h at constant temperature, filtering and washing to obtain a filter cake; adding water into the filter cake and pulping to obtain slurry with the solid content of 40 weight percent; 9.3g (NH)₄)₂HPO₄Dissolving in 90g of water, mixing with a filter cake, soaking, drying, and roasting at 550 ℃ for 2 hours to obtain the catalytic cracking catalyst B. The physicochemical properties of catalyst sample B are shown in Table 1, and after aging at 800 ℃ under 100% steam for 14 hours, the raw oil ACE evaluation was performed using the raw oil shown in Table 3, and the results are shown in Table 2.

Example 3

Taking 200g of the prepared first composition microspheres B1 (dry basis weight), adding water to prepare first composition microsphere slurry with the solid content of 10 weight percent, adding 33.1g of KOH (purity of 96 percent), heating to 30 ℃, stirring for 3 hours at constant temperature, filtering, and washing to be neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 34.2g of oxalic acid while stirring, slowly dropwise adding 235g of hydrochloric acid (the mass fraction of HCl is 10%) and 653.3g of fluorosilicic acid solution (the concentration is 3 wt%), heating to 70 ℃, stirring for 2 hours at constant temperature, filtering, washing and drying to obtain a dried filter cake; adding water into the dried filter cake and pulping to obtain slurry JY3 with the solid content of 40 wt%; at 12.8gH₃PO₄(85% strength) 180g of water was added to the slurry JMixing and soaking Y3, and oven drying; and roasting the obtained sample at 550 ℃ for 2 hours to obtain the catalyst C provided by the invention. The physicochemical properties of catalyst sample C are shown in Table 1; after aging at 800 ℃ under 100% steam for 14 hours, the raw oils shown in Table 3 were subjected to ACE evaluation, and the evaluation results are shown in Table 2.

Example 4

Taking 200g of the prepared catalyst B1 (dry basis weight), adding water to prepare slurry with the solid content of 10 weight percent, adding 21.2g of NaOH (with the purity of 96 percent), heating to 90 ℃, stirring for 2 hours at constant temperature, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain slurry with the solid content of 10 wt%, adding 5.6g of citric acid while stirring, then adding 247g of hydrochloric acid (the mass fraction of HCl is 10 wt%) and 966.7g of fluorosilicic acid solution (the concentration of fluosilicic acid is 3 wt%), heating to 30 ℃, stirring at constant temperature for 5.5h, filtering, washing and drying to obtain a composition DJ4 rich in mesopores; at 1.95gH₃PO₄(concentration 85%) adding 160g of water, mixing with the composition DJ4 rich in mesopores, soaking, and drying; and roasting the obtained sample at 550 ℃ for 2 hours in an atmosphere of 100% water vapor to obtain the catalytic cracking catalyst D provided by the invention. The physicochemical properties of catalyst sample D are shown in Table 1; after aging at 800 ℃ and 100% steam for 14 hours, the stock oil ACE evaluation was performed according to the method of example 1, and the evaluation results are shown in Table 2.

Comparative example 1

The basic procedure in this comparative example is as in example 1, except that the treatment with alkali and acid, the phosphorus modification treatment and the exchange of sodium with ammonium sulfate solution were not performed, and the sample obtained was comparative sample I. The physicochemical properties are shown in Table 1, and the results of ACE evaluation of the raw oil by the method of example 1 are shown in Table 2.

Comparative example 2

A catalyst was prepared by following the procedure of example 1 except that, in the acid treatment, only an organic acid and an inorganic acid were used without conducting the alkali treatment, and the fluorosilicic acid was replaced with an equimolar amount of hydrochloric acid. The physicochemical properties are shown in Table 1, and the results of ACE evaluation of the raw oil by the method of example 1 are shown in Table 2.

Comparative example 3

The basic procedure in this comparative example follows the procedure of example 1 except that the complex acid dealumination treatment was not performed prior to phosphorus modification and the sodium was washed with an ammonium nitrate solution exchange and the resulting sample was comparative sample III. The physical properties are shown in Table 1, and the results of ACE evaluation of the raw oil by the method of example 1 are shown in Table 2.

Comparative example 4

A catalytic cracking catalyst was prepared by following the procedure of example 1, except that the treatment with the complex acid was not conducted, the treatment with the fluorosilicic acid and oxalic acid was conducted, and the hydrochloric acid was replaced with an equimolar amount of oxalic acid, to obtain catalyst sample IV. The physicochemical properties are shown in Table 1, and the results of ACE evaluation of the raw oil by the method of example 1 are shown in Table 2.

Comparative example 5

A catalytic cracking catalyst was prepared by following the procedure of example 1 except that only hydrochloric acid treatment was used at the time of acid treatment in a molar amount equal to the total molar amount of the fluorosilicic acid, organic acid and inorganic acid used in example 1. The ACE evaluation of the stock oil was carried out in accordance with the method of example 1, and the evaluation results are shown in Table 2.

TABLE 1

TABLE 2

TABLE 3

Item	Raw oil
		Density (20 ℃ C.), g/cm³	0.9334
Dioptric light (70 degree)	1.5061
		Four components, m%
Saturated hydrocarbons	55.6
		Aromatic hydrocarbons	30
Glue	14.4
		Asphaltenes	<0.1
Freezing point, DEG C	34
		Metal content, ppm
Ca	3.9
		Fe	1.1
Mg	<0.1
		Na	0.9
Ni	3.1
		Pb	<0.1
V	0.5
		C m％	86.88
H m％	11.94
		S m％	0.7
M% of carbon residue	1.77

As can be seen from Table 2, compared with the contrast agent, the catalyst provided by the invention has high conversion rate for cracking hydrocarbon oil and high yield of propylene and BTX (benzene, toluene and xylene).

Claims

1. A catalytic cracking catalyst, comprising the following components in percentage by weight:

A) 5%~65% natural minerals on a dry basis;

B) 10%~60% oxide binder in terms of oxide;

C) 24% to 75% of a first molecular sieve on a dry basis, the first molecular sieve being an IMF structure molecular sieve; and

D) 0.1%~15% phosphorus additive based on P ₂ O ₅ ;

The ratio of the mesoporous proton acid amount of the catalytic cracking catalyst to the total acid amount is 20%-70%.

2 . The catalytic cracking catalyst according to claim 1 , wherein the content of the phosphorus additive is 0.5-6.5 wt %. 3 .

3. The catalytic cracking catalyst according to claim 2, wherein the content of the phosphorus additive is 2 to 5% by weight.

4. catalytic cracking catalyst according to claim 1, is characterized in that, the total specific surface area of described catalytic cracking catalyst is 240～350m ² /g, and the ratio that mesoporous proton acid amount accounts for total acid amount is 25%～50%. %.

5. The catalytic cracking catalyst according to claim 1, wherein the mesopore volume of the catalyst is 0.14～0.35ml/g, and the ratio of the mesopore volume to the total pore volume is 35%～60%.

6. The catalytic cracking catalyst according to claim 1, wherein the natural minerals are kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, hydrotalcite, bentonite and one or more of rectorites; the oxide is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and amorphous silicon-alumina.

7. a preparation method of the catalytic cracking catalyst described in any one of claims 1～6, comprising:

forming the first composition microspheres including the first molecular sieve, natural minerals, and oxide binder, and modifying the first composition microspheres; the first composition microspheres The modification treatment includes the following steps:

a, putting the first composition microspheres into an alkaline solution for processing, filtering and washing to obtain alkali-treated first composition microspheres;

b. The alkali-treated first composition microspheres obtained in step a are treated in a composite acid solution composed of fluorosilicic acid, organic acid and inorganic acid, filtered and washed, and optionally dried to obtain mesoporous-rich microspheres. The composition microspheres; or, the alkali-treated first composition microspheres obtained in step a are treated in a composite acid solution composed of fluorosilicic acid, organic acid and inorganic acid, filtered, optionally washed, and washed with ammonium exchange. Sodium treatment, filtration and optional washing, optional drying, to obtain mesoporous-rich composition microspheres; the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid;

c. Introducing phosphorus additives into the mesoporous-rich composition microspheres;

d. calcination at 400～800℃ for at least 0.5 hours.

8. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the catalytic cracking catalyst optionally contains a second molecular sieve, optionally contains an auxiliary component, and the formation comprises the first molecular sieve, The preparation steps of the first composition microspheres of natural minerals and oxide binders include:

The first molecular sieve, the natural mineral, the precursor sol of the oxide, the optional second molecular sieve, and the optional auxiliary components are mixed with water to be slurried, spray-dried, and optionally calcined.

9. catalytic cracking catalyst preparation method according to claim 7 is characterized in that, in the alkaline solution described in step a, comprises alkaline compound, and described alkaline compound is sodium hydroxide, potassium hydroxide, hydroxide One or more of lithium, ammonium hydroxide, and overbased sodium metaaluminate.

10. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the treatment described in the step a: comprising contacting the first composition microspheres with an alkaline solution, wherein the alkaline solution comprises an alkaline solution. Compound, the weight ratio of the basic compound of the first composition microsphere on a dry basis is 1: (0.01~0.35), among the basic compounds, the alkali metal compound is calculated as an alkali metal oxide, and the ammonium hydroxide is calculated as NH ₃ counts.

11. catalytic cracking catalyst preparation method according to claim 7 is characterized in that, in the treatment described in step a: the weight ratio of the first composition microsphere and water in dry basis weight is 1: (5- 20), the temperature of the treatment is from room temperature to 100°C, and the time is 0.2-4 hours.

12. The catalytic cracking catalyst preparation method according to claim 7, the condition of the treatment described in the step a is: the ratio of the weight of the first composition microsphere and the basic compound in terms of dry basis weight is 1: (0.05 ~ 0.25) or 1: (0.01 ~ 0.15), the alkali metal in the basic compound is calculated as the oxide, and the ammonium hydroxide is calculated as NH ₃ .

13. catalytic cracking catalyst preparation method according to claim 7, is characterized in that, organic acid described in step b is at least one in EDTA, oxalic acid, acetic acid, citric acid and sulfosalicylic acid .

14. catalytic cracking catalyst preparation method according to claim 7, is characterized in that, the condition of processing described in step b is: the first composition microsphere, fluorosilicic acid, organic acid and inorganic in dry basis weight The weight ratio of acid is 1:(0.003~0.3):(0.01~0.55):(0.01~0.45).

15. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the condition for the treatment described in the step b is: the first composition microspheres, fluorosilicic acid, organic acid and inorganic acid on a dry basis The weight ratio is 1:(0.005~0.3):(0.02~0.3):(0.02~0.3).

16 . The method for preparing a catalytic cracking catalyst according to claim 7 , wherein the temperature of the treatment in step b is 25-100° C. and the time is 0.5-6 hours. 17 .

17. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the ammonium exchange washing and sodium treatment process described in step b comprises the step of contacting the ammonium salt solution with the first composition microspheres after the acid treatment, so that the The ammonium exchange and sodium washing treatment make the sodium oxide content in the obtained catalytic cracking catalyst not more than 0.2% by weight.

18. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the introduction of the phosphorus additive in step C comprises contacting the mesoporous-rich composition microspheres with a phosphorus-containing compound to impregnate and/or ion-exchange. step.

19. The method for preparing a catalytic cracking catalyst according to claim 18, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

20. catalytic cracking catalyst preparation method according to claim 7, is characterized in that, the condition of the described roasting treatment of step d comprises: the atmosphere of roasting treatment is the mixture atmosphere of air atmosphere, nitrogen atmosphere or water vapor atmosphere or above-mentioned atmosphere; The roasting temperature is 400-800°C, and the roasting time is 0.5-8 hours.

21. The method for preparing a catalytic cracking catalyst according to claim 7, wherein the oxide binder precursor comprises silica sol, alumina sol, peptized pseudoboehmite, silica-alumina sol and phosphorus-containing sol One or more of the aluminum sols.

22. The method for preparing a catalytic cracking catalyst according to claim 7, characterized in that, based on the dry weight of the first composition microspheres, the first composition microspheres comprise: 5 %～65% of natural minerals, 10%～60% of oxide binder in terms of oxides and 24%～75% of first molecular sieves in dry basis; based on the weight of the catalytic cracking catalyst, all The catalytic cracking catalyst contains 0.1% to 15% phosphorus additive in terms of P ₂ O ₅ .

23. catalytic cracking catalyst preparation method according to claim 7, is characterized in that, described alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonium hydroxide solution, high alkali metaaluminum at least one of sodium solutions.

24. The method for preparing a catalytic cracking catalyst according to claim 7, characterized in that, the condition of the treatment described in the step b is: the first composition microsphere, fluorosilicic acid, organic acid and inorganic acid on a dry basis The weight ratio is 1:(0.005~0.17):(0.015~0.15):(0.02~0.15).

25. catalytic cracking catalyst preparation method according to claim 15, is characterized in that, the ratio of the weight of described first composition microsphere, fluorosilicic acid, organic acid and inorganic acid is 1:(0.005～0.1): (0.02~0.2): (0.02~0.15).

26. The method for preparing a catalytic cracking catalyst according to claim 17, wherein the ammonium salt is selected from at least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate .

27. The method for preparing a catalytic cracking catalyst according to claim 22, wherein the catalytic cracking catalyst contains 0.5 to 6.5% by weight of phosphorus additives.

28. The method for preparing a catalytic cracking catalyst according to claim 22, wherein the catalytic cracking catalyst contains 2 to 5% by weight of phosphorus additives.

29. A method for producing light olefins by catalytic cracking of hydrocarbons, comprising the step of contacting and reacting hydrocarbon oil with the catalytic cracking catalyst described in any one of claims 1 to 6.