CN107971018A - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents

Abstract

A catalytic cracking catalyst and a preparation method thereof, the catalyst includes 5-65% of natural minerals, 10-60% of an oxide binder, and 24-75% of a first molecular sieve, the first molecular sieve having a pore size smaller than The molecular sieve and the optional Y-type molecular sieve in the catalyst have mesoporous protonic acid content accounting for 20-70% of the total acid content. The preparation method of the catalyst includes the steps of forming a slurry including the first molecular sieve, natural minerals and inorganic oxide binder, spraying and drying, and treating with alkali and compound acid. The catalytic cracking catalyst used in 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 and its preparation method and reference.

Background technique

Low-carbon olefins such as ethylene, propylene, and butene are essential chemical raw materials and can be used to synthesize resins, fibers, and rubber. Among them, propylene is an important raw material used to manufacture petrochemical products after ethylene, and is mainly used to produce chemical products such as polypropylene, acrylonitrile, and propylene oxide. At present, propylene at home and abroad mainly comes from the by-products of thermal cracking to produce ethylene. The second largest source of propylene is the FCC unit, which provides about 30% of the demand. In the United States, the FCC unit provides the demand for propylene from petrochemical products. half of.

In recent years, the demand for propylene has grown rapidly. According to the forecast of HIS, by 2016, the growth rate of global propylene consumption will be about 5% on average, which is higher than the growth rate of ethylene by 3.4%. However, the propylene/ethylene ratio of steam cracking cannot be adjusted flexibly. Moreover, its reaction temperature is as high as 840-860°C, and its energy consumption accounts for about 40% of the energy consumption of the petrochemical industry. Therefore, it is an effective and efficient way to increase the production of propylene through FCC to meet the demand growth.

Beta molecular sieve is a high-silicon macroporous molecular sieve, which was first synthesized by Mobil in 1967. In 1988, Newsman and Kiggins determined the crystal structure of beta molecular sieve through modern techniques such as electron diffraction, high-resolution electron microscope and computer. Structural research shows that Beta molecular sieve has three intersecting 12-membered ring channels, the one-dimensional channel parallel to the (001) crystal plane has a 12-membered ring pore diameter of 0.57-0.75 nm, and the other parallel to the (100) crystal plane The diameter of the twelve-membered ring of the two-dimensional channel is 0.56-0.65 nm. Due to its unique pore structure, high acidity and good hydrothermal stability, Beta molecular sieve has broad prospects for industrial application and has been successfully used in petrochemical fields such as isomerization, catalytic cracking and alkylation of aromatics.

After the Y molecular sieve was successfully synthesized in 1964, it showed a good catalytic effect in the catalytic conversion of alkanes. The Y molecular sieve has a three-dimensional twelve-membered ring channel structure with a pore diameter of 0.74nm, and a supercage with a diameter of 1.3nm exists in the molecular sieve. Because Y molecular sieve has such structural characteristics, it has been widely used in catalytic cracking reactions and has excellent performance. With the demand for low-carbon olefins and other products, Y molecular sieves began to be compounded with other molecular sieves, such as ZSM-5, which can flexibly adjust the distribution of products.

CN103785460A proposes a catalyst for producing low-carbon olefins and a preparation method thereof. The catalyst system compounded by MFI molecular sieve and phosphorus-modified β molecular sieve is used for catalytic cracking of naphtha to produce propylene with higher low-carbon olefin production. Rate. The catalyst is used for catalytic cracking of heavy oil, has low activity and low yield of low-carbon olefins.

CN101837301A proposes a catalyst for catalytic cracking to increase production of propylene and a preparation method thereof, in which shape-selective molecular sieves (ZSM-5 or β molecular sieves) and Y-type molecular sieves are mixed and homogenized with a substrate to form a slurry, spray-dried, and then treated with an acidic solution to obtain catalytic cracking catalyst. The catalyst can greatly improve the yield and selectivity of propylene in catalytic cracking liquefied gas.

However, the existing cracking catalysts containing Y-type molecular sieves and shape-selective molecular sieves have low propylene selectivity.

Contents of the invention

One of the technical problems to be solved in the present invention is to provide a fluidized bed catalytic cracking catalyst, which has excellent hydrothermal stability and higher propylene selectivity, and the second purpose of the present invention is to provide the preparation of said catalyst methods and applications.

The invention provides a catalytic cracking catalyst, based on the weight of the catalyst, comprising (a) 5% to 65% of natural minerals on a dry basis; (b) 10% to 60% of oxides; and (c) 24% to 75% of the first molecular sieve, the first molecular sieve is a Y-type molecular sieve with a pore size smaller than The molecular sieve or the first molecular sieve has a pore size smaller than Two or more of the molecular sieves; the ratio of mesoporous protic acid to the total acid in the catalytic cracking catalyst is 20% to 70%, for example, 25% to 65%. The total specific surface area of the catalyst is preferably greater than 240 m ² /g.

Preferably, the mesopore volume of the catalytic cracking catalyst accounts for 35%-60% of the total pore volume, for example, 40%-60% or 45%-58% or 35-45%. The mesopore volume of the catalyst is 0.14-0.35ml/g, such as 0.16-0.32ml/g, such as 0.25-0.45ml/g or 0.15-0.30ml/g or 0.25-0.40ml/g. The mesopores refer to pores with a pore diameter of 2-100 nm.

Preferably, the total specific surface area (also referred to as specific surface area) of the catalytic cracking catalyst is 240-350 m ² /g, for example, 250-320 m ² /g.

The catalytic cracking catalyst provided by the present invention has more mesoporous protic acids, and the proportion of mesoporous protic acids to the total acid content is 20% to 70%, such as 25% to 65%, preferably, for example, 25%. ~50% or 30~55%.

The mesopore volume and total pore volume of the catalytic cracking catalyst are measured by nitrogen adsorption BET specific surface area method; the total specific surface area of the catalyst is measured by nitrogen adsorption BET specific surface area method; the mesoporous protonic acid of the catalyst is Refers to the dynamic diameter of The 2,6-di-tert-butylpyridine molecule is able to access the protonic acid. Mesoporous protic acid content was measured by 2,6-di-tert-butylpyridine adsorption infrared acid method; total acid content was measured by NH ₃ -TPD method.

The catalytic cracking catalyst provided by the present invention contains natural minerals, such as kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite One or more of bentonite and retort clay; the oxide binder is one or more of silica, alumina, zirconia, titanium oxide, and amorphous silica-alumina binder; The Y-type molecular sieve is one or more of DASY molecular sieves, DASY molecular sieves containing rare earths, USY molecular sieves, USY molecular sieves containing rare earths, REY molecular sieves, REHY molecular sieves, and HY molecular sieves, and the pore size is less than The molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The pore size is less than Two or more of the molecular sieves are two or more of MFI structure molecular sieves, IMF structure molecular sieves, BEA structure molecular sieves, and ferrierite. The MFI structure molecular sieve can be a sodium type MFI structure molecular sieve, or a modified MFI structure molecular sieve obtained by modifying a sodium type MFI structure molecular sieve, such as a hydrogen type MFI structure molecular sieve, an ammonium type MFI structure molecular sieve, phosphorus and /or transition metal molecular sieve with MFI structure, wherein the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The molecular sieve with the MFI structure is, for example, one or more of ZSM-5, ZSP, and ZRP molecular sieves. The ZSM-5 molecular sieve can be NaZSM-5, or a molecular sieve obtained by modifying the NaZSM-5 molecular sieve, such as HZSM-5, ammonium ZSM-5, ZSM-5 containing phosphorus and/or transition metals, wherein the transition metals are, for example, RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga one or more. The IMF structure molecular sieve can be a sodium type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve through various modification methods, such as ammonium type IMF structure molecular sieve, hydrogen type IMF structure molecular sieve, containing IMF molecular sieves of one or more of phosphorus and/or transition metals, such as 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 Na-type IM-5, or a modified IM-5 molecular sieve obtained by modifying NaIM-5, such as hydrogen-type IM-5, ammonium-type IM-5 and one or more modified IM-5 molecular sieves of phosphorus and/or transition metals, such as one of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga one or more species. The BEA structure molecular sieve can be a sodium type BEA structure molecular sieve, or a modified BEA structure molecular sieve obtained by modifying a sodium type BEA structure molecular sieve, such as a hydrogen type BEA structure molecular sieve, an ammonium type BEA structure molecular sieve, phosphorus and /or the BEA structure molecular sieve of transition metal, wherein said transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga one or more described BEA structure molecular sieves are such as The β molecular sieve can be a sodium type β molecular sieve, or a modified β molecular sieve obtained by modifying a sodium type β molecular sieve, such as one or more of Hβ, NH ₄ β molecular sieve, phosphorus and/or transition metals. Beta molecular sieve, the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The ferrierite, such as Fer molecular sieve, can be a sodium-type Fer molecular sieve, or a modified Fer molecular sieve obtained by modifying a sodium-type Fer molecular sieve, such as HFer, NH ₄ Fer molecular sieve, phosphorus and/or transition metal One or more modified Fer molecular sieves, the transition metals are, for example, one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.

Preferably, the Y-type molecular sieve and the pore size are smaller than The weight ratio of the molecular sieve is 1:8-4:0.1 or 0.3:1-20:1 or 0.15:1-1:1 or 1:4-4:0.1 or 0.3:1-20:1.

The present invention also provides a method for preparing the catalytic cracking catalyst, which includes preparing a Y-type molecular sieve with a pore size smaller than The microspherical composition of molecular sieves, natural minerals, and oxide binders, the present invention is called the first composition microspheres, and the first composition microspheres are modified; the first composition microspheres are modified; The ball modification process includes the following steps:

a. Put the microspheres of the first composition into an alkaline solution for treatment, filter and wash to obtain the microspheres of the first composition of alkali treatment;

b. Treat the alkali-treated first composition microspheres obtained in step a in a compound acid solution composed of fluosilicic acid, organic acid and inorganic acid, filter and wash, optionally exchange ammonium for sodium treatment, and optionally filter and optionally washed, optionally dried, to obtain mesoporous-rich microspheres of the composition.

c. Baking at 400-800°C for at least 0.5 hours.

In the method for preparing a catalytic cracking catalyst provided by the present invention, the basic solution described in step a includes a basic compound, preferably, the basic compound is a strongly basic inorganic compound, for example, the basic compound is hydrogen One or more of sodium, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and perbasic sodium metaaluminate. The alkaline solution used in step a is selected from at least one 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 alkaline compounds.

According to the method for preparing a catalytic cracking catalyst provided by the present invention, in one embodiment, the alkaline solution used in step a preferably includes peralkali sodium metaaluminate, preferably a perbasic sodium metaaluminate solution. Preferably, in the overalkali sodium metaaluminate solution, the Na ₂ O content is 270-310 g/L, the Al ₂ O ₃ content is 30-50 g/L, and the solution density is 1.25-1.45 g/mL.

According to the method for preparing a catalytic cracking catalyst provided by the present invention, the treatment described in step a: includes contacting the microspheres of the first composition with an alkaline solution, wherein the alkaline solution includes an alkaline compound, calculated by weight on a dry basis The weight ratio of the microspheres of the first composition to the basic compound calculated as alkali metal oxide (ammonium hydroxide is calculated as NH ₃ ) is 1:(0.01-0.35). Preferably, the weight ratio of the microspheres of the first composition on a dry basis to the alkali compound in terms of alkali metal oxide (ammonium hydroxide is in NH ₃ ) is 1: (0.05-0.25) or 1 : (0.01～0.15).

In the method for preparing a catalytic cracking catalyst provided by the present invention, in the treatment described in step a: the weight ratio of the microspheres of the first composition to water in terms of dry weight is 1: (5-20).

In the preparation method of catalytic cracking catalyst provided by the present invention, in the treatment described in step a: the temperature of the treatment is 25°C to 100°C, preferably 40～75°C or 45～65°C, and the treatment time is more than 10 minutes, such as 0.2 -6 hours or 0.2-4 hours or 0.3-3 hours.

In the preparation method of the catalytic cracking catalyst provided by the present invention, in step b, the alkali-treated microspheres of the first composition obtained in step a are treated in a solution of a compound acid composed of fluorosilicic acid, an organic acid and an inorganic acid, The treatment is to contact the alkali-treated microspheres of the first composition with an aqueous solution of a complex acid composed of fluorosilicic acid, an organic acid and an inorganic acid. The contact time is, for example, more than 10 minutes, for example, 0.2 to 10 hours or 0.5 to 6 hours, filtered, optionally washed. The filter cake obtained by filtering or the washed filter cake can also be contacted with an ammonium salt solution to carry out ammonium exchange and sodium washing treatment, so that the sodium oxide in the obtained catalyst does not exceed 0.2% by weight, preferably 0.15% by weight. The ammonium salt may be a common ammonium salt, for example, at least one selected from ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate.

In step b, the temperature of the treatment is 25-100°C, such as 30-75°C or 45-65°C.

According to the catalytic cracking catalyst preparation method of the present invention, wherein, the organic acid described in the step b can be selected from at least one of ethylenediaminetetraacetic acid, oxalic acid, acetic acid, citric acid and sulfosalicylic acid and is preferably oxalic acid, so Said inorganic acid can be selected from at least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid. Preferably, the organic acid in step b is oxalic acid, and the inorganic acid is hydrochloric acid.

In the catalytic cracking catalyst preparation method provided by the present invention, the conditions of the treatment described in step b are: the weight ratio of the first composition microspheres, fluosilicic acid, inorganic acid and organic acid in terms of dry weight is 1: (0.003～0.3):(0.01～0.45):(0.01～0.55).

Preferably, in the preparation method of the catalytic cracking catalyst provided by the present invention, the conditions of the treatment described in step b are: the weight ratio of the first composition microspheres, fluosilicic acid, organic acid and inorganic acid in terms of dry weight 1:(0.005～0.3):(0.02～0.3):(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 fluosilicic acid to the microspheres of the first composition is preferably (0.005-0.3): 1 or (0.005-02): 1 or (0.005-0.17): 1 or (0.005-0.1): 1; organic acid The weight ratio to the microspheres of the first composition is preferably (0.02-0.3): 1 or (0.015-0.15): 1 or (0.02-0.2): 1; the weight ratio of the inorganic acid to the microspheres of the first composition is preferably It is (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 method for preparing a catalytic cracking catalyst provided by the present invention, in step b, the weight ratio of water to the microspheres of the first composition on a dry basis is 3-20:1, for example, 4-15:1 or 5- 10:1.

According to the catalytic cracking catalyst preparation method of the present invention, wherein, the ammonium exchange washing sodium exchange process described in step b uses an ammonium salt solution to contact the composition obtained through the compound acid treatment, and the ammonium salt can be commonly used ammonium Salt, for example, at least one selected from ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, sodium acetate and ammonium nitrate. Ammonium salt exchange and washing Sodium treatment followed by filtration and optional washing to wash away the exchanged sodium and non-exchanged ammonium salts in the catalyst. For example, in ammonium exchange washing sodium, the weight ratio of the ammonium salt solution to the composition obtained through the compound acid treatment is 5-20:1, the concentration of the ammonium salt solution is 1-10% by weight, and the contact temperature is 30-80 °C, the contact time is 0.5-2 hours.

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

According to the catalytic cracking catalyst preparation method of the present invention, the conditions of the roasting treatment described in step c include: the atmosphere of the roasting treatment is an air atmosphere, a nitrogen atmosphere or a water vapor atmosphere or a mixture atmosphere of the above-mentioned atmosphere; the roasting temperature is 400-800 ° C, and the roasting The time is 0.5-8 hours. Preferably, the baking treatment is carried out at 500-600° C. for 0.5-8 hours.

According to the method of the present invention, the roasting process described in step c can be wet roasting, and said wet roasting is at 1 to 100% water vapor by volume (that is, the atmosphere contains 1 to 100% water vapor by volume), more preferably Under 100% water vapor atmosphere.

The catalytic cracking catalyst provided by the invention can be used to produce light olefins by catalytic cracking of hydrocarbon oil, and the method for producing light olefins by catalytic cracking of hydrocarbon oil comprises the step of contacting hydrocarbon oil with the catalytic cracking catalyst provided by the invention. The conditions of the reaction can refer to the conditions of the existing catalytic cracking to produce light olefins. The hydrocarbon oil is petroleum hydrocarbon, which may be a partial fraction of petroleum hydrocarbons or a full fraction of petroleum hydrocarbons, and is especially suitable for cracking heavy oil to produce light olefins. The heavy oils are, for example, vacuum residues, atmospheric residues, catalytic cracking light cycle oils, catalytic cracking heavy cycle oils, solvent deasphalted oils, lubricating oil refined oils, and hydrotreated oils obtained by hydrotreating the above oils one or more of.

The catalytic cracking catalyst provided by the present invention has rich mesoporous structure, suitable mesoporous acidity, high hydrothermal stability, and is used for catalytic cracking reaction of heavy oil, with high conversion rate, low yield of heavy oil and low liquefied gas The yield is high, the yield of coke is low, the yield of propylene is high, and the yield of BTX is high, especially the selectivity of propylene is good. The method for producing light olefins by catalytic cracking provided by the invention has higher hydrocarbon oil cracking activity, higher conversion rate, higher propylene yield and BTX yield than the existing method. The catalytic cracking catalyst preparation method provided by the present invention adopts Y-type molecular sieve and aperture less than Molecular sieves, or two or more molecular sieves with a pore size of less than 6.9 angstroms, are first made into catalysts, and then the pore structure of the molecular sieves is further adjusted by the method of alkali and acid coupling treatment, which improves the stability of the catalyst and low-carbon olefins and BTX selectivity rate.

Detailed ways

In the catalytic cracking catalyst provided by the present invention, natural minerals are contained, wherein said natural minerals are kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite A mixture of one or more of bentonite and retort clay. Based on the total amount of the catalyst, in percent by weight, the content of natural minerals in the catalyst provided by the invention on a dry basis is 5 to 65% by weight, preferably 8 to 60% by weight, for example, 15% to 60% by weight or 8% by weight. ~45% by weight or 20% to 55% by weight.

The catalytic cracking catalyst provided by the present invention contains an oxide binder component, and the oxide is one or both of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, amorphous silicon aluminum and aluminum phosphate materials. A mixture of more than one oxide binder derived from its corresponding oxide precursors such as oxide sol-state substances, such as silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol, and phosphorus-containing One or more of aluminum sols. Based on the total amount of the catalyst, the content of the oxide binder is 10% by weight to 60% by weight, preferably 15% by weight to 55% by weight, for example, 10% by weight to 30% by weight or 20% by weight. 50% by weight or 25 to 50% by weight or 12 to 28% by weight.

In the catalytic cracking catalyst provided by the present invention, the first molecular sieve is contained, and the first molecular sieve is a Y-type molecular sieve and the aperture is smaller than Molecular sieves, the Y-type molecular sieves are molecular sieves used for catalytic cracking catalysts, and the Y-type molecular sieves are, for example, DASY molecular sieves, DASY molecular sieves containing rare earths, USY molecular sieves, USY molecular sieves containing rare earths, REY molecular sieves, REHY molecular sieves, At least one of HY molecular sieves. Preferably, Y-type molecular sieve and pore size less than The weight ratio of the molecular sieve is 1:8-4:0.1 or 0.3:1-20:1 or 0.15:1-1:1 or 1:4-4:0.1 or 1:3-15:1. The content of the first molecular sieve is preferably 25-65% by weight, for example, 30-55% by weight or 30-65% by weight or 30-55% by weight or 35-50% by weight.

The pore size is less than The molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The MFI structure molecular sieve can be a sodium type MFI structure molecular sieve, or an MFI structure molecular sieve obtained by a sodium type MFI structure molecular sieve through various modification methods, such as an ammonium type MFI structure molecular sieve obtained by ammonium exchange, a hydrogen type MFI Structural molecular sieves, modified MFI structural molecular sieves containing one or more of phosphorus and/or transition metals. MFI structure molecular sieves such as one or more of ZSM-5, ZRP and ZSP molecular sieves, the ZSM-5 molecular sieves can be NaZSM-5, or molecular sieves obtained by modifying NaZSM-5 molecular sieves, such as HZSM-5 , ZSM-5 containing phosphorus and transition metals, wherein said transition metals are for example one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The IMF structure molecular sieve can be a sodium type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve through various modification methods, such as ammonium type IMF structure molecular sieve, hydrogen type IMF structure molecular sieve, containing IMF molecular sieves of one or more of phosphorus and/or transition metals, such as 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, may be Na-type IM-5, or a modified IM-5 molecular sieve obtained by modifying NaIM-5, such as hydrogen-type IM-5. The BEA structure molecular sieve is, for example, a β molecular sieve, which may be a sodium type β molecular sieve, or a modified β molecular sieve obtained by modifying a sodium type β molecular sieve, such as Hβ. The ferrierite, such as Fer molecular sieve, can be a sodium-type Fer molecular sieve, or a modified Fer molecular sieve obtained by modifying a sodium-type Fer molecular sieve, such as HFer, NH ₄ Fer molecular sieve, phosphorus and/or transition metal One or more modified Fer molecular sieves, the transition metals are, for example, one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The pore size is less than The molecular sieve is preferably sodium type, hydrogen type or ammonium type with a pore size smaller than of molecular sieves.

Sodium-type IMF-structured molecular sieves are well known to those skilled in the art, and can be purchased commercially and can be prepared by themselves. For example, the preparation steps of the sodium-type IMF-structured molecular sieve include: filtering the IMF-structured molecular sieve slurry obtained by crystallization with an amine method and After washing, a washed molecular sieve is obtained; wherein, in terms of sodium oxide and based on the total dry weight of the washed molecular sieve, the sodium content in the washed molecular sieve is less than 3.0% by weight; the washed molecular sieve is dried and air roasted Finally, the sodium-type IMF structure molecular sieve is obtained. The molecular sieve with the IMF structure is preferably a molecular sieve obtained by crystallization with an amine method. The crystallization with an amine method refers to the preparation of a molecular sieve by hydrothermal crystallization using a template agent. Taking the preparation of an IMF molecular sieve as an example, specific documents can refer to Chinese patents CN102452667A, CN103708491A, CN102452666A and CN103723740A. The air calcination is used to remove the template agent in the washed molecular sieve, the temperature of the air calcination can be 400-700° C., and the time can be 0.5-10 hours.

The cracking catalyst provided by the invention may also contain auxiliary components. On a dry basis, the content of the auxiliary component is not more than 30% by weight, for example, 0-30% by weight or 0.5-25% by weight. The auxiliary component is, for example, at least one of a desulfurization additive component, a denitrification additive component, and a combustion additive component.

The cracking catalyst provided by the present invention may also contain a second molecular sieve, and the second molecular sieve is other molecular sieves except the first molecular sieve, and these molecular sieves are often combined with the active components of the catalytic cracking catalyst. The content of the second molecular sieve is 0-20% by weight. The other molecular sieves are eg SAPO molecular sieves and MCM molecular sieves.

In the catalytic cracking catalyst preparation method provided by the present invention, first prepare Y-type molecular sieves with apertures smaller than Molecular sieves (also called molecular sieves with a pore size less than 0.69nm), natural minerals, and oxide binders are composed of microspheres, and then modified. The preparation includes Y-type molecular sieves with a pore size smaller than The microspherical composition of molecular sieves, natural minerals, and oxide binders can pass through: the Y-type molecular sieve with a pore size smaller than Molecular sieves, natural minerals, precursors of oxide binder components, optional second molecular sieves, optional auxiliary components, and water beating, spray drying, and optional roasting are prepared. The microspherical combination The present invention refers to the first composition microspheres. The spray drying and roasting are prior art, and there is no special requirement in the present invention. For example, the firing temperature can be 300-650°C or 350-500°C, and the firing time can be 0.5-10 hours. It can be baked in an air atmosphere, a nitrogen atmosphere, or an atmosphere containing water vapor.

The preparation method of the catalytic cracking catalyst provided by the present invention includes mixing and beating natural minerals, the first molecular sieve, an oxide binder such as oxide sol and/or oxide gel, and water. The amount of each component is such that the final catalyst contains, based on the total weight of the catalyst, 5% to 65% by weight of natural minerals, 10% to 60% by weight of oxides and 24% to 75% by weight of the second A molecular sieve. More preferably, the amount of each component is such that the composition of the final catalyst includes: the natural mineral content is 5% to 50% by weight on a dry basis, such as 8 to 45% by weight, and the content of the first molecular sieve on a dry basis 30% to 65% by weight, such as 30 to 55% by weight, the content of the oxide binder in terms of oxides is 15 to 55% by weight, such as 25 to 50% by weight or 15 to 45% by weight or 20 to 35% by weight % or 12% to 28% by weight.

The preparation method of the catalytic cracking catalyst provided by the present invention, the natural minerals include kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite And a mixture of one or more of retort soil and the like. The amount of natural minerals used is such that in the obtained catalytic cracking catalyst, based on the total amount of the catalyst, the content of natural minerals is 15% to 65% by weight, preferably 20% to 55% by weight.

In the preparation method of the catalytic cracking catalyst provided by the present invention, the precursor of the oxide binder is selected from silica, alumina, zirconia, titania, amorphous silica-alumina and aluminum phosphate material sol or gel One or more mixtures of the oxide binder precursors such as one or more of silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol, and phosphorus-containing aluminum sol. The amount of the precursor of the oxide binder is such that in the obtained catalytic cracking catalyst, based on the total amount of the catalyst, the content of the oxide binder is 10% by weight to 60% by weight, such as 10% by weight, based on the weight percentage of the oxide. % by weight to 30% by weight or 15% by weight to 35% by weight, preferably 12% by weight to 28% by weight.

The preparation method of described catalytic cracking catalyst provided by the present invention, the consumption of the first molecular sieve (being Y type molecular sieve and aperture less than The amount of molecular sieve or two or more pore sizes smaller than The amount of molecular sieve) so that in the obtained catalytic cracking catalyst, the content of the first molecular sieve on a dry basis is 24% by weight to 75% by weight, preferably 30% to 70% by weight or 25% to 65% by weight, for example, 30% to 55% by weight. weight%. Among them, the pore size of Y-type molecular sieve is smaller than The molecular sieve weight ratio is 1:8-4:0.1 or 0.3:1-20:1 or 0.15:1-1:1 or 1:4-4:0.1 or 1:3-15:1. The Y-type molecular sieve is, for example, DASY molecular sieve, one or more of DASY molecular sieve containing rare earth, USY molecular sieve, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve, HY molecular sieve.

The preparation method of the catalytic cracking catalyst provided by the present invention, the described aperture is less than The molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. The molecular sieve with the MFI structure is for example one or more of ZSM-5, ZRP and ZSP molecular sieves, the ZSM-5 molecular sieve can be NaZSM-5, or a molecular sieve obtained by modifying the NaZSM-5 molecular sieve, for example HZSM-5, ZSM-5 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 IMF structure molecular sieve can be a sodium type IMF structure molecular sieve, or a modified IMF structure molecular sieve obtained by modifying the IMF structure molecular sieve through various modification methods, such as ammonium type IMF structure molecular sieve, hydrogen type IMF structure molecular sieve, containing IMF molecular sieves of one or more of phosphorus and/or transition metals, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga . For example, IM-5 can be Na-type IM-5, or a modified IM-5 molecular sieve obtained by modifying NaIM-5, such as hydrogen-type IM-5, ammonium-type IM-5, and phosphorus and/or transition IM-5 molecular sieve modified by one or more metals, such as one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. . The BEA structure molecular sieve is, for example, a β molecular sieve, which may be a sodium type β molecular sieve, or a modified β molecular sieve obtained by modifying a sodium type β molecular sieve, such as Hβ, NH ₄ β molecular sieve, phosphorus and/or transition metal One or more modified β molecular sieves, the transition metals are one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The ferrierite, such as Fer molecular sieve, can be a sodium-type Fer molecular sieve, or a modified Fer molecular sieve obtained by modifying a sodium-type Fer molecular sieve, such as HFer, NH ₄ Fer molecular sieve, phosphorus and/or transition metal One or more modified Fer molecular sieves, the transition metal is one or more of RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The pore size is less than The molecular sieve is preferably sodium type, hydrogen type or ammonium type with a pore size smaller than of molecular sieves.

In the catalyst preparation method provided by the present invention, preferably, the weight of the first composition microspheres is used as a basis, and the natural ore in the first composition microspheres (also called the first microsphere composition) is calculated on a dry basis. The weight ratio of the substance, the first molecular sieve in terms of dry basis, and the oxide binder in terms of oxides is 5-65:24-75:10-60, preferably 8-55:30-65:15-55, more preferably 8-45: 30-55: 20-50. Preferably, the microspheres of the first composition contain 5% to 65% of natural minerals on a dry basis, 10% to 60% of an oxide binder on a dry basis and 24% to 75% on a dry basis. % of the first molecular sieve, preferably, based on the weight of the microspheres of the first composition, the composition of the first microspheres contains 8% by weight to 55% by weight of natural minerals on a dry basis. 15% to 55% by weight of the oxide binder based on the weight of the substance and 25% to 55% by weight of the first molecular sieve based on the dry basis. More preferably, the microspheres of the first composition contain 8 to 45% by weight of natural minerals on a dry basis, such as 20 to 45% by weight, and 20 to 50% by weight of oxides, such as 10% to 30%. A material binder and 30-55% by weight, for example, 35-50% by weight of the first molecular sieve on a dry basis.

In the method for preparing the catalyst provided by the present invention, in one embodiment, the precursor of the inorganic oxide binder, such as pseudoboehmite, alumina sol, silica sol, silica-alumina sol, silica-alumina gel, or two or more of them A variety of mixtures, mixed with natural minerals such as kaolin and water (such as decationized water and/or deionized water), prepared into a slurry with a solid content of 10 to 50% by weight, stirred evenly, optionally with inorganic acid such as hydrochloric acid , nitric acid, phosphoric acid or sulfuric acid to adjust the pH of the slurry to 1-4, such as 2-3, stir evenly, optionally after standing at 20-80°C for 0-2 hours, for example 0.3-2 hours, then add the first molecular sieve, the The first molecular sieve has a pore size smaller than Molecular sieves and Y-type molecular sieves or pore sizes smaller than Two or more of the molecular sieves are stirred evenly to form a first composition slurry, the solid content of the first composition slurry is, for example, 20-45 weight, and spray-dried to form a microspherical composition. Then the microsphere composition is calcined, for example, at 300-650, preferably 350-550° C., for 0.5-6 hours to obtain microspheres of the first composition. If the catalytic cracking catalyst includes an auxiliary component and/or a second molecular sieve, the first composition slurry also contains an auxiliary component and a second molecular sieve, any composition of the auxiliary component and the second molecular sieve before spray drying step into the first composition slurry.

The washing described in the present invention is well known to those skilled in the art. Without special instructions, it generally refers to washing with water. For example, the molecular sieve can be rinsed with water 5-10 times the weight of the molecular sieve.

In the method for preparing a catalytic cracking catalyst provided by the present invention, the prepared catalytic cracking catalyst has more mesoporous protic acids, and the proportion of mesoporous protic acids to the total acid content is 20% to 70%, for example, 25% to 65%. , preferably, for example, it may be 25% to 50% or 30 to 55%.

In the method for preparing a catalytic cracking catalyst provided by the present invention, the prepared catalytic cracking catalyst has a total specific surface area greater than 240m ² /g, for example, a total specific surface area (also called a specific surface area) of 240 to 350 m ² /g, for example 250 to 320 m ² /g.

In the method for preparing a catalytic cracking catalyst provided by the invention, the ratio of the mesoporous volume of the prepared catalytic cracking catalyst to the total pore volume is 35% to 60%, such as 40% to 60% or 45% to 58% or 35 to 45% %. The mesopore volume of the catalytic cracking catalyst is 0.14-0.35ml/g, for example, 0.15-0.30ml/g or 0.16-0.32ml/g.

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention. The instruments and reagents used in the examples of the present invention, unless otherwise specified, are those commonly used by those skilled in the art.

The effect of catalytic cracking catalyst on the yield of propylene and BTX in the catalytic cracking of petroleum hydrocarbons was evaluated by feed oil ACE. The method is as follows: the catalyst is aged at 800°C and 100% water vapor for 15 hours, and evaluated on a fixed fluidized bed micro-reactor ACE. The raw oil is hydrotreated oil (see Table 3 for composition and physical properties), and the evaluation condition is reaction temperature 530°C, regeneration temperature 620°C, agent-oil ratio 5 (weight ratio).

The specific surface area of the present invention is measured by the GBT5816-1995 standard method.

The pore volume of the present invention is measured by GB/T5816-1995 standard method.

The total acid content of the present invention is measured by the NH ₃ -TPD method, refer to the research method of solid catalyst, Petrochemical Industry, 30(12), 2001: 952.

The mesoporous protonic acid in the method of the present invention is determined by a 2,6-di-tert-butylpyridine adsorption infrared acid method. The specific method is: press the catalyst into a thin sheet of 10 mg/cm ² and put it into an infrared pool with a CaF ₂ window. Vacuum at 400°C first, then drop to 150°C to absorb 2,6-di-tert-butylpyridine for 15 minutes, and then vacuum for 1 hour. Cool down to room temperature to collect spectra, and calculate the amount of protonic acid. See Applied Catalysis A: General, 294, 2005:92.

The Na ₂ O content of the present invention is measured by the standard method of GB/T 30905-2014.

The RIPP standard method described in the present invention can refer specifically to "Petrochemical Analysis Methods", edited by Yang Cuiding et al., 1990 edition.

The following examples illustrate catalyst provided by the invention and preparation method thereof, wherein the properties of the raw materials used are as follows: kaolin (Suzhou China Kaolin Company, solid content 75% by weight), halloysite (Sanhe white mine in Zunyi, Guizhou, solid content 75% by weight) % by weight), rectorite (Hubei Zhongxiang rectorite mine, solid content 75% by weight), montmorillonite (Hongshi bentonite company, Chaoyang City, Liaoning Province, solid content 75% by weight), pseudo-boehmite (Shandong Aluminum Industry company, solid content 65% by weight, peptize with concentration 31% by weight hydrochloric acid earlier when using, and the mol ratio of described hydrochloric acid and the pseudo-boehmite calculated by alumina is 0.20), aluminum sol (Qilu Catalyst Branch Company , alumina content is 22.5% by weight), silica sol (Qingdao Ocean Chemical Co., Ltd., silica content 25.5% by weight, pH value 3.0), phosphorus-containing aluminum sol (P content 16% by weight, Al content 8% by weight, pH value 2.0), IM-5 molecular sieve (produced by Changling Branch of Sinopec Catalyst Co., Ltd., synthesized by amine method, sodium type, silicon-aluminum ratio (SiO ₂ /Al ₂ O ₃ molar ratio, the same below) is 30), ZSM -5 molecular sieve (Sinopec Catalyst Co., Ltd. Qilu Branch, NaZSM-5, the ratio of silicon to aluminum is 44), β molecular sieve (produced by the catalyst branch of Sinopec Catalyst Co., Ltd., Hβ, the ratio of silicon to aluminum is 30), REY molecular sieve ( Qilu Branch of Sinopec Catalyst Co., Ltd., rare earth content is 10% by mass), DASY molecular sieve (Qilu Branch of Sinopec Catalyst Co., Ltd., rare earth content (calculated as RE ₂ O ₃ ) is 1.5% by weight). USY molecular sieve (Sinopec Catalyst Co., Ltd. Qilu Branch, rare earth content (calculated as RE ₂ O ₃ ) is 1.5% by weight, and the silicon-aluminum ratio SiO ₂ /Al ₂ O ₃ molar ratio is 5.8). ZRP-1 molecular sieve, product of Qilu Branch of Sinopec Catalyst Co., Ltd., with a silicon-aluminum ratio (SiO ₂ /Al ₂ O ₃ molar ratio) of 40.

The solid content is the weight ratio of the amount of solid product obtained by calcining the substance at 800° C. for 1 hour to the substance.

Example 1

267g aluminum sol was mixed with 168g kaolin, and it was formulated with decationized water into a slurry with a solid content of 31% by weight. After stirring for 0.5 hours, the molecular sieve slurry containing 24gUSY, 45gβ molecular sieve and 45g ferrierite was added to form a composition slurry ( solid content is 35% by weight), stirred evenly, and spray-dried to make composition microspheres, and then calcined the composition microspheres at 500° C. for 1 hour to obtain the first composition microspheres A1.

Take 200 g of the first composition microspheres A1 (mass on a dry basis, the same below) prepared above, add water and beat to obtain a slurry with a solid content of 10% by weight, add 11.4 g of high-alkali sodium metaaluminate solution (Na ₂ O is 290 g/ L, Al ₂ O ₃ is 40g/L, the solution density is 1.353g/mL), warming up to 50°C and stirring at a constant temperature for 0.5h, filtering and washing until neutral (washing to neutral means that the washing liquid after washing is neutral, pH6～8); add water to the filter cake and beat to obtain a slurry with a solid content of 10% by weight, add 5.3g oxalic acid during stirring, then add 51g hydrochloric acid (HCl mass fraction 10%) and 33.4g fluorosilicic acid solution (the content of fluorosilicic acid concentration of 3% by weight), heated up to 50° C. and stirred at a constant temperature for 1 h, filtered, washed, and dried to obtain the catalytic cracking catalyst A provided by the present invention. The physical and chemical properties of catalyst sample A are listed in Table 1. After aging at 800°C for 17 hours and 100% steam, the feed oil ACE was evaluated. The results are listed in Table 2. The properties of the feed oil used for evaluation are listed in Table 3.

Example 2

Mix 411.8g silica sol with 80g montmorillonite, and use decationized water to prepare it into a slurry with a solid content of 30% by weight. After stirring for 2 hours, add the slurry formed by 75gREY molecular sieve and 60gZSM-5 molecular sieve and water, stir Uniform, form the first composition slurry (solid content is 35% by weight), spray-dry to make composition microspheres, then bake the composition microspheres at 350° C. for 2 hours to obtain the first composition microspheres B1.

Take 200 g of the first composition microsphere B1 (mass on a dry basis) prepared above, add water to prepare the first composition microsphere slurry with a solid content of 10% by weight, add 16 g of NaOH (purity 96%), heat up to 70° C. and stir at a constant temperature for 0.3 h, filter and wash to neutrality; the filter cake is beaten with water to obtain a slurry with a solid content of 10% by weight, add 16g oxalic acid in the stirring, then add 38g hydrochloric acid (HCl mass fraction 10%) and 35g fluorosilicic acid solution (concentration 3 % by weight), heated to 80° C. and stirred at a constant temperature for 0.8 h, filtered, washed, and dried to obtain catalytic cracking catalyst B provided by the present invention. The physical and chemical properties of catalyst sample B are listed in Table 1. After aging at 800°C and 100% steam for 17 hours, the feedstock oils shown in Table 3 were used for ACE evaluation of the feedstock oil, and the results are listed in Table 2.

Example 3

Mix 400g of aluminum sol with 80g of montmorillonite, and prepare it into a slurry with a solid content of 30% by weight with decationized water, stir for 1 hour, and add the slurry including 30g of ZRP‐1 molecular sieve, 60g of IM‐5 molecular sieve and 60g of β molecular sieve , stirred to form a first composition slurry (solid content is 35% by weight), spray-dried to make a microsphere composition. Then the microsphere composition was calcined at 350° C. for 2 hours to obtain microsphere C1 of the first composition.

Take 200 g of the first composition microspheres C1 (mass on a dry basis) prepared above, add water to prepare the first composition microsphere slurry with a solid content of 10% by weight, add 19 g of KOH (purity: 96%), heat up to 60° C. and stir at a constant temperature for 1 h , filtered, washed to neutrality; the filter cake was beaten with water to obtain a slurry with a solid content of 10% by weight, 26g oxalic acid was added during stirring, and then 250g sulfuric acid solution was added at a speed of 30-80ml/min (H ₂ SO ₄ mass fraction 10 %) and 95g of fluosilicic acid solution (fluosilicic acid concentration: 3% by weight), heated to 70° C. and stirred at a constant temperature for 2 hours, filtered, washed, and dried to obtain catalyst C provided by the present invention. Physicochemical properties of catalyst sample C; after aging at 800°C, 17h, and 100% water vapor, the feedstock oil shown in Table 3 was used for ACE evaluation of feedstock oil, and the evaluation results of conversion rate, gas yield, and coke amount are listed in Table 2 .

Example 4

Take 200 g of catalyst C1 (mass on a dry basis) prepared above, add water to prepare a slurry with a solid content of 10% by weight, add 30 g of NaOH (purity 96%), heat up to 90° C. and stir at a constant temperature for 2 hours, filter and wash until neutral; filter cake Add water and beat to obtain a slurry with a solid content of 10% by weight, add 33g oxalic acid during stirring, then add 70g hydrochloric acid (HCl mass fraction 10% by weight) and 667g fluosilicic acid solution (concentration 3% by weight), heat up to 30°C and stir at a constant temperature for 5.5 h, filtering, washing and drying the catalytic cracking catalyst D provided by the invention. The physical and chemical properties of catalyst sample D; after aging at 800°C and 100% steam for 17 hours, the ACE evaluation of the feedstock oil, the evaluation results of conversion rate, gas yield, and coke amount are listed in Table 2.

Example 5

Mix 353g of silica sol with 80g of montmorillonite, and use decationized water to prepare it into a slurry with a solid content of 10-50% by weight, stir evenly, and add 45g of DASY molecular sieve and 60g of magnesium alkali on a dry basis after standing for 1 hour Zeolite and 45g IM‐5 were stirred evenly to form a composition slurry (solid content was 35% by weight), spray-dried to make a microspherical composition, and then the microspherical composition was roasted at 350° C. for 2 hours to obtain the first composition microspherical composition. Ball D1.

Take 200 g of the first composition microsphere D1 (dry basis mass) prepared above, add water to prepare the first composition microsphere slurry with a solid content of 10% by weight, add 22g NaOH (purity 96%), heat up to 30°C and stir at a constant temperature 3h, filter, wash to neutrality; Add water to the filter cake and beat to obtain a solid content of 10% by weight alkali treatment composition slurry, add 5g of citric acid during stirring, then add 120g of hydrochloric acid (10% by weight of HCl mass fraction) and 55g of fluorine Silicic acid solution (fluosilicic acid concentration: 3% by weight), heated to 60° C. and stirred at a constant temperature for 2.5 hours, filtered, washed, and dried to obtain the catalytic cracking catalyst E provided by the present invention. The physical and chemical properties of catalyst sample E are shown in Table 1. After aging at 800°C for 17 hours and 100% water vapor, the feedstock oil was evaluated by ACE. The evaluation results such as conversion rate, gas yield, and coke amount are listed in Table 2.

Example 6

Take 200 g of the first composition D1 (mass on a dry basis) prepared above, add water to prepare a slurry with a solid content of 10% by weight, add 25 g of KOH (purity: 96%), heat up to 50° C. and stir at a constant temperature for 0.5 h, filter and wash until neutral; The filter cake is beaten with water to obtain a slurry with a solid content of 10% by weight, 35g of oxalic acid is added during stirring, then 50g of nitric acid solution (10% by mass fraction of nitric acid) and 90g of fluorosilicic acid solution (3% by weight of concentration) are slowly added, and the temperature is raised to 50 Stir at constant temperature for 1 h at ℃, filter, wash and dry to obtain catalyst sample F. The physicochemical properties of catalyst sample F are evaluated by ACE of raw material oil after aging at 800 °C for 17 h with 100% steam. The results are listed in Table 2.

Comparative example 1

In this comparative example, the basic process is according to the method of Example 1, the difference is that no alkali and acid treatment are used to modify the treatment, and ammonium sulfate solution is used to exchange and wash sodium, and the obtained sample is comparative sample I. Its physical and chemical properties, raw oil ACE evaluation results are listed in Table 2 (the evaluation method is the same as that of Example 1, and the evaluation method of the following comparative examples is the same as this).

Comparative example 2

The catalyst was prepared according to the method of Example 1, except that alkali treatment was not carried out, and only organic and inorganic acids were used during acid treatment, and hydrofluorosilicic acid was replaced by equimolar hydrochloric acid.

Comparative example 3

The basic process in this comparative example is according to the method of embodiment 1, and the difference is that the compound acid treatment is not carried out, and ammonium nitrate solution is exchanged and washed to reduce the sodium content, and the obtained sample is comparative sample III. Its physical and chemical properties, raw oil ACE evaluation results are listed in Table 2.

Comparative example 4

Catalytic cracking catalyst was prepared according to the method of Example 1, the difference was that the compound acid was not used, but treated with fluorosilicic acid and oxalic acid, and the hydrochloric acid was replaced by oxalic acid in an equimolar amount to obtain catalyst sample IV. Its physical and chemical properties are listed in Table 1, and the ACE evaluation of the raw material oil is carried out according to the method of Example 1, and the results are listed in Table 2.

Comparative example 5

The catalytic cracking catalyst was prepared according to the method of Example 1, the difference was that the compound acid was not used for processing and hydrochloric acid was used for processing. The obtained sample was Comparative Sample V. Its physical and chemical properties, raw oil ACE evaluation results are listed in Table 2.

Table 1

V _mesopores /V _{total pores} is the ratio of mesopore volume to total pore volume

Table 2

table 3

project Raw oil Density (20℃), g/ ^cm3 0.9334 Refraction (70℃) 1.5061 Four components, m% saturated hydrocarbon 55.6 Aromatics 30 colloid 14.4 asphaltenes <0.1 freezing point, ℃ 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 Hm% 11.94 Sm% 0.7 Carbon residue m% 1.77

As can be seen from Table 2, compared with the contrast agent, the catalyst provided by the invention is used for the high conversion rate of hydrocarbon oil cracking, the yield of propylene and BTX (benzene, toluene, xylene) is higher, the selectivity of liquefied gas increases, and the oil slurry selectivity is significantly reduced.

Claims (20)

1. A catalytic cracking catalyst comprising the following components in weight percent: A) 5% to 65% natural minerals on a dry basis; B) 10% to 60% oxide binder based on oxide; C) 24% to 75% of the first molecular sieve on a dry basis, the first molecular sieve is a Y-type molecular sieve with a pore size smaller than molecular sieve, or the first molecular sieve has a pore size smaller than Two or more of the molecular sieves; The mesoporous protonic acid content of the catalytic cracking catalyst accounts for 20% to 70% of the total acid content. 2. The catalytic cracking catalyst according to claim 1, characterized in that the total specific surface area of the catalyst is 240-350 m ² /g, and the proportion of mesoporous protic acid to the total acid is 25%-50%. 3. catalytic cracking catalyst according to claim 1, is characterized in that, the mesopore volume of described catalyst is 0.14～0.35ml/g such as 0.15～0.30ml/g, and the ratio of mesopore volume and total pore volume is 35% to 60%. 4. catalyst according to claim 1, is characterized in that, described natural mineral matter comprises kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite One or more of bentonite and retort clay; the oxide is one or more of silicon oxide, aluminum oxide, zirconia, titanium oxide, and amorphous silica-alumina; the Y-type molecular sieve It is at least one of DASY molecular sieve, DASY molecular sieve containing rare earth, USY molecular sieve, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve, HY molecular sieve, and the pore size is less than The molecular sieve is at least one of MFI structure molecular sieve, IMF structure molecular sieve, BEA structure molecular sieve and ferrierite. 5. according to the described catalyzer of claim 1, it is characterized in that, described first molecular sieve is Y-type molecular sieve and aperture is less than The molecular sieve, the Y-type molecular sieve and the pore size is less than The weight ratio of the molecular sieve is 1:8-4:0.1 or 0.3:1-20:1 or 0.15:1-1:1. 6. A preparation method for catalytic cracking catalyst, comprising: Forming the first composition microspheres comprising the first molecular sieve, natural minerals, and oxide binder, and modifying the first composition microspheres; the first molecular sieve is a Y-type molecular sieve and a pore size less than The molecular sieve or the first molecular sieve has a pore size smaller than Two or more of the molecular sieves, the modification of the microspheres of the first composition comprises the following steps: a. Put the microspheres of the first composition into an alkaline solution for treatment, filter and wash to obtain the microspheres of the first composition of alkali treatment; b. The alkali-treated first composition microspheres obtained in step a are treated in a complex acid solution composed of fluosilicic acid, organic acid and inorganic acid, filtered and washed to obtain mesoporous-rich composition microspheres or, the alkali-treated first composition microspheres obtained in step a are treated in a compound acid solution composed of fluosilicic acid, organic acid and inorganic acid, filtered, optionally washed, ammonium exchanged and washed with sodium, filtered and optionally washing to obtain mesoporous-rich microspheres of the composition; c. Baking at 400-800°C for at least 0.5 hours. 7. preparation method according to claim 6, is characterized in that, described catalytic cracking catalyst optionally contains the second molecular sieve, optionally contains auxiliary component, and described formation comprises described first molecular sieve, natural mineral 1. The preparation steps of the first composition microspheres of the oxide binder include: The first molecular sieve, the natural mineral, the precursor sol of the oxide, the optional second molecular sieve, the optional auxiliary component and water are mixed and beaten, spray-dried, and optionally roasted. 8. the preparation method according to claim 6 is characterized in that, comprises basic compound in the basic solution described in step a, and described basic compound is sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrogen One or more of ammonium oxide, high alkali sodium metaaluminate; preferably, the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonium hydroxide solution, high alkali metaaluminate At least one of sodium aluminate solutions. 9. The preparation method according to claim 6, wherein the treatment in step a includes contacting the microspheres of the first composition with an alkaline solution, wherein the alkaline solution includes an alkaline compound to The weight ratio of the microspheres of the first composition in terms of dry weight to the basic compound in terms of alkali metal oxide (ammonium hydroxide is calculated as NH ₃ ) is 1:(0.01˜0.35). 10. The preparation method according to claim 6, characterized in that, in the treatment described in step a: the weight ratio of the microspheres of the first composition on a dry basis to water is 1: (5-20), The temperature of the treatment is from room temperature to 100° C., and the time is 0.2-4 hours. 11. according to the method for claim 6, the condition of processing described in the step a is: the first composition microsphere in dry basis weight and alkali metal oxide (ammonium hydroxide is in _NH ) in basic compound The weight ratio is 1:(0.05-0.25) or 1:(0.01-0.15). 12. according to the method for claim 6, organic acid described in step b is at least one in ethylenediaminetetraacetic acid, oxalic acid, acetic acid, citric acid and sulfosalicylic acid, and described mineral acid is hydrochloric acid, sulfuric acid and at least one of nitric acid. 13. The method according to claim 6, characterized in that, the conditions of the treatment described in step b are: the weight ratio of the first composition microspheres, fluosilicic acid, organic acid and inorganic acid in terms of dry weight is 1:(0.003～0.3):(0.01～0.55):(0.01～0.45). 14. The method according to claim 6, characterized in that, the conditions of the treatment described in step b are: the weight ratio of the first composition microspheres, fluosilicic acid, organic acid and inorganic acid on a dry basis weight basis is 1 :(0.005～0.3):(0.02～0.3):(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). 15. The method according to claim 6, characterized in that, the temperature of the treatment in step b is 25-100°C, and the time is 0.5-6 hours. 16. according to the method for claim 6, it is characterized in that, the ammonium exchange washing sodium treatment process described in step b comprises the step that ammonium salt solution is contacted with the first composition microsphere after acid treatment, and described ammonium salt is catalytic Cracking catalyst prepares the ammonium salt commonly used in exchange washing, can be selected from at least one in ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium acetate and ammonium nitrate; The sodium oxide content of the cracking catalyst is preferably not more than 0.2% by weight. 17. according to the method for claim 6, it is characterized in that, the condition of the described roasting treatment of step c comprises: the atmosphere of roasting treatment is the mixture atmosphere of air atmosphere, nitrogen atmosphere or water vapor atmosphere or above-mentioned atmosphere; Calcination temperature is 400-800 ℃, the roasting time is 0.5-8 hours. 18. according to the described catalytic cracking catalyst preparation method of claim 8, it is characterized in that, described oxide binder precursor sol is silica sol, aluminum sol, peptized pseudo-boehmite, silica-alumina sol and containing One or more of the aluminum phosphate sols. 19. According to the preparation method of catalytic cracking catalyst according to claim 6, it is characterized in that, based on the weight of the first composition microsphere, the first composition microsphere comprises: 14%～ 65% of natural minerals, 10% to 60% of oxide binder in terms of oxides and 24% to 75% of first molecular sieve in terms of dry basis. 20. A method for producing light olefins by catalytic cracking of hydrocarbons, comprising the step of contacting hydrocarbon oil with the cracking catalyst according to any one of claims 1-5.