CN112138712A

CN112138712A - Catalytic cracking catalyst, preparation method thereof and hydrocarbon oil catalytic cracking method

Info

Publication number: CN112138712A
Application number: CN201910580180.8A
Authority: CN
Inventors: 欧阳颖; 刘建强; 罗一斌; 庄立; 李明罡; 舒兴田; 毛国芳; 张巍
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: 2019-06-28
Filing date: 2019-06-28
Publication date: 2020-12-29
Anticipated expiration: 2039-06-28
Also published as: CN112138712B

Abstract

The invention relates to a catalytic cracking catalyst, a preparation method thereof and a hydrocarbon oil catalytic cracking method, wherein the catalyst contains 1-30 wt% of Y-type molecular sieve based on the dry weight of the catalyst, 5-55 wt% of MFI structure molecular sieve rich in mesoporous phosphorus and metal based on the dry weight, 1-60 wt% of inorganic binder based on the dry weight, and optionally 0-60 wt% of second clay based on the dry weight, and the inorganic binder comprises phosphorus-aluminum inorganic binder and/or other inorganic binders. The catalyst of the invention has better ethylene selectivity in the catalytic cracking reaction of petroleum hydrocarbon and can produce more propylene and BTX.

Description

Catalytic cracking catalyst, preparation method thereof and hydrocarbon oil catalytic cracking method

Technical Field

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

Background

The Fluid Catalytic Cracking (FCC) has the characteristics of short flow and good economic benefit, and is one of the main processing means for crude oil lightening in China. At present, domestic finished oil supply and demand are in conflict, and important organic chemical raw materials such as ethylene, propylene and the like need to be imported in large quantities for a long time. To meet the market demand, the development of competitive chemical raw material production technology is receiving attention.

The cracking reaction of hydrocarbons at high temperature is to convert long-chain hydrocarbons into low-carbon olefins such as ethylene and propylene with high added values. Generally, the cracking of hydrocarbons can be divided into carbonium ion mechanism and radical mechanism, depending on the mechanism. The carbonium ion mechanism needs to be capable of occurring under the action of an acid catalyst, the required reaction temperature is relatively low, the cracking product takes propylene as a characteristic product, the free radical mechanism generally reacts under the condition of thermal initiation, and the cracking product takes ethylene as a characteristic product. In fact, hydrocarbons undergo both carbonium and free radical reactions under catalytic cracking reaction conditions. However, because the reaction temperature is low, the initiation speed of free radicals is low, the reaction process is mainly based on the carbonium ion reaction, the propylene yield is high, the ethylene yield is low, and the prior art cannot achieve large-scale fine free regulation and control on the ethylene/propylene ratio in the product.

In the catalytic thermal cracking catalyst for producing light olefins in high yield, ZSM-5 molecular sieve is generally used as the active component, and the molecular sieve property is adjusted to mainly increase the yield of C3-C5-olefins, so that the ethylene yield is not very high.

CN1072032C discloses a molecular sieve composition for catalytic cracking to produce ethylene and propylene in high yield, which is prepared from SiO₂/Al₂O₃The five-membered ring molecular sieve with the molar ratio of 15-60 is prepared by activating and modifying P, alkaline earth metal and transition metal. P of modified molecular sieve₂O₅2 to 10 wt%, 0.3 to 5 wt% of an alkaline earth metal oxide, and 0.3 to 5 wt% of a transition metal oxide. The structure and active center of the molecular sieve have high thermal and hydrothermal stability.

CN1147420A discloses a molecular sieve containing phosphorus and rare earth and having MFI structure, and the anhydrous chemical composition of the molecular sieve is aRE₂O₃bNa₂OAl₂O₃cP₂O₅dSiO₂Wherein a is 0.01 to 0.25, b is 0.005 to 0.02, c is 0.2 to 1.0, and d is 35 to 120. The molecular sieve has excellent hydrothermal activity stability and good low-carbon olefin selectivity when being used for high-temperature conversion of hydrocarbons.

In the prior art, the modulation of the properties of the molecular sieve has an unobvious effect on the improvement of the yield and the selectivity of ethylene.

Disclosure of Invention

The invention aims to provide a catalytic cracking catalyst, a preparation method thereof and a hydrocarbon oil catalytic cracking method.

In order to achieve the above object, the present invention provides in a first aspect a catalytic cracking catalyst comprising 1 to 30 wt% of a Y-type molecular sieve based on the weight of the catalytic cracking catalyst on a dry basis, 5 to 55 wt% of a mesoporous rich phosphorus and metal containing MFI structure molecular sieve based on the weight of the catalytic cracking catalyst on a dry basis, 1 to 60 wt% of an inorganic binder based on the weight of the dry basis, and optionally 0 to 60 wt% of a second clay based on the weight of the dry basis; the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders;

n (SiO) of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores₂)/n(Al₂O₃) Greater than 15 and less than 70; with P₂O₅The phosphorus content of the MFI structure molecular sieve rich in the mesoporous phosphorus and the metal is 1-15 wt% based on the dry weight of the MFI structure molecular sieve rich in the mesoporous phosphorus and the metal; the content of a loading metal M1 in the MFI structure molecular sieve rich in mesoporous phosphorus and metal is 1-10 wt% and the content of a loading metal M2 in the MFI structure molecular sieve rich in mesoporous phosphorus and metal is 0.1-5 wt% based on the dry weight of the MFI structure molecular sieve rich in mesoporous phosphorus and metal, wherein the loading metal M1 is selected from one or two of lanthanum and cerium, and the loading metal M2 is selected from one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the phosphorus and metal rich MFI structure molecular sieve in the total pore volume is 40-70%, the mesopore volume and the total pore volume of the phosphorus and metal rich MFI structure molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers.

Optionally, the RE distribution parameter D of the mesoporous phosphorus and metal rich molecular sieve satisfies: d is more than or equal to 0.9 and less than or equal to 1.3, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of the crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face.

Alternatively, n (SiO) of the phosphorus and metal rich mesoporous MFI structure molecular sieve₂)/n(Al₂O₃) Greater than 18 and less than 60; with P₂O₅The phosphorus content of the MFI structure molecular sieve which is rich in mesoporous phosphorus and metal is 3-12 wt% based on the dry weight of the molecular sieve; the content of the loaded metal M1 in the MFI structure molecular sieve rich in mesoporous is 3-8 wt% and the content of the loaded metal M2 in the MFI structure molecular sieve rich in mesoporous is 0.5-3 wt% based on the dry weight of the MFI structure molecular sieve rich in mesoporous and containing phosphorus and metal; the proportion of the mesopore volume of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores accounts for 45-65% of the total pore volume.

Optionally, the catalytic cracking catalyst contains 2-45 wt% of a phosphorus-aluminum inorganic binder based on the dry weight of the catalytic cracking catalyst and/or no more than 30 wt% of other inorganic binders based on the dry weight of the catalytic cracking catalyst.

Optionally, the aluminophosphate inorganic binder is an aluminophosphate glue and/or a aluminophosphate inorganic binder containing a first clay; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the other inorganic binder includes at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass.

Optionally, the second clay is at least one selected from the group consisting of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite, and rectorite.

Optionally, the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

In a second aspect, the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising: mixing and pulping the Y-type molecular sieve, the phosphorus-and metal-containing MFI structure molecular sieve rich in mesopores and an inorganic binder, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the mesoporous-rich phosphorus-and-metal-containing MFI structure molecular sieve, the inorganic binder and the second clay is (1-30): (5-55): (1-60): (0-60);

the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; n (SiO) of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores₂)/n(Al₂O₃) Greater than 15 and less than 70; with P₂O₅The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; the content of a load metal M1 in the molecular sieve is 1-10 wt% and the content of a load metal M2 is 0.1-5 wt% based on the dry weight of the molecular sieve, wherein the load metal M1 is selected from one or two of lanthanum and cerium, and the load metal M2 is selected from one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 40-70%, the mesopore volume and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers.

Optionally, the method further comprises: washing and optionally drying the product obtained by roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature of the roasting treatment is 300-650 ℃, and the roasting time is 0.5-12 h.

Optionally, the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve; the second clay is at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite.

Optionally, the binder comprises the phosphor-aluminum inorganic binder and the other inorganic binder; the amount of the phosphorus-aluminum inorganic binder is 2 to 45 parts by weight on a dry basis relative to 1 to 30 parts by weight of the Y-type molecular sieve on a dry basis; the dosage of the other inorganic binders is 1 to 30 weight portions; wherein the other inorganic binder comprises at least one of pseudoboehmite, alumina sol, silica alumina sol and water glass; the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay.

Optionally, the method further comprises: preparing the first clay-containing aluminophosphate inorganic binder by the following steps:

pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide source is 15-40 parts by weight of Al₂O₃(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis;

adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al to 1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.

Optionally, the method further comprises: the phosphorus-and metal-rich MFI structure molecular sieve is prepared by the following steps:

a. filtering and washing the crystallized MFI structure molecular sieve slurry to obtain a water-washed molecular sieve; wherein the sodium content of the washed molecular sieve is less than 5 wt% based on the total dry basis weight of the washed molecular sieve based on sodium oxide;

b. b, desiliconizing the washed molecular sieve obtained in the step a in an alkaline solution, and filtering and washing to obtain an alkaline washed molecular sieve;

c. b, performing ammonium exchange treatment on the alkali washing molecular sieve obtained in the step b to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content of less than 0.2 wt.% based on sodium oxide and based on total dry basis weight of the ammonium exchanged molecular sieve;

d. and c, carrying out phosphorus modification treatment, metal loading treatment and third roasting treatment on the ammonium exchange molecular sieve obtained in the step c to obtain the phosphorus and metal containing MFI structure molecular sieve rich in mesopores.

Optionally, the step d is selected from one or more of the following ways:

mode (1): c, simultaneously carrying out the phosphorus modification treatment and the loading treatment of the loaded metal on the ammonium exchange molecular sieve obtained in the step c, and then carrying out the third roasting treatment;

mode (2): c, sequentially carrying out load treatment on the ammonium exchange molecular sieve obtained in the step c by using a load metal M1 and third roasting treatment in a water vapor atmosphere, and then carrying out load treatment on the load metal M2, phosphorus modification treatment and third roasting treatment in an air atmosphere;

mode (3): c, carrying out loading treatment on the ammonium exchange molecular sieve obtained in the step c by using a loading metal M1, and then carrying out loading treatment on a loading metal M2, phosphorus modification treatment and third roasting treatment;

mode (4): and c, carrying out phosphorus modification treatment, loading treatment of the loaded metal M2 and third roasting treatment in an air atmosphere on the ammonium exchange molecular sieve obtained in the step c, and then carrying out loading treatment of the loaded metal M1 and third roasting treatment in a water vapor atmosphere.

Optionally, the MFI structure molecular sieve in the MFI structure molecular sieve slurry obtained by crystallization is a ZSM-5 molecular sieve, and the silica-alumina ratio is less than 80;

if the MFI structure molecular sieve slurry obtained by crystallization is prepared by adopting a template method, the step b further comprises the following steps: and drying and fourth roasting the washed molecular sieve to remove the template agent, and then carrying out desiliconization treatment.

Optionally, in step b, the alkali in the alkali solution is sodium hydroxide and/or potassium hydroxide; the conditions of the desiliconization treatment include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature is 10 ℃ to 100 ℃ and the time is 0.2-4 hours.

Optionally, in step c, the ammonium exchange treatment conditions include: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10), the temperature is 10 ℃ to 100 ℃, and the time is 0.2-4 hours;

the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.

Optionally, in step d, the phosphorus modification treatment comprises: impregnating and/or ion-exchanging the molecular sieve with at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate;

the loading treatment of the loaded metal comprises: loading a compound containing a supported metal onto the molecular sieve by impregnation and/or ion exchange one or more times;

the conditions of the third roasting treatment include: the atmosphere is air atmosphere and/or water vapor atmosphere, the roasting temperature is 400-800 ℃, and the roasting time is 0.5-8 hours.

A third aspect of the present disclosure provides a catalytic cracking catalyst prepared by the method of the second aspect of the present disclosure.

A fourth aspect of the present disclosure provides a method for catalytic cracking of a hydrocarbon oil, the method comprising: under catalytic cracking reaction conditions, the hydrocarbon oil is contacted and reacted with the catalytic cracking catalyst described in the first and third aspects of the present disclosure.

Optionally, the catalytic cracking reaction conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, direct current wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction products.

The inventor of the invention unexpectedly finds that the MFI structure molecular sieve containing phosphorus and metal prepared by desiliconizing the MFI structure molecular sieve by a chemical method, washing sodium and then carrying out phosphorus modification treatment and metal loading treatment can be applied to catalytic cracking and catalytic cracking processes and can be used as an active component of a catalyst or an auxiliary agent.

The catalytic cracking catalyst provided by the invention contains the MFI structure molecular sieve after desiliconization treatment, has rich mesoporous structure, is beneficial to the migration of rare earth into molecular sieve pore channels, and strengthens the synergistic effect of the rare earth and the molecular sieve acid center.

The catalytic cracking catalyst provided by the invention has the characteristics of strong cracking capability, good shape-selective performance, high ethylene yield and ethylene selectivity, and high propylene and BTX yield and selectivity.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

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 invention provides a catalytic cracking catalyst, which contains 1-30 wt% of Y-type molecular sieve based on the dry weight of the catalytic cracking catalyst, 5-55 wt% of MFI structure molecular sieve rich in mesoporous phosphorus and metal based on the dry weight of the catalytic cracking catalyst, 1-60 wt% of inorganic binder based on the dry weight of the catalytic cracking catalyst and optional 0-60 wt% of second clay based on the dry weight of the catalytic cracking catalyst, wherein the inorganic binder comprises phosphorus-aluminum inorganic binder and/or other inorganic binders; n (SiO) of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores₂)/n(Al₂O₃) Greater than 15 and less than 70; with P₂O₅The phosphorus content of the MFI structure molecular sieve which is rich in mesoporous phosphorus and metal is 1-15 wt% based on the dry weight of the molecular sieve; said enrichment being based on the metal-bearing oxide and on the dry weight of the molecular sieveThe content of a load metal M1 in the mesoporous MFI structure molecular sieve containing phosphorus and metal is 1-10 wt%, and the content of a load metal M2 is 0.1-5 wt%, wherein the load metal M1 is selected from one or two of lanthanum and cerium, and the load metal M2 is selected from one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the phosphorus and metal rich MFI structure molecular sieve in the total pore volume is 40-70%, the mesopore volume and the total pore volume of the phosphorus and metal rich MFI structure molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers. Preferably, the n (SiO) of the mesoporous rich phosphorus and metal containing MFI structure molecular sieve₂)/n(Al₂O₃) Greater than 18 and less than 60; with P₂O₅Taking the dry basis weight of the phosphorus and metal rich MFI structure molecular sieve as a reference, wherein the phosphorus content of the phosphorus and metal rich MFI structure molecular sieve is 3-12 wt%; the content of the loaded metal M1 in the MFI structure molecular sieve rich in mesoporous phosphorus and metal is 3-8 wt% and the content of the loaded metal M2 is 0.5-3 wt%, based on the oxide of the loaded metal and the dry weight of the MFI structure molecular sieve rich in mesoporous phosphorus and metal; the proportion of the mesopore volume of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores accounts for 45-65% of the total pore volume.

The catalytic cracking catalyst provided by the invention has the performance of promoting the free radical reaction, can realize the purpose of modulating the cracking activity and the product distribution by modulating the proportion of the carbonium ion route and the free radical route at the catalytic cracking temperature, can improve the yield and the selectivity of ethylene, and can produce more propylene and BTX.

According to the invention, RE distribution parameter D of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores meets the following requirements: d is more than or equal to 0.9 and less than or equal to 1.3, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of the crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face. When RE distribution parameter D of the MFI structure molecular sieve rich in mesoporous phosphorus and metal meets the range, more rare earth exists in the pore channel, and the catalyst containing the molecular sieve has the advantage of further improving the yield of ethylene, propylene and BTX.

According to the catalytic cracking catalyst of the present invention, it is well known to those skilled in the art to determine the rare earth content of the phosphorus and metal rich mesoporous MFI structure molecular sieve by TEM-EDS method, wherein the geometric center is also well known to those skilled in the art, and can be calculated according to a formula, which is not repeated in the present invention, and the geometric center of the general symmetric figure is the intersection of the connecting lines of the relative vertexes, for example, the geometric center of the hexagonal crystal face of the conventional hexagonal plate-shaped ZSM-5 is at the intersection of three relative vertexes.

In accordance with the catalytic cracking catalyst of the present invention, the binder may be well known to those skilled in the art, for example, the binder may include a phosphor-aluminum inorganic binder and/or other inorganic binders. Preferably, the binder comprises a phosphoaluminate inorganic binder and a further inorganic binder, for example the binder may comprise from 2 to 45 wt% of the phosphoaluminate inorganic binder, based on the total weight of the binder, and no more than 30 wt%, for example from 1 to 30 wt%, based on the weight of the binder, on a dry basis.

According to the present disclosure, the aluminophosphate inorganic binder may be a first clay-containing aluminophosphate inorganic binder and/or a aluminophosphate glue.

In one embodiment, the phosphorus-aluminum inorganic binder comprises Al based on the dry weight of the phosphorus-aluminum inorganic binder₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80 wt% of phosphorus component and 0-40 wt% of first clay calculated by dry basis weight, and the P/Al weight ratio is 1.0-6.0, pH value is 1-3.5, and solid content is 15-60 wt%; for example, including Al₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80 wt% of a phosphorus component and 1-40 wt% of a first clay, based on dry weight; preferably contains Al₂O₃15-35% by weight, calculated as P, of an aluminium component₂O₅50-75 wt% of a phosphorus component and 8-35 wt% of a first clay, calculated on a dry basis, and preferably having a P/Al weight ratio of 1.2-6.0, more preferably 2.0-5.0, and a pH value of 1.5-3.0.

In another embodiment, the phosphorus aluminum inorganic binder comprises Al based on the dry weight of the phosphorus aluminum inorganic binder₂O₃20-40% by weight, calculated as P, of an aluminium component₂O₅60-80% by weight of a phosphorus component.

Clays are well known to those skilled in the art in light of this disclosure, and the first clay may be at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth, preferably including rectorite, more preferably rectorite; the additional inorganic binder may be selected from one or more of inorganic oxide binders conventionally used in catalytic cracking catalysts or catalyst binder components other than the aluminophosphate and aluminophosphate inorganic binders, preferably from at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass, more preferably from at least one of pseudoboehmite and alumina sol.

In the catalytic cracking catalyst according to the present invention, the clay is well known to those skilled in the art, and the second clay may be at least one selected from the group consisting of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and rectorite, and is preferably kaolin, metakaolin, rectorite. The catalyst of the present invention preferably contains 5 to 55 wt% of the second clay, for example 12 to 28 wt% or 15 to 40 wt% of the second clay, based on the total weight of the catalyst.

In the catalytic cracking catalyst, the molecular sieve is a Y-type molecular sieve and an MFI structure molecular sieve rich in mesoporous phosphorus and metal, and preferably, the Y-type molecular sieve and the MFI structure molecular sieve rich in mesoporous phosphorus and metal account for 6-85 wt% of the dry basis of the catalyst, and more preferably 20-60 wt%. Further, the Y-type molecular sieve accounts for 1-30 wt% of the dry basis of the catalyst, and the MFI structure molecular sieve rich in mesoporous phosphorus and metal accounts for 5-55 wt% of the dry basis of the catalyst.

The Y-type molecular sieve is used for a catalytic cracking catalyst, and the Y-type molecular sieve is at least one of PSRY (polystyrene-associated ternary copolymer) and PSRY-S (polystyrene-associated ternary copolymer) molecular sieves, PSRY-S molecular sieves containing rare earth, USY molecular sieves containing rare earth, REY molecular sieves, REHY molecular sieves and HY molecular sieves. Preferably, the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve rich in mesoporous phosphorus and metal is 1: 4-4: 0.1.

In one embodiment according to the present disclosure, the catalyst comprises 5-40 wt% of a phosphorus-aluminum inorganic binder, 1.5-25 wt% of a Y-type molecular sieve, 10-50 wt% of a mesoporous rich phosphorus and metal containing MFI structure molecular sieve, 5-55 wt% of a second clay, 5-25 wt% of other inorganic binders.

The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps: mixing and pulping the Y-type molecular sieve, the phosphorus-and metal-containing MFI structure molecular sieve rich in mesopores and an inorganic binder, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the mesoporous-rich phosphorus-and-metal-containing MFI structure molecular sieve, the inorganic binder and the second clay is (1-30): (5-55): (1-60): (0-60); on a dry basis, relative to 1-30 parts by weight of the Y-type molecular sieve, the mesoporous-rich phosphorus-and-metal MFI structure molecular sieve is used in an amount of 5-55 parts by weight, the inorganic binder is used in an amount of 1-60 parts by weight, and the second clay is used in an amount of 0-60 parts by weight.

The inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; n (SiO) of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores₂)/n(Al₂O₃) Greater than 15 and less than 70; with P₂O₅The molecular sieve has a phosphorus content based on the dry weight of the molecular sieveIn an amount of 1-15 wt%; the content of a load metal M1 in the molecular sieve is 1-10 wt% and the content of a load metal M2 is 0.1-5 wt% based on the dry weight of the molecular sieve, wherein the load metal M1 is selected from one or two of lanthanum and cerium, and the load metal M2 is selected from one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 40-70%, the mesopore volume and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers.

According to the present disclosure, the method may further comprise: washing and optionally drying the product obtained by roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature can be 300-650 ℃, for example 400-600 ℃, preferably 450-550 ℃, and the roasting time can be 0.5-6 hours or 0.5-2 hours; the washing can be one of ammonium sulfate, ammonium nitrate and ammonium chloride, and the washing temperature can be 40-70 ℃; the temperature of the drying treatment can be 100-200 ℃, for example 110-180 ℃, and the drying time can be 0.5-24 h, for example 0.5-12 h.

For example, in one embodiment, the catalytic cracking catalyst may be prepared by: mixing an inorganic 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 gel) with a second clay (such as kaolin) and water (such as deoxidized ionized water and/or deionized water), preparing slurry with the solid content of 10-50 wt%, uniformly stirring, adjusting the pH of the slurry to 1-4 by using an inorganic acid (such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid), keeping the pH value, standing and aging at 20-80 ℃ for 0-2 hours, adding the alumina sol and/or the silica sol after 0.3-2 hours, stirring for 0.5-1.5 hours to form colloid, and then adding a molecular sieve, wherein the molecular sieve comprises the phosphorus-metal containing MFI structure molecular sieve rich in mesopores and a Y-type molecular sieve to form catalyst slurry, and the solid content of the catalyst slurry is 20-45 wt%, continuously stirring and then spray drying to prepare the microsphere catalyst. Then, the microspherical catalyst is calcined at 300 to 650 ℃, preferably 450 to 550 ℃ for 0.5 to 6 hours or 0.5 to 2 hours, washed with ammonium sulfate (wherein the washing temperature can be 40 to 70 ℃, the weight ratio of ammonium sulfate to microspherical catalyst: water is 0.2 to 0.8:1:5 to 15) until the content of sodium oxide is less than 0.25 wt%, washed with water, filtered, and then dried.

In the method according to the present invention, the Y-type molecular sieve includes, for example, at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve, and an HY molecular sieve; the second clay is at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite.

In accordance with the present disclosure, the inorganic binder may be of a type conventional in the art, preferably including a phosphoaluminous inorganic binder and/or other inorganic binders.

In one embodiment, the inorganic binder comprises the phosphor-aluminum inorganic binder and the other inorganic binder, and the phosphor-aluminum inorganic binder may be used in an amount of 2 to 45 parts by weight, preferably 5 to 40 parts by weight, on a dry basis, relative to 1 to 30 parts by weight, on a dry basis, of the Y-type molecular sieve; the other inorganic binder may be used in an amount of 1 to 30 parts by weight, preferably 5 to 25 parts by weight. Wherein the aluminophosphate inorganic binder can be an aluminophosphate glue and/or a aluminophosphate inorganic binder comprising a first clay; the other inorganic binder may include at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass.

The preparation method of the catalytic cracking catalyst provided by the present disclosure can mix and pulp the phosphorus and metal rich MFI structure molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, which are rich in mesopores, and the order of charging the inorganic binders has no special requirements, for example, the phosphorus-aluminum inorganic binder, other inorganic binders, the molecular sieve and the second clay can be mixed and beaten (when the second clay is not contained, the relevant charging step can be omitted), preferably, the phosphorus-aluminum inorganic binder is added after the second clay, the molecular sieve and other inorganic binders are mixed and beaten, which is beneficial to improving the activity and selectivity of the catalyst.

The preparation method of the catalytic cracking catalyst provided by the disclosure further comprises the step of spray drying the slurry obtained by pulping. Methods of spray drying are well known to those skilled in the art and no particular requirement of the present disclosure exists.

Further, the method of the present disclosure may further comprise preparing the first clay-containing aluminophosphate inorganic binder by:

According to the present disclosure, the alumina source may be at least one selected from the group consisting of rho-alumina, x-alumina, eta-alumina, gamma-alumina, kappa-alumina, sigma-alumina, theta-alumina, gibbsite, metaflumite, nordstrandite, diaspore, boehmite, and pseudoboehmite from which the aluminum component of the first clay-containing aluminophosphate inorganic binder is derived. The first clay can be one or more of high alumina, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, and preferably rectorite. The concentrated phosphoric acid may be present in a concentration of 60 to 98 wt.%, more preferably 75 to 90 wt.%. The feed rate of phosphoric acid is preferably 0.01 to 0.10kg of phosphoric acid per minute per kg of alumina source, more preferably 0.03 to 0.07kg of phosphoric acid per minute per kg of alumina source.

In the embodiment, due to the introduction of the clay, the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer among materials in the preparation process, but also avoids the solidification of the binder caused by nonuniform local instant violent reaction, heat release and overtemperature, and the bonding performance of the obtained binder is equivalent to that of the phosphorus-aluminum binder prepared by a method without introducing the clay; in addition, the method introduces clay, especially rectorite with a layered structure, improves the heavy oil conversion capability of the catalyst, and enables the obtained catalyst to have better selectivity.

The method according to the present disclosure may further include: the phosphorus and metal containing MFI structure molecular sieve rich in mesopores is prepared by the following steps:

d. and c, carrying out phosphorus modification treatment, loading treatment of loading metals (the loading metals comprise loading metal M1 and loading metal M2) and third roasting treatment on the ammonium exchange molecular sieve obtained in the step c to obtain the phosphorus and metal containing MFI structure molecular sieve rich in mesopores.

According to the invention, said step d may be selected in one or more of the following ways:

mode (1): and c, simultaneously carrying out the phosphorus modification treatment and the loading treatment of the loaded metal on the ammonium exchange molecular sieve obtained in the step c, and then carrying out the third roasting treatment.

Mode (2): and c, sequentially carrying out load treatment of the load metal M1 and third roasting treatment in a water vapor atmosphere on the ammonium exchange molecular sieve obtained in the step c, and then carrying out load treatment of the load metal M2, phosphorus modification treatment and third roasting treatment in an air atmosphere. By adopting the method, more rare earth can be contained in the pore canal of the molecular sieve, thereby improving the yield of ethylene, propylene and BTX.

Mode (3): and c, carrying out loading treatment on the ammonium exchange molecular sieve obtained in the step c by using loading metal M1, and then carrying out loading treatment on loading metal M2, phosphorus modification treatment and third roasting treatment.

According to the present invention, the MFI structure molecular sieve slurry obtained by crystallization is well known to those skilled in the art, and may be obtained by amine-free crystallization, or may be a molecular sieve slurry prepared by a template method, for example, the MFI structure molecular sieve in the MFI structure molecular sieve slurry obtained by crystallization is a ZSM-5 molecular sieve, and the silica-alumina ratio is less than 80. If the MFI structure molecular sieve slurry obtained by the crystallization is prepared by a template method, step b may further include: the desiliconization treatment is carried out after the washed molecular sieve is dried and calcined to remove the template agent, and the drying and calcining temperature is well known to those skilled in the art and is not described in detail.

According to the present invention, the alkaline solution in step b is well known to the person skilled in the art, and the alkaline in said alkaline solution may be an inorganic alkaline, such as sodium hydroxide and/or potassium hydroxide. The conditions of the desiliconization treatment may include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature may be 10 ℃ to 100 ℃, for example 15 ℃ to 90 ℃, and the time may be 0.2-4 hours, for example 0.5-2 hours.

According to the present invention, the ammonium exchange treatment in step c is well known to those skilled in the art, for example, the conditions of the ammonium exchange treatment include: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10) the temperature may be from 10 ℃ to 100 ℃, for example from 15 ℃ to 90 ℃, and the time may be from 0.2 to 4 hours, for example from 0.5 to 2 hours, and the ammonium salt may be a commonly used inorganic ammonium salt, for example one or more selected from ammonium chloride, ammonium sulfate and ammonium nitrate.

According to the present invention, in step d, the phosphorus modification treatment is used for loading phosphorus in the molecular sieve, and may include, for example: at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate is impregnated and/or ion-exchanged with the molecular sieve. The loading treatment is used for loading a metal in a molecular sieve, and for example, the loading treatment of the loaded metal may include: loading the supported metal on the molecular sieve by impregnating and/or ion-exchanging a compound containing the supported metal once or in multiple times. The phosphorus modification treatment and the supporting treatment may be performed together or separately.

According to the invention, in step d, the calcination treatment is well known to the person skilled in the art, for example the conditions of the third calcination treatment may include: the atmosphere is air atmosphere and/or water vapor atmosphere, the baking temperature is 400-800 ℃, such as 460-720 ℃ or 410-680 ℃, and the baking temperature can be 0.5-8 hours, such as 1.0-6.5 hours or 2.5-7 hours.

The invention also provides the catalytic cracking catalyst prepared by the method.

The invention also provides a method for carrying out catalytic cracking on hydrocarbon oil by using the catalytic cracking catalyst.

The method may be conventional in the art, and for example, the hydrocarbon oil is contacted with the catalytic cracking catalyst of the present invention under catalytic cracking conditions. The catalytic cracking catalyst provided by the invention can be used for catalytic cracking of various hydrocarbon oils. The hydrocarbon oil may be selected from one or more of various petroleum fractions, such as crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiled, coker wax oil, and coal liquefaction product. The hydrocarbon oil can contain heavy metal impurities such as nickel, vanadium and the like, and sulfur and nitrogen impurities, for example, the content of sulfur in the hydrocarbon oil can be up to 3.0 weight percent, the content of nitrogen can be up to 2.0 weight percent, and the content of metal impurities such as vanadium, nickel and the like can be up to 3000 ppm; catalytic cracking conditions may be conventional in the art, preferably including: the reaction temperature is 500 ℃ and 800 ℃ such as 520 ℃ and 680 ℃.

The present invention will be further illustrated by the following examples, but the present invention is not limited thereto, and 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 catalyst on the yield, selectivity and BTX yield of ethylene and propylene in the catalytic cracking of petroleum hydrocarbon is evaluated by adopting a fixed bed micro-reaction. The prepared catalyst sample is aged for 17 hours at 800 ℃ under 100 percent water vapor on a fixed bed aging device, and is evaluated on the micro-reaction of heavy oil, wherein the raw oil is VGO, the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the agent-oil ratio is 3.2.

The crystallinity of the process of the invention is determined using the standard method of ASTM D5758-2001(2011) e 1.

N (SiO) of the process of the invention₂)/n(Al₂O₃) Namely, the silicon-aluminum ratio is calculated by the contents of silicon oxide and aluminum oxide, and the contents of the silicon oxide and the aluminum oxide are measured by the GB/T30905-2014 standard method.

The phosphorus content of the method is determined by adopting a GB/T30905-2014 standard method, and the content of the load metal is determined by adopting the GB/T30905-2014 standard method.

The specific surface area of the method of the invention is determined using the GB5816 standard method.

The pore volume of the process of the invention is determined using the GB5816 standard method.

The sodium content of the method is determined by adopting the GB/T30905-2014 standard method.

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

The D value is calculated as follows: selecting a crystal grain and a certain crystal face of the crystal grain in a transmission electron mirror to form a polygon, wherein the polygon has a geometric center, an edge and a 10% distance H from the geometric center to the edge (different edge points and different H values), respectively selecting any one of regions in the inward H distance of the edge of the crystal face which is larger than 100 square nanometers and any one of regions in the outward H distance of the geometric center of the crystal face which is larger than 100 square nanometers, measuring the rare earth content (if two kinds of rare earth exist, measuring the total rare earth content), namely RE (S1) and RE (C1), calculating D1 to RE (S1)/RE (C1), respectively selecting different crystal grains to measure for 5 times, and calculating the average value to be D.

Some of the raw materials used in the examples had the following properties:

the pseudoboehmite is an industrial product produced by Shandong aluminum industry company, and the solid content is 60 percent by weight; the aluminum sol is an industrial product, Al, produced by the Qilu division of the medium petrochemical catalyst₂O₃The content was 21.5 wt%; the silica sol is an industrial product, SiO, produced by the middle petrochemical catalyst Qilu division₂The content was 28.9% by weight, Na₂The O content is 8.9 percent; the kaolin is kaolin specially used for a catalytic cracking catalyst produced by Suzhou kaolin company, and has the solid content of 78 weight percent. Fe₂O₃The content of Na was 2.0 wt%₂The O content was 0.03% by weight, and the solid content was 77% by weight; the rectorite is produced by Taixiang famous stream rectorite development Limited company in Hubei province, and the content of the quartz sand<3.5 wt.% of Al₂O₃39.0 wt.% of Fe₂O₃The content of Na was 2.0 wt%₂The O content was 0.03% by weight, and the solid content was 77% by weight; SB aluminum hydroxide powder, manufactured by Condex, Germany, Al₂O₃The content was 75% by weight; gamma-alumina, manufactured by Condex, Germany, Al₂O₃The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, and is produced in Beijing chemical plant. HRY (Long-range catalyst division, rare earth content 10 wt%), PSRY molecular sieves (Long-range catalyst division).

Example 1

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) the mother liquor was filtered off and washed with water to Na₂The content of O is lower than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing to obtain the final productThe solution is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added₄Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na₂The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 9.7g of H₃PO₄(concentration 85% by weight), 4.6g Fe (NO)₃)₃·9H₂O and 8.1gLa (NO)₃)₃·6H₂And O, uniformly mixing, soaking, drying and roasting at 550 ℃ for 2 hours. The molecular sieve A is obtained, and the physicochemical property data are shown in Table 1.

Example 2

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) the mother liquor was filtered off and washed with water to Na₂The content of O is lower than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added₄Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na₂The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 5.8g of H₃PO₄(concentration 85% by weight), 3.1g Fe (NO)₃)₃·9H₂O and 4.9gCe (NO)₃)₂·6H₂And O, uniformly mixing, soaking, drying and roasting at 550 ℃ for 2 hours. The molecular sieve B is obtained, and the physicochemical property data are shown in Table 1.

Example 3

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) the mother liquor was filtered off and washed with water to Na₂The content of O is lower than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, washingWashing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added₄Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na₂The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 11.6g H₃PO₄(concentration 85% by weight), 6.2g Fe (NO)₃)₃·9H₂O、8.1gLa(NO₃)₃·6H₂O and 4.9gCe (NO)₃)₂·6H₂And O, uniformly mixing, soaking, drying and roasting at 550 ℃ for 2 hours. The molecular sieve C is obtained, and the physicochemical property data are shown in Table 1.

Comparative example 1

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) with NH₄Cl exchange washing to Na₂The O content is less than 0.2 wt%; taking 50g (dry basis) of the molecular sieve, adding water, pulping to obtain molecular sieve pulp with the solid content of 40 weight percent, adding 7.7g H₃PO₄(concentration 85% by weight), 4.6g Fe (NO)₃)₃·9H₂O and 8.1gLa (NO)₃)₃·6H₂And O, uniformly mixing, soaking, drying and roasting at 550 ℃ for 2 hours. Molecular sieve D1 was obtained, and the physicochemical property data are shown in Table 1.

Comparative example 2

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) the mother liquor was filtered off and washed with water to Na₂The content of O is lower than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added₄Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na₂The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake and pulping to obtain molecular sieve slurry with the solid content of 40 weight percentAdding 9.7g H₃PO₄(concentration 85% by weight) and 4.6g Fe (NO)₃)₃·9H₂And (3) uniformly mixing and soaking O, drying, and roasting at 550 ℃ for 2 hours. Molecular sieve D2 was obtained, and the physicochemical property data are shown in Table 1.

Comparative example 3

The crystallized ZSM-5 molecular sieve (produced by catalyst Qilu division, synthesized by amine-free method, n (SiO)₂)/n(Al₂O₃) 27) the mother liquor was filtered off and washed with water to Na₂The content of O is lower than 5.0 weight percent, and a filter cake is obtained by filtration; adding 100g (dry basis) of the molecular sieve into 1000g of 2.0% NaOH solution, heating to 65 ℃, reacting for 30min, rapidly cooling to room temperature, filtering, and washing until the filtrate is neutral. Then, the filter cake was added to 800g of water and slurried, 40g of NH was added₄Cl, heating to 75 ℃, and carrying out exchange treatment for 1h until Na₂The O content is lower than 0.2 weight percent, and a molecular sieve filter cake is obtained after filtering and washing; taking 50g (dry basis) of the molecular sieve filter cake, adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 40 weight percent, and adding 9.7g of H₃PO₄(concentration 85% by weight) and 8.1gLa (NO)₃)₃·6H₂And O, uniformly mixing, soaking, drying and roasting at 550 ℃ for 2 hours. Molecular sieve D3 was obtained, and the physicochemical property data are shown in Table 1.

Examples 4-7 provide a phosphoaluminate inorganic binder for use in the present disclosure.

Example 4

This example prepared a phosphoaluminate inorganic binder as described in the present disclosure.

1.91 kg of pseudoboehmite (containing Al)₂O₃1.19 kg), 0.56 kg kaolin (0.5 kg on a dry basis) and 3.27 kg decationized water, stirring and adding 5.37 kg concentrated phosphoric acid (85% by mass) into the slurry, wherein the adding speed of the phosphoric acid is 0.04 kg phosphoric acid/min/kg alumina source, heating to 70 ℃, and then reacting for 45 minutes at the temperature to obtain the phosphorus-aluminum inorganic binder. The material ratio is shown in Table 2, and the Binder Binder1 is obtained.

Examples 5 to 7

The phosphor-aluminum inorganic Binder was prepared by the method of example 4, and the material ratio is shown in table 2, to obtain Binder 2-4.

Examples 8-12 provide catalytic cracking catalysts of the present disclosure, and comparative examples 4, 5, 6 provide comparative catalytic cracking catalysts.

Example 8

Adding decationized water and alumina sol into A, Y molecular sieves (PSRY molecular sieves), kaolin and pseudo-boehmite to pulp for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuing to pulp for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in the embodiment 4, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain C1, wherein the mixture ratio is shown in Table 3.

Comparative examples 4, 5 and 6

A catalytic cracking catalyst was prepared as described in example 8, except that A was replaced with molecular sieves D1, D2 and D3, respectively, to obtain DC1, DC2 and DC3, the proportions of which are shown in Table 3.

Example 9

Adding decationized water and alumina sol into B, Y molecular sieves (PSRY molecular sieves), kaolin and pseudo-boehmite to pulp for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuing to pulp for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in the example 5, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain C2, wherein the mixture ratio is shown in Table 3.

Example 10

Adding decationized water and alumina sol into C, Y molecular sieves (HRY molecular sieves), kaolin and pseudo-boehmite to pulp for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, continuing to pulp for 45 minutes, adding the phosphorus-aluminum inorganic binder prepared in the example 6, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain C3, wherein the mixture ratio is shown in Table 3.

Example 11

Adding decationized water and silica sol into a molecular sieve A, Y type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to be 3.0, then continuously pulping for 45 minutes, then adding the phosphorus-aluminum inorganic binder prepared in the embodiment 4, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain C4, wherein the mixture ratio is shown in Table 3.

Example 12

Adding decationized water into A, Y molecular sieve (PSRY molecular sieve) and kaolin, pulping for 120 minutes, adding the phosphorus-aluminum inorganic binder prepared in example 4 to obtain slurry with the solid content of 30 weight percent, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres at 500 ℃ for 1 hour to obtain C5, wherein the mixture ratio is shown in Table 3.

Example 13

Mixing a precursor (alumina sol) of an inorganic oxidation binder and kaolin according to the raw material proportion shown in Table 3, preparing the mixture into slurry with the solid content of 30 weight percent by using decationized water, uniformly stirring, adjusting the pH value of the slurry to 2.8 by using hydrochloric acid, standing and aging for 1 hour at 55 ℃, adding an MFI structure molecular sieve and a Y type molecular sieve (PSRY molecular sieve) which are rich in mesoporous phosphorus and metal to form catalyst slurry (the solid content is 35 weight percent), continuously stirring, and performing spray drying to prepare the microspherical catalyst. The microspherical catalyst was then calcined at 500 ℃ for 1 hour, washed with ammonium sulfate (where ammonium sulfate: microspherical catalyst: water 0.5:1:10) at 60 ℃ to a sodium oxide content of less than 0.25 wt%, then rinsed with deionized water and filtered, and then dried at 110 ℃ to give catalyst C6, the proportions of which are shown in table 3.

Examples 14-19 catalysts C1-C6 prepared in the examples of the present disclosure were evaluated for reaction performance using a fixed bed micro-reverse evaluation apparatus to demonstrate the catalytic cracking reaction effect of the catalytic cracking catalysts provided by the present disclosure.

Examples 14 to 19

The catalysts C1-C6 were subjected to aging treatment at 800 ℃ under a 100% steam atmosphere for 17 hours, respectively. And (3) loading the aged catalyst into a fixed bed micro-reaction reactor, and carrying out catalytic cracking on the raw oil shown in the table 4 under the evaluation conditions of the reaction temperature of 620 ℃, the regeneration temperature of 620 ℃ and the catalyst-to-oil ratio of 3.2. The reaction results for each catalyst are given in table 5.

Comparative examples 7 to 9 catalysts DC1, DC2, DC3 prepared in comparative examples of the present disclosure were subjected to performance evaluation in a fixed bed microreaction evaluation apparatus to illustrate the case of using comparative catalysts.

Comparative examples 7 to 9 the same feed oil was catalytically cracked by the same method as in example 14, except that the catalysts used were DC1, DC2 and DC3, respectively, which had been subjected to the same aging method as in example 14. The reaction results for each catalyst are given in table 5.

Examples 20-25 catalysts C1-C6 were subjected to an aging treatment at 800℃ under a 100% steam atmosphere for 17 hours, respectively. The aged catalyst was loaded into a fixed bed micro-reactor, and naphtha shown in Table 6 was catalytically cracked under the evaluation conditions of a reaction temperature of 620 ℃, a regeneration temperature of 620 ℃ and a catalyst-to-oil ratio of 3.2. The results of the individual catalyst reactions are given in table 7.

Comparative examples 10 to 12 catalysts DC1, DC2, DC3 prepared in comparative examples of the present disclosure were subjected to performance evaluation using a fixed bed microreflection evaluation apparatus to illustrate the case of using comparative catalysts.

Comparative examples 10 to 12 the same feed oil was catalytically cracked by the same method as in example 20, except that the catalysts used were DC1, DC2 and DC3, respectively, which had been subjected to the same aging method as in example 20. The results of the individual catalyst reactions are given in table 7.

TABLE 1

TABLE 2

Examples	Example 4	Example 5	Example 6	Example 7
					Binder numbering	Binder1	Binder2	Binder3	Binder4
Pseudo-boehmite, kg	1.91			1.60
					Al₂O₃，kg	1.19			1.00
SB，kg		0.94
					Al₂O₃，kg		0.70
γ-Al₂O₃，kg			0.58
					Al₂O₃，kg			0.58
Rectorite, kg		1.28	1.93
					Dry basis, kg		1.00	1.50
Kaolin clay, kg	0.56
					Dry basis, kg	0.50
Phosphoric acid, kg	5.37	5.36	4.03	6.50
					P₂O₅，kg	3.31	3.30	2.92	4.0
De-cationized water, kg	3.27	6.71	20.18	4.40
					Total amount of kg	11.11	14.29	25.00	12.5
Total dry basis, kg	5.00	5.00	5.00	5.00
					Binder solid content, kg/kg	0.45	0.35	0.20	0.40
P/Al	2.29	3.89	4.19	3.30
					Al₂O₃To weight percent	23.82	14.00	11.53	20.00
P₂O₅To weight percent	66.18	66.00	58.47	80.00
					First clay, weight%	10.00	20.00	30.00	0.00
pH	2.20	2.37	1.78	2.46

TABLE 3

TABLE 4

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

TABLE 5

TABLE 6

Raw materials	Naphtha (a)
		Density (20 ℃ C.)/(g.m)^-3)	735.8
Vapor pressure/kPa	32
		Mass group composition/%)
Alkane hydrocarbons	51.01
		N-alkanes	29.40
Cycloalkanes	38.24
		Olefins	0.12
Aromatic hydrocarbons	10.52
		Distillation range/. degree.C
First run	45.5
		5％	72.5
10％	86.7
		30％	106.5
50％	120.0
		70％	132.7
90％	148.5
		95％	155.2
End point of distillation	166.5

TABLE 7

As can be seen from the data in tables 5 and 7, when different feedstock oils are catalytically cracked, the catalyst containing the ZSM-5 molecular sieve rich in mesopores and modified with rare earth, phosphorus and transition metal shows excellent performance of producing more ethylene and more propylene and BTX, wherein the yield of ethylene, propylene and BTX is the highest with the catalysts containing a proper amount of aluminophosphate and other inorganic binders, while the yield of ethylene is significantly lower with the catalysis containing the molecular sieve not modified with rare earth or the catalysis containing the ZSM-5 molecular sieve modified with rare earth but not expanded with pore, and the yield of propylene and BTX is lower with the catalysts containing the molecular sieve modified with rare earth but not modified with transition metal although the yield of ethylene is higher.

The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A catalytic cracking catalyst, characterized in that the catalytic cracking catalyst contains 1-30 wt% of Y-type molecular sieve based on dry weight, 5-55 wt% of MFI structure molecular sieve rich in phosphorus and metal of mesoporous, 1-60 wt% of inorganic binder based on dry weight, and optionally 0-60 wt% of second clay based on dry weight; the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders;

2. The catalytic cracking catalyst of claim 1, wherein the mesoporous, phosphorus and metal rich molecular sieve has a RE distribution parameter D satisfying: d is more than or equal to 0.9 and less than or equal to 1.3, wherein D is RE (S)/RE (C), RE (S) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the edge of the crystal face of the molecular sieve crystal grain to the inside H by adopting a TEM-EDS method, RE (C) represents the content of rare earth in a region which is arbitrarily more than 100 square nanometers in the distance from the geometric center of the crystal face of the molecular sieve crystal grain to the outside H by adopting the TEM-EDS method, and H is 10 percent of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face.

3. The catalytic cracking catalyst of claim 1 or 2, wherein the phosphorus and metal rich mesoporous MFI structure molecular sieve n (SiO)₂)/n(Al₂O₃) Greater than 18 and less than 60; with P₂O₅The phosphorus content of the MFI structure molecular sieve which is rich in mesoporous phosphorus and metal is 3-12 wt% based on the dry weight of the molecular sieve; the content of the loaded metal M1 in the MFI structure molecular sieve rich in mesoporous is 3-8 wt% and the content of the loaded metal M2 in the MFI structure molecular sieve rich in mesoporous is 0.5-3 wt% based on the dry weight of the MFI structure molecular sieve rich in mesoporous and containing phosphorus and metal; the proportion of the mesopore volume of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores accounts for 45-65% of the total pore volume.

4. The catalytic cracking catalyst of claim 1, wherein the catalytic cracking catalyst contains 2 to 45 wt% of the aluminophosphate inorganic binder on a dry basis weight and/or no more than 30 wt% of other inorganic binders on a dry basis weight, based on the dry basis weight of the catalytic cracking catalyst.

5. The catalytic cracking catalyst of claim 4, wherein the aluminophosphate inorganic binder is an aluminophosphate glue and/or a first clay-containing aluminophosphate inorganic binder; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80% by weight of a phosphorus component andmore than 0 and not more than 40 wt% of first clay on a dry basis, wherein the weight ratio of P/Al of the phosphorus-aluminum inorganic binder containing the first clay is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the other inorganic binder includes at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass.

6. The catalytic cracking catalyst of claim 1, wherein the second clay is at least one selected from the group consisting of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and rectorite.

7. The catalytic cracking catalyst of claim 1, wherein the Y-type molecular sieve comprises at least one of PSRY molecular sieve, PSRY-S molecular sieve, PSRY molecular sieve containing rare earth, PSRY-S molecular sieve containing rare earth, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

8. A method of preparing a catalytic cracking catalyst, the method comprising: mixing and pulping the Y-type molecular sieve, the phosphorus-and metal-containing MFI structure molecular sieve rich in mesopores and an inorganic binder, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the mesoporous-rich phosphorus-and-metal-containing MFI structure molecular sieve, the inorganic binder and the second clay is (1-30): (5-55): (1-60): (0-60);

the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; n (SiO) of the phosphorus and metal-containing MFI structure molecular sieve rich in mesopores₂)/n(Al₂O₃) Greater than 15 and less than 70; with P₂O₅The phosphorus content of the molecular sieve is 1-15 wt% based on the dry weight of the molecular sieve; by oxidation of supported metalsCalculated by the substance and based on the dry weight of the molecular sieve, the content of the load metal M1 in the molecular sieve is 1-10 wt%, and the content of the load metal M2 is 0.1-5 wt%, wherein the load metal M1 is selected from one or two of lanthanum and cerium, and the load metal M2 is selected from one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 40-70%, the mesopore volume and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the mesopore volume is the pore volume with the pore diameter of more than 2 nanometers and less than 100 nanometers.

9. The method of claim 8, wherein the method further comprises: washing and optionally drying the product obtained by roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature of the roasting treatment is 300-650 ℃, and the roasting time is 0.5-12 h.

10. The method of claim 8, wherein the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve, and a HY molecular sieve; the second clay is at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite.

11. The method of claim 8, wherein the binder comprises the phosphor-aluminum inorganic binder and the other inorganic binder; the amount of the phosphorus-aluminum inorganic binder is 2 to 45 parts by weight on a dry basis relative to 1 to 30 parts by weight of the Y-type molecular sieve on a dry basis; the dosage of the other inorganic binders is 1 to 30 weight portions; wherein the other inorganic binder comprises at least one of pseudoboehmite, alumina sol, silica alumina sol and water glass; the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay.

12. The method of claim 11, wherein the method further comprises: preparing the first clay-containing aluminophosphate inorganic binder by the following steps:

13. The method of claim 8, wherein the method further comprises: the phosphorus-and metal-rich MFI structure molecular sieve is prepared by the following steps:

14. The method of claim 13, wherein step d is selected from one or more of the following:

15. The process of claim 13, wherein the MFI structure molecular sieve in the slurry of MFI structure molecular sieves obtained by the crystallization is a ZSM-5 molecular sieve having a silica to alumina ratio of less than 80;

16. The method according to claim 13, wherein in step b, the alkali in the alkali solution is sodium hydroxide and/or potassium hydroxide; the conditions of the desiliconization treatment include: the weight ratio of alkali to water in the molecular sieve and the alkali solution is 1: (0.1-2): (5-15) the temperature is 10 ℃ to 100 ℃ and the time is 0.2-4 hours.

17. The method of claim 13, wherein in step c, the ammonium exchange treatment conditions comprise: the weight ratio of the molecular sieve, the ammonium salt and the water on a dry basis is 1: (0.1-1): (5-10), the temperature is 10 ℃ to 100 ℃, and the time is 0.2-4 hours;

18. The method of claim 13 or 14, wherein in step d, the phosphorus modification treatment comprises: impregnating and/or ion-exchanging the molecular sieve with at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate;

19. A catalytic cracking catalyst prepared by the method of any one of claims 8 to 18.

20. A method for catalytic cracking of hydrocarbon oil, comprising: a hydrocarbon oil is brought into contact with the catalytic cracking catalyst according to any one of claims 1 to 7 and 19 under catalytic cracking reaction conditions.

21. The method of claim 20, wherein the catalytic cracking reaction conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, direct current wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction products.