CN114505092B

CN114505092B - Catalytic cracking auxiliary agent, preparation method and hydrocarbon oil catalytic cracking method

Info

Publication number: CN114505092B
Application number: CN202011169092.8A
Authority: CN
Inventors: 罗一斌; 王成强; 欧阳颖; 邢恩会; 舒兴田
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: 2020-10-28
Filing date: 2020-10-28
Publication date: 2023-03-10
Anticipated expiration: 2040-10-28
Also published as: CN114505092A

Abstract

A catalytic cracking assistant is characterized in that the catalytic cracking assistant contains 5-75 wt% of phosphorus modified MFI structure molecular sieve based on the dry basis of the catalytic cracking assistant; wherein, the K value of the phosphorus modified MFI structure molecular sieve satisfies that: k is more than or equal to 70% and less than or equal to 90%, and K = P1/P2 × 100%, wherein P1 represents the phosphorus content in the area of a 100 square nanometer region within the vertical depth of any crystal face of the molecular sieve crystal grain of 0-2 nm determined by the XPS method, and P2 represents the phosphorus content in the area of a 100 square nanometer region within the thickness interval of 5-10 nm of the vertical depth of any crystal face of the molecular sieve crystal grain determined by the EPMA method.

Description

Catalytic cracking auxiliary agent, preparation method and hydrocarbon oil catalytic cracking method

Technical Field

The invention relates to a catalytic cracking auxiliary agent, a preparation method and application, in particular to a catalytic cracking auxiliary agent containing a molecular sieve, a preparation method and application of the auxiliary agent in catalytic cracking of hydrocarbon oil.

Background

The ZSM-5 molecular sieve with MFI structure is a widely used zeolite molecular sieve catalytic material developed by Mobil corporation of America in 1972. The molecular sieve has a three-dimensional crossed pore channel structure, wherein the pore channel along the axial direction a is a straight pore, the cross section dimension of the pore channel is 0.54 multiplied by 0.56nm and is approximately circular, and the pore channel along the axial direction b is a Z-shaped pore, the cross section dimension of the pore channel is 0.51 multiplied by 0.56nm and is oval. The molecular sieve has special shape-selective catalytic action and has ten-membered ring in the pore mouth and size between that of small-pore zeolite and that of large-pore zeolite. ZSM-5 has a unique pore channel structure, has the characteristics of good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like. The ZSM-5 molecular sieve is introduced into catalytic cracking and carbon four-hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin by utilizing the shape selectivity of the molecule.

Since 1983, ZSM-5 molecular sieve was applied to the catalytic cracking process as an octane number promoter for catalytic cracking, aiming at improving the octane number of the catalytic cracking gasoline and the selectivity of low-carbon olefin. US3758403 originally reported that ZSM-5 was used as an active component for increasing propylene yield to prepare an FCC catalyst together with REY, and US5997728 disclosed that ZSM-5 molecular sieve without any modification was used as an aid for increasing propylene yield, and their propylene yields were not high. Although the ZSM-5 molecular sieve has good shape-selective performance and isomerization performance, the defects are that the hydrothermal stability is poor, and the catalyst is easy to inactivate under severe high-temperature hydrothermal conditions, so that the catalytic performance is reduced.

In the 80 s of the 20 th century, mobil company found that phosphorus can improve the hydrothermal stability of the ZSM-5 molecular sieve, and meanwhile, phosphorus can improve the yield of low-carbon olefin after modifying the ZSM-5 molecular sieve. Conventional additives typically contain phosphorus activated ZSM-5, which selectively converts primary cracking products (e.g., gasoline olefins) to C3 and C4 olefins. After being synthesized, the ZSM-5 molecular sieve is modified by introducing a proper amount of inorganic phosphorus compound, and can stabilize framework aluminum under severe hydrothermal conditions.

CN 106994364A discloses a method for modifying ZSM-5 molecular sieve by phosphorus, which comprises mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with ZSM-5 molecular sieve with high alkali metal ion content to obtain P/P mixture containing phosphorus ₂ O ₅ At least 0.1wt% of the mixture, drying, roasting, further carrying out an ammonium exchange step and a water washing step so that the content of alkali metal ions therein is reduced to less than 0.10wt%, and then carrying out a drying and hydrothermal aging step at 400-1000 ℃ and 100% steam. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content and hasExcellent cracking conversion rate and propylene selectivity, and high liquefied gas yield.

In CN1506161A, a method for modifying a hierarchical pore ZSM-5 molecular sieve is disclosed, which comprises the following conventional steps: synthesizing → filtering → ammonium exchanging → drying → roasting to obtain the hierarchical pore ZSM-5 molecular sieve, then modifying the hierarchical pore ZSM-5 molecular sieve with phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve. Wherein, P ₂ O ₅ The loading is generally in the range from 1 to 7% by weight. However, phosphoric acid or ammonium phosphate can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, and only phosphate radical entering pores is interacted with framework aluminum in the hydrothermal treatment process to keep B acid centers and reduce the distribution of the phosphorus species.

Although the ZSM-5 molecular sieve is modified by adopting a proper amount of inorganic phosphide, the framework dealumination can be slowed down, the hydrothermal stability is improved, and phosphorus atoms can be combined with distorted four-coordination framework aluminum to generate weak B acid centers, so that the higher conversion rate of long paraffin cracking and the higher selectivity of light olefin are achieved, the excessive inorganic phosphide is used for modifying the ZSM-5 molecular sieve, so that the pore channels of the molecular sieve can be blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, in the prior art, phosphoric acid or ammonium phosphate salts can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, the coordination of phosphorus and framework aluminum is insufficient, the utilization efficiency of phosphorus is low, and the phosphorus modification does not always obtain a satisfactory hydrothermal stability improvement result. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus-modified ZSM-5 molecular sieve and further improve the cracking activity.

Disclosure of Invention

One of the purposes of the invention is to provide a catalytic cracking assistant taking a phosphorus modified ZSM-5 molecular sieve based on the dispersion degree of high-phosphorus species as an active component; the other purpose is to provide a preparation method of the catalytic cracking auxiliary agent; the third purpose is to provide the application of the catalytic cracking assistant.

In order to achieve one of the above objects, the invention provides a catalytic cracking assistant according to the first aspect, wherein the catalytic cracking assistant comprises 5-75 wt% of phosphorus-modified MFI-structured molecular sieve based on the dry weight of the catalytic cracking assistant; wherein, the K value of the phosphorus modified MFI structure molecular sieve satisfies the following conditions: k is more than or equal to 70% and less than or equal to 90%, and K = P1/P2 × 100%, wherein P1 represents the phosphorus content in the area of 100 square nanometers within the vertical depth of any crystal face of the molecular sieve crystal grain measured by the XPS method of 0-2 nm, and P2 represents the phosphorus content in the area of 100 square nanometers within the thickness interval of 5-10 nm of any crystal face of the molecular sieve crystal grain measured by the EPMA method.

Preferably, said K value of said phosphorus modified MFI structure molecular sieve satisfies: k is more than or equal to 75% and less than or equal to 90%, and preferably, the K value satisfies the following condition: k is more than or equal to 78 percent and less than or equal to 85 percent.

The phosphorus content of the phosphorus modified MFI structure molecular sieve is P ₂ O ₅ The molar ratio of the alumina to the alumina is more than or equal to 0.01, preferably more than or equal to 0.2, more preferably more than or equal to 0.3, and most preferably 0.4 to 0.7.

Preferably, the phosphorus modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve. The microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, preferably 20-200. The multi-stage pore ZSM-5 molecular sieve has the mesoporous volume accounting for more than 10 percent of the total pore volume, the average pore diameter of 2-20 nm and the molar ratio of silicon oxide to aluminum oxide of 15-1000, preferably 20-200.

The catalytic cracking assistant also contains 1-40 wt% of binder and 0-65 wt% of second clay based on the dry basis of the catalytic cracking assistant. Preferably, the binder comprises a phosphorus-aluminum inorganic binder. More preferably, the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay.

In order to achieve the second object, the invention provides a preparation method of a catalytic cracking assistant, which comprises mixing and pulping a phosphorus-modified MFI structure molecular sieve, a binder and an optionally added second clay, and spray-drying the mixture to obtain the catalytic cracking assistant, and is characterized in that the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with the temperature of 40-150 ℃, preferably 50-150 ℃, and more preferably 70-130 ℃ with the MFI structure molecular sieve with the temperature of 40-150 ℃, preferably 50-150 ℃, and more preferably 70-130 ℃ at substantially the same temperature for at least 0.1 hour by an impregnation method, drying the mixture, and roasting the mixture at 200-600 ℃ in an air or steam atmosphere for at least 0.1 hour; or, after mixing and pulping the phosphorus-containing compound, the MFI structure molecular sieve and water, raising the temperature to 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃, keeping the temperature for at least 0.1 hour, drying, and roasting at 200-600 ℃ in the air or steam atmosphere for at least 0.1 hour.

The phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium and 1, 3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

The phosphorus-containing compound is calculated by phosphorus, the MFI structure molecular sieve is calculated by aluminum, and the molar ratio of the phosphorus-containing compound to the MFI structure molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5.

More preferably, the phosphorus-containing compound is a mixture of boron phosphate and one or more selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, and the weight ratio of boron phosphate in the mixture is 10% to 80%, preferably 20% to 40%.

The weight ratio of the water sieve to the contact is 0.5-1; the roasting is carried out at the temperature of 450-550 ℃ in the air atmosphere.

The binder preferably comprises a phosphorus aluminium inorganic binder. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay; based on the weight of the phosphorus-aluminum inorganic binder containing the first clay on a dry basisThe phosphorus-aluminum inorganic binder containing the first clay contains Al ₂ O ₃ 15-40% by weight calculated as P of an aluminium component ₂ O ₅ 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, wherein the P/Al weight ratio 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 binder may further comprise at least one other inorganic binder selected from the group consisting of pseudoboehmite, alumina sol, silica alumina sol, and water glass.

The second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.

In the preparation method, the binder comprises 3-39 wt% of the phosphorus-aluminum inorganic binder in terms of dry basis and 1-30 wt% of the other inorganic binders in terms of dry basis based on the catalytic cracking assistant.

The preparation method also comprises the following steps: carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalytic cracking assistant; wherein the roasting temperature of the first roasting is 300-650 ℃, and the roasting time is 0.5-8 h; the drying temperature is 100-200 ℃, and the drying time is 0.5-24 h.

The preparation method further comprises the following steps of preparing the first clay-containing phosphorus-aluminum inorganic binder: 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 to 40 weight portions of Al ₂ O ₃ 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 =1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is phosphorusThe weight of the phosphorus in the acid is calculated by the simple substance, and the weight of the aluminum in the alumina source is calculated by the simple substance.

In order to achieve the third object, the invention provides an application of a catalytic cracking assistant, namely a method for catalytic cracking of hydrocarbon oil, which comprises the following steps: under the condition of catalytic cracking, the hydrocarbon oil is contacted and reacted with the catalytic cracking auxiliary agent. For example, the hydrocarbon oil is contacted and reacted with a catalyst mixture containing the catalytic cracking assistant and the catalytic cracking catalyst; in the catalyst mixture, the content of the catalytic cracking assistant is 0.1-30 wt%. Wherein the catalytic cracking 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, straight-run wax oil, propane light/heavy deoiled oil, coker wax oil and coal liquefaction products.

The catalytic cracking auxiliary agent provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbon, and has higher liquefied gas yield.

Detailed Description

The catalytic cracking assistant provided by the invention takes the dry weight of the catalytic cracking assistant as a reference, and the catalytic cracking assistant contains 5-75 wt% of phosphorus modified MFI structure molecular sieve; wherein, the K value of the phosphorus modified MFI structure molecular sieve satisfies the following conditions: k is more than or equal to 70% and less than or equal to 90%, and K = P1/P2 × 100%, wherein P1 represents the phosphorus content in the area of a 100 square nanometer region within the vertical depth of any crystal face of the molecular sieve crystal grain of 0-2 nm determined by the XPS method, and P2 represents the phosphorus content in the area of a 100 square nanometer region within the thickness interval of 5-10 nm of the vertical depth of any crystal face of the molecular sieve crystal grain determined by the EPMA method.

The catalytic cracking assistant of the invention, wherein the K value in the phosphorus modified MFI structure molecular sieve meets the following requirements: k is more than or equal to 75% and less than or equal to 90%, and preferably, the K value satisfies the following condition: k is more than or equal to 78 percent and less than or equal to 85 percent.

The phosphorus content of the phosphorus modified MFI structure molecular sieve is P ₂ O ₅ The molar ratio of the alumina to the alumina is more than or equal to 0.01, and the preferred molar ratio isThe molar ratio is not less than 0.2, more preferably not less than 0.3, and most preferably 0.4 to 0.7.

Preferably, the phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve. The microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, preferably 20-200. The multi-stage pore ZSM-5 molecular sieve has the mesoporous volume accounting for more than 10 percent of the total pore volume, the average pore diameter of 2-20 nm and the molar ratio of silicon oxide to aluminum oxide of 15-1000, preferably 20-200.

In the catalytic cracking assistant of the present invention, the catalytic cracking assistant may contain 5 to 75 wt%, preferably 8 to 60 wt%, of the phosphorus-modified MFI-structured molecular sieve, 1 to 40 wt% of a binder, and 0 to 65 wt% of a second clay, based on the dry basis of the catalytic cracking assistant. The binder may be an inorganic oxide binder, such as one or more of pseudo-boehmite, alumina sol, silica alumina sol, and water glass, conventionally used as a co-agent or catalyst binder component, as is well known to those skilled in the art. Preferably, the binder contains a phosphor-aluminum inorganic binder, i.e. a phosphor-aluminum inorganic binder or a mixture of a phosphor-aluminum inorganic binder and other inorganic binders.

The inorganic binder is preferably a phosphor-aluminum glue and/or a phosphor-aluminum inorganic binder containing a first clay. The phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry basis of the phosphorus-aluminum inorganic binder containing the first clay ₂ O ₃ 15-40 wt.%, preferably 15-35 wt.%, calculated as P, of an aluminium component ₂ O ₅ 45-80 wt.%, preferably 50-75 wt.% of a phosphorus component and more than 0 and not more than 40 wt.%, preferably 8-35 wt.%, on a dry basis, of a first clay, and the phosphorus aluminum inorganic binder containing the first clay has a P/Al weight ratio of 1.0-6.0, preferably 1.2-6.0, more preferably 2.0-5.0, a ph of 1-3.5, preferably 2.0-3.0, and a solids content of 15-60 wt.%. For example, one embodiment of the phosphorus aluminum inorganic binder comprises Al based on the dry weight of the phosphorus aluminum inorganic binder ₂ O ₃ 20-40% by weight calculated as aluminum component and calculated as P ₂ O ₅ 60-80 wt% of a phosphorus component.

The first clay may be at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth; the additional inorganic binder may be selected from one or more of inorganic oxide binders conventionally used in catalytic cracking aids 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.

The catalytic cracking assistant of the present invention further comprises 0 to 65 wt%, preferably 5 to 55 wt%, of a second clay, based on the dry weight of the catalytic cracking assistant. The second clay is also well known to those skilled in the art, and is, for example, at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

In one embodiment of the catalytic cracking aid of the present invention, the catalytic cracking aid comprises 20-60 wt% of the phosphorus-modified MFI structure molecular sieve, 5-35 wt% of the binder, and 5-55 wt% of the second clay, based on the dry basis of the catalytic cracking aid.

The invention also provides a preparation method of the catalytic cracking assistant, which comprises the steps of mixing and pulping the phosphorus-modified MFI structure molecular sieve, the binder and the optional second clay, and spray-drying to obtain the catalytic cracking assistant, and is characterized in that the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with the temperature of 40-150 ℃, preferably 50-150 ℃ and more preferably 70-130 ℃ with an MFI structure molecular sieve with the temperature of 40-150 ℃, preferably 50-150 ℃ and more preferably 70-130 ℃ at the basically same temperature for at least 0.1 hour by using an impregnation method, drying, and roasting at 200-600 ℃ in an air or steam atmosphere for at least 0.1 hour; or, after mixing and pulping the phosphorus-containing compound, the MFI structure molecular sieve and water, heating to 40-150 ℃, preferably 50-150 ℃, more preferably 70-130 ℃, keeping for at least 0.1 hour, drying, and roasting at 200-600 ℃ for at least 0.1 hour in the air or steam atmosphere.

In the preparation of the phosphorus modified MFI structure molecular sieve, the MFI structure molecular sieve can be a hydrogen type microporous ZSM-5 molecular sieve or a hydrogen type hierarchical ZSM-5 molecular sieve. They are reduced to Na by ammonium exchange ₂ O<0.1wt% is obtained, the silica to alumina ratio (molar ratio of silica to alumina) is in the range of 10 or more, usually 10 to 200.

In the preparation of the phosphorus modified MFI structure molecular sieve, the phosphorus-containing compound is counted by phosphorus, the hydrogen type ZSM-5 molecular sieve or the hydrogen type hierarchical pore ZSM-5 molecular sieve is counted by aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen type ZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5. The phosphorus-containing compound is selected from organic phosphorus, such as trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bis triethyl phosphonium, etc., inorganic phosphide, such as one of phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, boron phosphate or a mixture thereof, etc. The inventors have found that when boron phosphate is used as one of the phosphorus-containing compounds and hydrothermal calcination is carried out at 300 to 500 ℃, phosphorus has a better dispersion in the molecular sieve, and therefore, a preferred combination of the phosphorus-containing compounds is a mixture of boron phosphate and a compound selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate. In the mixture containing boron phosphate, the weight ratio of the boron phosphate is 10-80%, preferably 20-40%, and more preferably 25-35%.

In the preparation of the phosphorus modified MFI structure molecular sieve, the contacting is carried out by contacting an aqueous solution of a phosphorus-containing compound having a temperature of 0 to 150 ℃ with a hydrogen MFI structure molecular sieve having a temperature of 0 to 150 ℃ at substantially the same temperature for at least 0.1 hour by an impregnation method. For example, the contacting may be performed at a normal temperature range of 0 to 30 ℃, preferably, at a higher temperature range of 40 ℃ or higher, for example, 50 to 150 ℃, more preferably, 70 to 130 ℃, which may provide a better effect that the phosphorus species are dispersed better, the phosphorus is more easily migrated into the crystals of the hydrogen MFI structure molecular sieve to be bonded to the framework aluminum, the coordination degree of phosphorus and the framework aluminum is further improved, and finally, the hydrothermal stability of the molecular sieve is improved. The substantially same temperature means that the temperature difference between the aqueous solution of the phosphorus-containing compound and the hydrogen MFI structure molecular sieve is within. + -. 5 ℃. For example, the aqueous solution of the phosphorus-containing compound is heated to a temperature of 80 ℃ and the HZSM-5 molecular sieve is heated to a temperature of 75 to 85 ℃.

In the preparation of the phosphorus modified MFI structure molecular sieve, the contact can also be that a phosphorus compound, a hydrogen MFI structure molecular sieve and water are mixed and then are kept for at least 0.1 hour at the temperature of between 0 and 150 ℃. For example, after mixing, the mixture is kept at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, in order to obtain better effects, namely, better dispersion of phosphorus species, easier migration of phosphorus into molecular sieve crystal to combine with framework aluminum, further increase coordination degree of phosphorus and framework aluminum, and finally improve hydrothermal stability of the molecular sieve, the phosphorus-containing compound, the hydrogen type MFI structure molecular sieve and water are mixed and then kept at a higher temperature range of 40 ℃ or higher for 0.1 hour, for example, a temperature range of 50 to 150 ℃, more preferably a temperature range of 70 to 130 ℃.

In the preparation of the phosphorus modified MFI structure molecular sieve, the weight ratio of the water sieve is 0.5-1, and the time is 0.5-40 hours. The calcination is preferably carried out at 450 to 550 ℃ in an air atmosphere.

In the preparation method of the catalytic cracking assistant, the binder contains a phosphorus-aluminum inorganic binder and other inorganic binders, and the weight and dosage ratio of the phosphorus-modified MFI structure molecular sieve, the phosphorus-aluminum inorganic binder and the other inorganic binders can be (10-75): (3-39): (1 to 30), preferably (10 to 75): (8-35): (5-25); wherein the phosphorus-aluminum inorganic binder can be phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay; the other inorganic binder may include at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass. The preparation method can be mixing and pulping the phosphorus modified MFI structure molecular sieve, the phosphorus aluminum inorganic binder and other inorganic binders, and the charging sequence is not specially required, for example, the phosphorus aluminum inorganic binder, other inorganic binders, the phosphorus modified MFI structure molecular sieve and the second clay can be mixed (when the second clay is not contained, the related charging step can be omitted) and pulping, preferably, the second clay, the phosphorus modified MFI structure molecular sieve and other inorganic binders are mixed and pulped and then added into the phosphorus aluminum inorganic binder, which is beneficial to improving the activity and selectivity of the auxiliary agent.

The preparation method of the catalytic cracking assistant also comprises the step of spray drying the slurry obtained by pulping. Spray drying methods are well known to those skilled in the art and there is no particular requirement for the present invention. Optionally, the preparation method may further include: and carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalytic cracking assistant. Wherein, the roasting temperature of the first roasting can be 300-650 ℃, for example 400-600 ℃, preferably 450-550 ℃, and the roasting time can be 0.5-8 hours; the washing can adopt one of ammonium sulfate, ammonium chloride and ammonium nitrate, and the washing temperature can be 40-70 ℃; the temperature of the drying treatment may be 100 to 200 ℃, for example, 100 to 150 ℃, and the drying time may be 0.5 to 24 hours, for example, 1 to 12 hours.

One specific embodiment of the preparation method of the catalytic cracking assistant is as follows: mixing the binder, the second clay and water (such as decationized water and/or deionized water) to prepare slurry with the solid content of 10-50 wt%, uniformly stirring, adjusting the pH of the slurry to 1-4 by using inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, keeping the pH value, standing and aging for 0-2 hours (such as 0.3-2 hours) at 20-80 ℃, adding inorganic binders such as aluminum sol and/or silica sol, stirring for 0.5-1.5 hours to form colloid, then adding the phosphorus modified MFI structure molecular sieve to form assistant slurry, wherein the solid content of the assistant slurry is 20-45 wt%, continuously stirring, and performing spray drying to prepare the microsphere assistant. The microsphere aid is then subjected to a first calcination, for example at 350 to 650 ℃ or 400 to 600 ℃, preferably 450 to 550 ℃, for 0.5 to 6 hours or 0.5 to 2 hours, washed with ammonium sulfate (where the washing temperature may be 40 to 70 ℃, ammonium sulfate: microsphere aid: water =0.2 to 0.8 (weight ratio) to a sodium oxide content of less than 0.25 wt%, washed with water and filtered, and then dried.

In the preparation method of the catalytic cracking assistant, the phosphorus-aluminum inorganic binder containing the first clay can be prepared by adopting 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 to 40 weight portions of Al ₂ O ₃ (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 =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. The alumina source may be at least one selected from the group consisting of rho-alumina, x-alumina, η -alumina, γ -alumina, κ -alumina, σ -alumina, θ -alumina, gibbsite, surge, nordstrandite, diaspore, boehmite, and pseudo-boehmite from which the aluminum component of the first clay-containing aluminophosphate inorganic binder is derived. The first clay can be one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, and preferably the 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 the 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 above embodiment, the introduction of the clay into the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer between materials during the preparation process, but also avoids the binder solidification caused by nonuniform, local, instantaneous, violent reaction, exothermic and ultrastable heat release of the materials, and the binding 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 composition, and enables the obtained auxiliary agent to have better selectivity.

The invention further provides an application of the catalytic cracking assistant, namely a method for catalytic cracking of hydrocarbon oil, which comprises the following steps: under the condition of catalytic cracking, the hydrocarbon oil is in contact reaction with the catalytic cracking assistant.

The method for catalytic cracking of hydrocarbon oil of the present invention comprises: under the catalytic cracking condition, the hydrocarbon oil is in contact reaction with a catalytic mixture containing the catalytic cracking auxiliary agent and a catalytic cracking catalyst; in the catalytic mixture, the content of the catalytic cracking assistant is 0.1-30 wt%.

Optionally, the catalytic cracking 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, straight-run wax oil, propane light/heavy deoiled oil, coker wax oil and coal liquefaction products.

The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.

And carrying out surface scanning analysis on the chemical components of the micro-area by adopting an EPMA/SEM combined method to perform phosphorus content quantitative analysis corresponding to the depth structure, wherein a dispersion degree K value refers to the percentage of the phosphorus content on the surface of the molecular sieve crystal grain and the phosphorus content on the depth interface of the molecular sieve crystal grain, wherein K = P1 (XPS)/P2 (EPMA)%, P1 (XPS) indicates that the phosphorus content of any crystal face depth of the molecular sieve crystal grain quantitatively determined by adopting the XPS method is less than the phosphorus content of the micro-area with the thickness of 2nm, and P2 (EPMA) indicates that the phosphorus content of the micro-area with the thickness of 5-10 nm is obtained by utilizing Focused Ion Beam (FIB) cutting and quantitatively determined by adopting the EPMA method.

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 micro-reaction device is adopted to evaluate the influence of the catalytic cracking auxiliary agent on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon.

The prepared catalytic cracking assistant sample is aged for 17 hours at 800 ℃ under 100 percent water vapor on a fixed bed aging device, and is evaluated on a micro-reaction device, wherein the raw material oil is VGO or naphtha, and the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the agent-oil ratio is 3.2. Microreaction activity was measured using ASTM D5154-2010 standard method.

The RIPP standard method provided by the invention can be seen in petrochemical analysis methods, edition such as Yangcui, 1990 edition.

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 catalyst ₂ O ₃ The content was 21.5% by weight. The silica sol is an industrial product, siO, produced by the middle petrochemical catalyst Qilu division ₂ Content 28.9 wt%, na ₂ The 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. The rectorite is produced by Hubei Zhongxiang Mingliu rectorite development Limited company and the content of the quartz sand<3.5 wt.% of Al ₂ O ₃ 39.0 wt.% of Na ₂ The O content was 0.03% by weight, and the solids content was 77% by weight. SB aluminum hydroxide powder, manufactured by Condex, germany, al ₂ O ₃ The content was 75% by weight. Gamma-alumina, manufactured by Condex, germany, al ₂ O ₃ The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, and is produced in Beijing chemical plant.

Examples 1-13 illustrate the phosphorus-modified hierarchical pore ZSM-5 molecular sieve employed in the catalytic cracking aid of the present invention and its preparation.

Example 1-1

Taking 18.5g of diammonium hydrogen phosphate and 108g of hydrogen type multi-stage hole ZSM-5 molecular sieve (provided by Qilu Branch of China petrochemical catalyst company, the relative crystallinity is 88.6 percent, the molar ratio of silicon oxide to aluminum oxide is 20.8 ₂ The O content is from 0.017 percent by weight, and the specific surface area is 373m ² G, totalPore volume of 0.256ml/g, mesoporous volume of 0.119ml/g, average pore diameter of 5.8nm, the same applies hereinafter) and 60g of deionized water were mixed and slurried, heated to 100 ℃ and held for 2 hours, dried in an oven at 110 ℃ and air-calcined at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ1-1.

Comparative examples 1 to 1

The same as example 1-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D1-1.

Examples 1 to 2

Similar to example 1-1, except that after drying, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample was treated at 450 ℃ for 0.5h under a 60% steam atmosphere and was identified as GPZ1-2.

Comparative examples 1 to 2

The same as example 1-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D1-2. The phosphorus dispersity K of GPZ-1, D1-1, GPZ1-2 and D1-2 is shown in Table 1.

TABLE 1

Example 2-1

Mixing 18.5g of diammonium hydrogen phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 120g of deionized water, beating into slurry, keeping the slurry at 70 ℃ for 2 hours, drying the slurry in an oven at 110 ℃, and roasting the slurry at 550 ℃ for 2 hours to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as GPZ2-1.

Comparative example 2-1

The same as example 2-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D2-1.

Examples 2 to 2

Similar to example 2-1, except that after drying, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample was treated at 600 ℃ for 2 hours under 50% steam atmosphere and was identified as GPZ2-2.

Comparative examples 2 to 2

The same as example 2-2, except that the hydrogen type multi-stage pore ZSM-5 molecular sieve, denoted as D2-2, was impregnated with a phosphorus-containing aqueous solution at 20 ℃.

The phosphorus dispersity K for GPZ2-1, D2-1, GPZ2-2 and D2-2 is shown in Table 2.

TABLE 2

Example 3-1

Dissolving 11.8g of phosphoric acid in 60g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 108g of a hydrogen type multistage hole ZSM-5 molecular sieve; and respectively heating the phosphorus-containing aqueous solution and the hydrogen-type hierarchical pore ZSM-5 molecular sieve to 80 ℃, mixing and contacting for 4 hours, drying in an oven at 110 ℃, and roasting in air at 550 ℃ for 2 hours to obtain the phosphorus-modified hierarchical pore ZSM-5 molecular sieve, wherein the molecular sieve is marked as GPZ3-1.

Comparative example 3-1

The same as example 3-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D3-1.

Examples 3 to 2

The difference from example 3-1 is that after drying, the porous ZSM-5 molecular sieve containing phosphorus was treated at 430 ℃ for 2 hours in an atmosphere of 100% steam, and the sample was identified as GPZ3-2.

Comparative examples 3 and 2

The same as example 3-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D3-2. The phosphorus dispersity K of GPZ3-1, D3-1, GPZ3-2 and D3-2 is shown in Table 3.

TABLE 3

Example 4-1

9.3g of diammonium hydrogen phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 90 ℃ for 2 hours, and after the slurry is dried in an oven at 110 ℃, the slurry is roasted for 2 hours at 550 ℃ in air to obtain the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, which is marked as GPZ4-1.

Comparative example 4-1

The same as example 4-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D4-1.

Example 4-2

Similar to example 4-1, except that after drying, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample was treated at 350 ℃ for 2 hours under a 100% steam atmosphere and was identified as GPZ4-2.

Comparative examples 4 to 2

The same as example 4-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D4-2. The phosphorus dispersity K of GPZ4-1, D4-1, GPZ4-2 and D4-2 is shown in Table 4.

TABLE 4

Example 5-1

Mixing 9.7g of trimethyl phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 80g of deionized water, beating into slurry, heating to 120 ℃, keeping the temperature for 8 hours, drying in a drying oven at 110 ℃, and roasting in air at 550 ℃ for 2 hours to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as GPZ5-1.

Comparative example 5-1

The same as example 5-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D5-1.

Examples 5 and 2

The same as example 5-1, except that after drying, the calcination treatment was carried out at 500 ℃ for 4 hours in a 40% steam atmosphere, and the obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample was designated as GPZ5-2.

Comparative examples 5 to 2

The same as example 5-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D5-2. The phosphorus dispersity K for GPZ5-1, D5-1, GPZ5-2 and D5-2 is shown in Table 5.

TABLE 5

Example 6-1

Mixing and pulping 13.2g of boron phosphate, 108g of hydrogen type hierarchical pore ZSM-5 molecular sieve and 100g of deionized water, keeping the mixture at 150 ℃ for 2 hours, drying the mixture in an oven at 110 ℃, and roasting the mixture at 550 ℃ for 2 hours to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as GPZ6-1.

Comparative example 6-1

The same as example 6-1, except that the hydrogen type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D6-1.

Example 6 to 2

The same as example 6-1, except that the phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample obtained by hydrothermal calcination treatment at 350 ℃ in a 60% steam atmosphere for 4 hours after drying was designated as GPZ6-2.

Comparative examples 6 to 2

The same as example 6-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D6-2. The phosphorus dispersity K for GPZ6-1, D6-1, GPZ6-2 and D6-2 is shown in Table 6.

TABLE 6

Example 7-1

Dissolving 16.3g of triphenyl phosphine in 80g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 108g of a hydrogen type multistage hole ZSM-5 molecular sieve; and respectively heating the phosphorus-containing aqueous solution and the hydrogen-type hierarchical pore ZSM-5 molecular sieve to 80 ℃, mixing and contacting for 4 hours, drying in an oven at 110 ℃, and roasting for 2 hours at 550 ℃ to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, wherein the sample is marked as GPZ7-1.

Comparative example 7-1

The same as example 7-1, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D7-1.

Example 7-2

Similar to example 7-1, except that after drying, the product was calcined at 600 ℃ in a 50% steam atmosphere for 2 hours to obtain a phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample, which was designated GPZ7-2.

Comparative examples 7 to 2

The same as example 7-2, except that the hydrogen type multi-stage pore ZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D7-2. The phosphorus dispersity K for GPZ7-1, D7-1, GPZ7-2 and D7-2 is shown in Table 7.

TABLE 7

Example 8-1

The difference from example 4-1 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the diammonium phosphate to the crystalline boron phosphate is 3. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ8-1.

Example 8 to 2

The difference from example 4-2 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the diammonium phosphate to the crystalline boron phosphate is 3. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ8-2.

Example 9-1

The difference from example 4-1 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the two is 2. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ9-1.

Example 9-2

The difference from example 4-2 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the two is 2. And (3) marking the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve as GPZ9-2.

Example 10-1

The difference from example 4-1 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the diammonium phosphate to the crystalline boron phosphate is 1. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ10-1.

Example 10-2

The difference from example 4-2 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the diammonium phosphate to the crystalline boron phosphate is 1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ10-2.

The phosphorus dispersion degree K of GPZ8-1, GPZ8-2, GPZ9-1, GPZ9-2, GPZ10-1 and GPZ10-2 is shown in Table 8.

TABLE 8

Example 11-1

The same as example 8-1, except that the phosphorus source was phosphoric acid and crystalline boron phosphate in a weight ratio of 3. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ11-2.

Example 11-2

The same as example 8-2, except that the phosphorus source was phosphoric acid and crystalline boron phosphate in a weight ratio of 3. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ11-2.

Example 12-1

The same as example 9-1, except that the phosphorus source was phosphoric acid and crystalline boron phosphate, in a weight ratio of 2. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ12-1.

Example 12-2

The same as example 9-2, except that the phosphorus source was phosphoric acid and crystalline boron phosphate, and the weight ratio of the two was 2. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ12-2.

Example 13-1

The same as example 10-1, except that the phosphorus source was phosphoric acid and crystalline boron phosphate, and the weight ratio of the two was 1. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as GPZ13-1.

Example 13-2

The same as example 10-2, except that the phosphorus source was phosphoric acid and crystalline boron phosphate, and the weight ratio of the two was 1. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as GPZ13-2.

The phosphorus dispersity K of GPZ11-1, GPZ11-2, GPZ12-1, GPZ12-2, GPZ13-1 and GPZ13-2 is shown in Table 9.

TABLE 9

As can be seen from the data in tables 1-9 above, the phosphorus modified multi-stage pore ZSM-5 molecular sieves of the present invention all had higher degrees of dispersion of phosphorus, e.g., GPZ8-2, sample modified with a bisphospho source of phosphoric acid and crystalline boron phosphate of example 8-2, achieved a dispersion K of 85%.

Examples 14-26 illustrate phosphorus modified microporous ZSM-5 molecular sieves and methods of preparation employed in the catalytic cracking aids of the present invention.

Example 14-1

16.2g of diammonium hydrogen phosphate and 113g of HZSM-5 molecular sieve (provided by Qilu Branch of China petrochemical catalyst Co., ltd., relative crystallinity of 91.1%, molar ratio of silica to alumina of 24.1, na were used as the material ₂ The content of O is 0.039 weight percent% and specific surface area of 353m ² Per g, total pore volume of 0.177ml/g, the same applies hereinafter) and 60g of deionized water, heating to 100 ℃ and holding for 2 hours, drying at 110 ℃ and treating at 550 ℃ for 0.5 hour in an air atmosphere. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated GPZ14-1.

Comparative example 14-1

Comparative example 14-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 14-1 except that the HZSM-5 molecular sieve was impregnated with the aqueous solution containing phosphorus at 20 ℃ for 2 hours by the impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and was designated D14-1.

Example 14-2

The same as example 14-1 except that the treatment was carried out at 550 ℃ in an air atmosphere of 500 ℃ and 50% water vapor atmosphere for 0.5 hour. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ14-2.

Comparative example 14 to 2

The same as example 14-2, except that the hydrogen-type multi-stage pore ZSM-5 molecular sieve was impregnated with the aqueous solution containing phosphorus at 20 ℃ for 2 hours by the impregnation method. A phosphorus modified ZSM-5 molecular sieve comparison sample was obtained and is noted as D14-2. The phosphorus dispersity K for GPZ14-1, D14-1, GPZ14-2 and D14-2 is shown in Table 10.

TABLE 10

Example 15-1

16.2g of diammonium hydrogen phosphate, 113g of HZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 70 ℃ for 2 hours, and the slurry is dried at 110 ℃ and treated at 550 ℃ for 2 hours in air atmosphere to obtain a phosphorus modified ZSM-5 molecular sieve sample, which is marked as GPZ15-1.

Comparative example 15-1

Comparative example 15-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 15-1 except that the HZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃ by an impregnation method. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as D15-1.

Example 15-2

The same as example 15-1 except that the treatment was carried out at 550 ℃ in an air atmosphere, 600 ℃ in a 30% water vapor atmosphere, for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ15-2.

Comparative examples 15 to 2

The same as example 15-2, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and was designated D15-2.

The phosphorus dispersity K of GPZ15-1, D15-1, GPZ15-2 and D15-2 is shown in Table 11.

TABLE 11

Example 16-1

Dissolving 10.4g of phosphoric acid in 60g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 113gHZSM-5 molecular sieve; and respectively heating the phosphorus-containing aqueous solution and the HZSM-5 molecular sieve to 80 ℃, mixing and contacting for 4 hours, drying at 110 ℃, and treating for 2 hours at 550 ℃ in an air atmosphere to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as GPZ16-1.

Comparative example 16-1

Comparative example 16-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 16-1, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as D16-1.

Example 16-2

Example 16-2 illustrates a phosphorus-containing microporous ZSM-5 molecular sieve and process of the present invention.

The same as example 16-1, except that the treatment was carried out at 400 ℃ in an air atmosphere of 550 ℃ and 100% water vapor atmosphere for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ16-2.

Comparative example 16-2

The same as example 16-2, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and was designated D16-2.

The phosphorus dispersity K for GPZ16-1, D16-1, GPZ16-2 and D15-2 is shown in Table 12.

TABLE 12

Example 17-1

8.1g of diammonium hydrogen phosphate, 113g of HZSM-5 molecular sieve and 120g of deionized water are mixed and beaten into slurry, the slurry is kept at 90 ℃ for 4 hours, and the slurry is dried at 110 ℃ and treated at 550 ℃ for 2 hours in air atmosphere to obtain a phosphorus modified ZSM-5 molecular sieve sample, which is marked as GPZ17-1.

Comparative example 17-1

Comparative example 17-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 17-1 except that the HZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃ by an impregnation method. The comparative sample of the phosphorus modified ZSM-5 molecular sieve obtained was designated as D17-1.

Example 17-2

The same as example 17-1 except that the treatment was carried out at 550 ℃ in an air atmosphere of 300 ℃ and 100% water vapor atmosphere for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ17-2.

Comparative examples 17 to 2

The same as example 17-2, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and recording the sample as D17-2.

The phosphorus dispersity K for GPZ17-1, D17-1, GPZ17-2 and D17-2 is shown in Table 13.

Watch 13

Example 18-1

Mixing 8.5g of trimethyl phosphate, 113g of HZSM-5 molecular sieve and 80g of deionized water, pulping, heating to 120 ℃, keeping the temperature for 8 hours, drying at 110 ℃, and treating for 2 hours at 550 ℃ in an air atmosphere to obtain a phosphorus modified ZSM-5 molecular sieve sample, which is marked as GPZ18-1.

Comparative example 18-1

Comparative example 18-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as in example 18-1 except that the HZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃ by an impregnation method. The comparative sample of the phosphorus modified ZSM-5 molecular sieve obtained was designated as D18-1.

Example 18-2

The same as example 18-1 except that the treatment was carried out at 550 ℃ in an air atmosphere of 500 ℃ and 80% water vapor atmosphere for 4 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ18-2.

Comparative example 18-2

The same as example 18-2, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was designated D18-2.

The phosphorus dispersity K for GPZ18-1, D18-1, GPZ18-2 and D18-2 is shown in Table 14.

TABLE 14

Example 19-1

After 11.6g of boron phosphate, 113g of HZSM-5 molecular sieve and 100g of deionized water are mixed and beaten into slurry, the slurry is kept at 150 ℃ for 2 hours, dried at 110 ℃ and treated at 550 ℃ for 2 hours in air atmosphere, and the obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ19-1.

Comparative example 19-1

Comparative example 19-1 illustrates the process conventional in the industry and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 19-1 except that the HZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃ by an impregnation method. The comparative sample of the phosphorus modified ZSM-5 molecular sieve obtained was designated as D19-1.

Example 19-2

The same as example 19-1, except that the treatment was carried out at 400 ℃ in an air atmosphere of 550 ℃ and 100% water vapor atmosphere for 4 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated GPZ19-2.

Comparative example 19-2

The same as example 19-2, except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was designated D19-2.

The phosphorus dispersity K for GPZ19-1, D19-1, GPZ19-2 and D19-2 is shown in Table 15.

Watch 15

Example 20-1

Dissolving 14.2g of triphenyl phosphine in 80g of deionized water, and stirring for 2 hours to obtain a phosphorus-containing aqueous solution; taking 113g of HZSM-5 molecular sieve; and respectively heating the phosphorus-containing aqueous solution and the HZSM-5 molecular sieve to 80 ℃, mixing and contacting for 4 hours, drying at 110 ℃, and treating for 2 hours at 550 ℃ in an air atmosphere to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as GPZ20-1.

Comparative example 20-1

Comparative example 20-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 20-1 except that the HZSM-5 molecular sieve was impregnated with an aqueous solution containing phosphorus at 20 ℃ by an impregnation method. The comparative sample of the phosphorus modified ZSM-5 molecular sieve obtained was designated as D20-1.

Example 20-2

The same as example 20-1 except that the treatment was carried out at 550 ℃ in an air atmosphere of 600 ℃ and 30% water vapor atmosphere for 4 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as GPZ20-2.

Comparative example 20-2

The same as example 20-2, except that the HZSM-5 molecular sieve was impregnated with a phosphorus-containing aqueous solution at 20 ℃ by an impregnation method. And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and recording the sample as D20-2.

The phosphorus dispersity K for GPZ20-1, D20-1, GPZ20-2 and D20-2 is shown in Table 16.

TABLE 16

Example 21-1

The same as example 17-1, except that the phosphorus source was diammonium hydrogen phosphate and crystalline boron phosphate in a weight ratio of 3. The resulting phosphorous containing ZSM-5 molecular sieve sample was designated GPZ21-1.

Example 21-2

The same as example 17-2, except that the phosphorus sources were diammonium hydrogen phosphate and crystalline boron phosphate, in a weight ratio of 3. The resulting phosphorous containing ZSM-5 molecular sieve sample was designated GPZ21-2.

Example 22-1

The same as in example 17-1, except that the bisphosphine source is, for example, diammonium hydrogen phosphate and crystalline boron phosphate, in a weight ratio of 2. The resulting phosphorous containing ZSM-5 molecular sieve sample was designated GPZ22-1.

Example 22-2

The difference from example 17-2 is that the phosphorus sources are diammonium phosphate and crystalline boron phosphate, and the weight ratio of the two is 2. The resulting phosphorous containing ZSM-5 molecular sieve sample was designated GPZ23-2.

Example 23-1

The same as example 17-1, except that the phosphorus sources were diammonium hydrogen phosphate and crystalline boron phosphate, in a weight ratio of 1. The resulting phosphorous containing ZSM-5 molecular sieve sample was designated GPZ23-1.

Example 23-2

Same as the embodiment17-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the diammonium hydrogen phosphate to the crystalline boron phosphate is 1. The obtained ZSM-5 molecular sieve containing phosphorus was designated GPZ23-2.

The phosphorus dispersity K of GPZ21-1, GPZ21-2, GPZ22-1, GPZ22-2, GPZ23-1 and GPZ23-2 is shown in Table 17.

TABLE 17

Example 24-1 to example 26-2

The phosphorus dispersion degree K of each of the samples obtained by replacing the phosphorus source in example 21-1 to example 23-2 with phosphoric acid and crystalline boron phosphate in the following order by 3.

Watch 18

Examples 27-30 illustrate the use of a phosphorus aluminum inorganic binder in the catalytic cracking aid of the present invention.

Example 27

1.91 kg of pseudoboehmite (containing Al) ₂ O ₃ 1.19 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 mixture ratio of the materials is shown in the table 19, and the sample number is Binder1.

Examples 28 to 30

A phosphorus-aluminum inorganic Binder was prepared by the method of example 27 in accordance with the material proportions shown in Table 19 and the sample numbers of Binder2, binder3 and Binder4.

Watch 19

Examples 31-56 provide catalytic cracking aids of the present invention and comparative examples 31-56 illustrate comparative catalytic cracking aids. Of these, examples 31-43 are multi-stage pore ZSM-5 molecular sieves and examples 44-56 are microporous ZSM-5 molecular sieves.

Example 31-1

Taking the phosphorus modified molecular sieve GPZ1-1 prepared in the example 1-1, kaolin and pseudo-boehmite, adding decationized water and aluminum sol for 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 continuing pulping for 45 minutes, then adding the phosphorus-aluminum inorganic Binder Binder1 prepared in the example 8, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, roasting the microspheres for 1 hour at 500 ℃ to obtain a catalytic cracking auxiliary sample, the number of which is CAZ1-1, wherein the mixture ratio of the molecular sieve GPZ1-1, the kaolin 23, the Binder1 is 18 percent, and the pseudo-boehmite is prepared by using Al ₂ O ₃ Calculated as Al) 5%, alumina sol (calculated as Al) ₂ O ₃ Calculated) is 4 percent.

A fixed bed micro-reaction device is adopted to evaluate the reaction performance of 100 percent of balancing agent and the blending of the balancing agent into the CAZ1-1 so as to illustrate the catalytic cracking reaction effect of the catalytic cracking auxiliary agent provided by the disclosure.

The auxiliary agent CAZ1-1 is aged for 17 hours at 800 ℃ under the condition of 100% water vapor atmosphere. Mixing aged CAZ1-1 with industrial FCC equilibrium catalyst (industrial FCC equilibrium catalyst of DVR-3, light oil with micro-reverse activity of 63). And (3) loading the mixture of the balancing agent and the auxiliary agent into a fixed bed micro-reactor, and carrying out catalytic cracking on the raw oil shown in the table 20 under the evaluation conditions of the reaction temperature of 620 ℃, the regeneration temperature of 620 ℃ and the agent-oil ratio of 3.2. Table 21 gives the results of the reactions, including the blank test agents.

Watch 20

Item	Raw oil
		Density (20 ℃ C.), g/cm ³	0.9334
Dioptric light (70 degree)	1.5061
		Four components, m%
Saturated hydrocarbons	55.6
		Aromatic hydrocarbons	30
Gum material	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

Example 31-2

The same as in example 31-1 except that GPZ1-1 was replaced with GPZ1-2, which was a phosphorus-modified molecular sieve prepared in example 1-2. Preparing a catalytic cracking assistant sample with the number of CAZ1-2.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 21.

Comparative example 31-1

The same as in example 12-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was replaced with a comparative sample D1-1 of comparative example 1-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ1-1.

Comparative example 31-2

The same as in example 31-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was replaced with comparative sample D1-2 of comparative example 1-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ1-2.

TABLE 21

Example 32-1

The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ2-1 prepared in example 2-1. And preparing a catalytic cracking auxiliary agent sample with the serial number of CAZ2-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 22.

Example 32-2

The same as example 32-1 except that GPZ2-1 was replaced with GPZ2-2, which was prepared in example 2-2. Preparing a catalytic cracking assistant sample with the number of CAZ2-2.

Comparative example 32-1

The same as in example 32-1 except that GPZ2-1, a phosphorus-modified molecular sieve, was replaced with D2-1, a comparative sample of comparative example 2-1. A comparative sample of the catalytic cracking auxiliary agent is prepared and numbered DCAZ2-1.

Comparative example 32-2

The same as in example 32-1 except that GPZ2-1, a phosphorus-modified molecular sieve, was replaced with a comparative sample D2-2 of comparative example 2-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ2-2.

TABLE 22

Example 33-1

The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ3-1 prepared in example 3-1. Preparing a catalytic cracking assistant sample with the number of CAZ3-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 23.

Example 33-2

The same as in example 31-1 except that GPZ1-1 was replaced with GPZ3-2, which was prepared in example 3-2. Preparing a catalytic cracking assistant sample with the number of CAZ3-2.

Comparative example 33-1

The same as in example 31-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was replaced with the comparative sample D3-1 of comparative example 3-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ3-1.

Comparative example 33-2

The same as in example 31-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was replaced with a comparative sample D3-2 of comparative example 3-2. A comparative sample of the catalytic cracking auxiliary agent is prepared and numbered DCAZ3-2.

TABLE 23

Example 34-1

The same as in example 31-1, except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ4-1 prepared in example 4-1. Preparing a catalytic cracking auxiliary agent sample with the number of CAZ4-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 24.

Example 34-2

The same as in example 34-1, except that the phosphorus-modified molecular sieve GPZ4-1 was replaced with the phosphorus-modified molecular sieve GPZ4-2 prepared in example 4-2. Preparing a catalytic cracking assistant sample with the number of CAZ4-2.

Comparative example 34-1

The same as in example 34-1 except that GPZ4-1, a phosphorus-modified molecular sieve, was replaced with D4-1, a comparative sample of comparative example 4-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ4-1.

Comparative example 34-2

The difference from example 34-1 is that the phosphorus-modified molecular sieve therein was replaced with comparative sample D4-2 of comparative example 2-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ4-2.

Watch 24

Example 35-1

The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ5-1 prepared in example 5-1. Preparing a catalytic cracking assistant sample with the number of CAZ5-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 25.

Example 35-2

The same as in example 35-1 except that the phosphorus-modified molecular sieve GPZ5-1 was replaced with the phosphorus-modified molecular sieve GPZ5-2 prepared in example 5-2. Preparing a catalytic cracking assistant sample with the number of CAZ5-2.

The evaluation was made in the same manner as in example 35-1, and the results are shown in Table 25.

Comparative example 35-1

The same as in example 35-1 except that GPZ5-1, a phosphorus-modified molecular sieve, was replaced with D5-1, a comparative sample of comparative example 5-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ5-1.

Comparative example 35-2

The same as in example 35-1 except that GPZ5-1, a phosphorus-modified molecular sieve, was replaced with D5-2, a comparative sample of comparative example 2-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ5-2.

TABLE 25

Example 36-1

The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ6-1 prepared in example 6-1. Preparing a catalytic cracking assistant sample with the number of CAZ6-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 26.

Example 36-2

The same as in example 36-1, except that GPZ6-1, a phosphorus-modified molecular sieve, was replaced with GPZ6-2, a phosphorus-modified molecular sieve prepared in example 6-2. Preparing a catalytic cracking assistant sample with the number of CAZ6-2.

The evaluation was made in the same manner as in example 36-1, and the results are shown in Table 26.

Comparative example 36-1

The same as in example 36-1 except that GPZ6-1, a phosphorus-modified molecular sieve, was used in place of the comparative sample D6-1 of comparative example 6-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ6-1.

Comparative example 36-2

The same as in example 36-1 except that GPZ6-1, a phosphorus-modified molecular sieve, was replaced with D6-2, a comparative sample of comparative example 6-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ6-2.

Watch 26

Example 37-1

The same as in example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieve GPZ7-1 prepared in example 7-1. Preparing a catalytic cracking assistant sample with the number of CAZ7-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 27.

Example 37-2

The same as in example 37-1 except that the phosphorus-modified molecular sieve GPZ7-1 was replaced with the phosphorus-modified molecular sieve GPZ7-2 prepared in example 7-2. And preparing a catalytic cracking assistant sample with the number of CAZ7-2.

Comparative example 37-1

The same as in example 37-1 except that GPZ7-1, a phosphorus-modified molecular sieve, was replaced with D7-1, a comparative sample of comparative example 7-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ7-1.

Comparative example 37-2

The same as in example 37-1 except that GPZ7-1, a phosphorus-modified molecular sieve, was replaced with a comparative sample D7-2 of comparative example 7-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ7-2.

Watch 27

Examples 38 to 43

The same as example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieves GPZ8-1 to GPZ13-2 prepared in examples 8-1 to 13-2, respectively. Preparing catalytic cracking assistant samples which are sequentially numbered from CAZ8-1 to CAZ13-2.

The results of the same evaluation as in example 31-1 are shown in tables 28 and 29, respectively.

Watch 28

Watch 29

Examples 44 to 56

Examples 44-56 are the auxiliary agents CAZ 14-CAZ 26 containing microporous ZSM-5 (GPZ 14-GPZ 26) in sequence, and the material ratios correspond to examples 31-43, for example, in example 44-1, GPZ1-1 is replaced by GPZ14-1, in example 44-2, GPZ1-2 is replaced by GPZ14-2, and so on, until example 56-1, GPZ14-1 is replaced by GPZ26-1, in example 56-2, GPZ14-2 is replaced by GPZ 26-2. The evaluation was made in the same manner as in example 31-1, and the results are shown in tables 30 to 42, respectively.

Comparative examples 44 to 56

Comparative examples 44-56 are comparative aids DCAZ-14 to DCAZ-26 containing microporous ZSM-5 (D14-D26) in this order, respectively, and the material ratios correspond to examples 44-50, respectively, e.g., in comparative example 44-1, GPZ1-1 was replaced with D14-1, in comparative example 44-2, GPZ1-2 was replaced with D14-2, etc., until in comparative example 56-1, GPZ14-1 was replaced with D26-1, and in comparative example 50-2, GPZ14-2 was replaced with D26-2.

The evaluation was made in the same manner as in example 31-1, and the results are shown in tables 30 to 42, respectively.

Watch 30

Watch 31

Watch 32

Watch 33

Watch 34

Watch 35

Watch 36

Watch 37

Watch 38

Watch 39

Watch 40

Watch 41

Watch 42

Examples 57 to 62

The same as example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced with the phosphorus-modified molecular sieves GPZ21-1 to GPZ26-2 prepared in examples 21-1 to 26-2, respectively. Preparing catalytic cracking assistant samples which are sequentially numbered from CAZ27-1 to CAZ32-2.

The evaluation was made in the same manner as in example 31-1, and the results are shown in tables 43 and 44, respectively.

Watch 43

Watch 44

Example 63-1

The difference from example 31-1 is that a phosphorus aluminum inorganic Binder was substituted for Binder2 prepared in example 28. The catalytic cracking assistant is prepared, and the number is CAZ33-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 45.

Example 63-2

The difference from example 31-2 is that the phosphorus aluminum inorganic Binder was replaced with Binder2 prepared in example 28. The catalytic cracking assistant is prepared, and the number is CAZ33-2.

Example 64-1

The difference from example 31-1 is that the phosphorus aluminum inorganic Binder was replaced with Binder3 prepared in example 29. The catalytic cracking assistant is prepared, and is numbered CAZ34-1.

Example 64-2

The difference from example 31-2 is that the phosphorus aluminum inorganic Binder was replaced with Binder3 prepared in example 29. The catalytic cracking assistant is prepared, and is numbered CAZ34-2.

Example 65-1

The difference from example 31-1 is that a phosphorus aluminum inorganic Binder was substituted with Binder4 prepared in example 30. The catalytic cracking auxiliary agent is prepared, and the serial number is CAZ35-1.

Example 65-2

The difference from example 31-2 is that a phosphorus aluminum inorganic Binder was substituted for Binder4 prepared in example 30. The catalytic cracking assistant is prepared, and is numbered CAZ35-2.

TABLE 45

Example 66-1

The same as example 31-1 except that the phosphorus-modified ZSM-5 molecular sieve sample GPZ was 1-1 wt%, kaolin clay was 18 wt%, the aluminophosphate inorganic Binder Binder3 was 22 wt%, pseudoboehmite was 10wt%, and alumina sol was 5 wt%. The catalytic cracking assistant is prepared, and the number is CAZ36-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 46.

Example 66-2

The same as example 66-1 except that GPZ1-1 was replaced with GPZ1-2. The catalytic cracking assistant is prepared, and the number is CAZ36-2.

Comparative example 66-1

The same as example 66-1, except that GPZ1-1 was replaced with D1-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ36-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 46.

Comparative example 66-2

The same as in example 22-1 except that GPZ1-1 was replaced with D1-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ36-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 46.

TABLE 46

Example 67-1

The same as example 44-1, except that the phosphorus-modified ZSM-5 molecular sieve sample GPZ was 14-1 wt%, kaolin clay was 24 wt%, the aluminophosphate inorganic Binder Binder4 was 20 wt%, pseudoboehmite was 6 wt%, and silica sol was 10 wt%. The catalytic cracking assistant is prepared, and the number is CAZ37-1.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 47.

Example 67-2

The same as in example 67-1, except that GPZ14-1 was replaced with GPZ14-2. The catalytic cracking auxiliary agent with the number of CAZ37-2 is prepared.

Comparative example 67-1

The same as in example 67-1, except that GPZ14-1 was replaced with D14-1. A comparative sample of catalytic cracking aid was prepared, numbered DCAZ37-1.

Comparative example 67-2

The same as example 67-1 except that GPZ14-1 was replaced with D14-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ37-2.

Watch 47

Example 68-1

Mixing the adhesive aluminium sol and kaolin, preparing the mixture into slurry with the solid content of 30 weight percent by using decationized water, stirring the slurry evenly, and adding hydrochloric acidThe slurry pH was adjusted to 2.8, and after aging by standing at 55 ℃ for 1 hour, the phosphorus-modified molecular sieve GPZ1-1 prepared in example 1-1 was added to form a catalyst slurry (solid content: 35% by weight), which was further stirred and spray-dried to prepare a microspherical catalyst. The microspheroidal catalyst was then calcined at 500 ℃ for 1 hour, then washed with ammonium sulfate (where ammonium sulfate: microspheroidal catalyst: water = 0.5. The mixture ratio is 50% of molecular sieve, 23% of kaolin and aluminium sol (Al) ₂ O ₃ Calculated) 27 percent.

The evaluation was made in the same manner as in example 31-1, and the results are shown in Table 48.

Example 68-2

The same as example 68-1 except that GPZ1-1 was replaced with GPZ1-2, which was prepared in example 1-2. And preparing a catalytic cracking assistant sample with the number of CAZ38-2.

Comparative example 68-1

The same as in example 68-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was used in place of the comparative sample D1-1 of comparative example 1-1. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ38-1.

Comparative example 68-2

The same as in example 68-1 except that GPZ1-1, a phosphorus-modified molecular sieve, was replaced with a comparative sample D1-2 of comparative example 1-2. A comparative sample of the catalytic cracking assistant was prepared and numbered DCAZ38-2.

Watch 48

Example 69-1 and example 69-2

Example 69-1 and example 69-2 used were the catalytic cracking assistants CAZ1-1 and CAZ1-2 of example 31-1 and example 31-2, respectively. The feed oil for catalytic cracking was naphtha shown in Table 49.

The evaluation conditions were a reaction temperature of 620 ℃, a regeneration temperature of 620 ℃ and an agent-to-oil ratio of 3.2.

Table 50 shows the weight composition of the respective catalytic cracking assistant-containing catalyst mixtures and the reaction results.

Comparative examples 69-1 and 69-2

The comparative catalytic cracking assistants DCAZ1-1 and DCAZ1-2 of comparative example 31-1 and comparative example 31-2 were used, respectively, in the same manner as in example 69-1.

The weight composition of each of the catalyst mixtures containing the comparative sample of catalytic cracking aid and the results of the reaction are shown in Table 50.

Watch 49

Starting materials	Naphtha (a)
		Density (20 ℃ C.)/(g.m) ^-3 )	735.8
Vapor pressure/kPa	32
		Mass group composition/%)
Paraffin hydrocarbon	51.01
		N-alkanes	29.40
Cycloalkanes	38.24
		Olefins	0.12
Aromatic hydrocarbons	10.52
		Distillation range/. Degree C
First distillation	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

Watch 50

Example 70-1 and example 70-2

Example 70-1 and example 70-2 used were the catalytic cracking assistants CAZ14-1 and CAZ14-2 of example 44-1 and example 44-2, respectively. The feed oil for catalytic cracking was naphtha shown in Table 49.

Table 51 shows the composition by weight of the respective catalyst mixtures containing the catalytic cracking assistants and the reaction results.

Comparative examples 70-1 and 70-2

The comparative catalytic cracking aids DCAZ14-1 and DCAZ14-2 of comparative example 44-1 and comparative example 44-2 were used, respectively, in the same manner as in example 70-1.

The weight composition of each of the catalyst mixtures containing the comparative sample of catalytic cracking aid and the results of the reaction are shown in Table 51.

Watch 51

The preferred embodiments of the present invention have been described in detail, however, the present invention 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 invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

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. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present application can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.

Claims

1. A catalytic cracking assistant is characterized in that the catalytic cracking assistant contains 5-75 wt% of phosphorus modified MFI structure molecular sieve based on the dry basis of the catalytic cracking assistant; wherein, the K value of the phosphorus modified MFI structure molecular sieve satisfies the following conditions: k is more than or equal to 70% and less than or equal to 90%, and K = P1/P2 × 100%, wherein P1 represents the phosphorus content in the area of a 100 square nanometer region within the vertical depth of any crystal face of the molecular sieve crystal grain of 0-2 nm determined by the XPS method, and P2 represents the phosphorus content in the area of a 100 square nanometer region within the thickness interval of 5-10 nm of the vertical depth of any crystal face of the molecular sieve crystal grain determined by the EPMA method.

2. The catalytic cracking aid of claim 1, wherein the K value of the phosphorus-modified MFI structure molecular sieve satisfies: k is between 75 and 90 percent.

3. The catalytic cracking aid of claim 1, wherein the K value of the phosphorus-modified MFI structure molecular sieve satisfies: k is more than or equal to 78 percent and less than or equal to 85 percent.

4. The catalytic cracking aid of claim 1, wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P ₂ O ₅ The molar ratio of the alumina to the alumina is more than or equal to 0.01.

5. The catalytic cracking aid of claim 1, wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P ₂ O ₅ The molar ratio of the alumina to the alumina is more than or equal to 0.2.

6. The catalytic cracking aid of claim 1, wherein the phosphorus-modified MFI structure molecular sieve has a phosphorus content of P ₂ O ₅ The molar ratio of the alumina to the alumina is more than or equal to 0.3.

7. The catalytic cracking aid of claim 1, wherein the phosphorus-modified MFI structure molecular sieve has phosphorus content of P ₂ O ₅ The molar ratio of the alumina to the alumina is 0.4-0.7.

8. The catalytic cracking aid of claim 1, wherein the phosphorus-modified MFI structure molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve.

9. The catalytic cracking aid of claim 8, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15 to 1000.

10. The catalytic cracking aid of claim 8, wherein the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 20 to 200.

11. The catalytic cracking assistant of claim 8, wherein the hierarchical pore ZSM-5 molecular sieve has a mesopore volume accounting for more than 10% of the total pore volume, an average pore diameter of 2 to 20nm, and a silica/alumina molar ratio of 15 to 1000.

12. The catalytic cracking aid of claim 8, wherein the hierarchical pore ZSM-5 molecular sieve has a silica/alumina molar ratio of 20 to 200.

13. The catalytic cracking assistant according to claim 1, further comprising 1 to 40 wt% of a binder and 0 to 65 wt% of a second clay, based on the dry weight of the catalytic cracking assistant.

14. A catalytic cracking aid according to claim 13, wherein the binder comprises a phosphorus-aluminum inorganic binder.

15. A catalytic cracking aid according to claim 14, wherein the aluminophosphate inorganic binder is an aluminophosphate glue and/or a first clay-containing aluminophosphate inorganic binder.

16. A preparation method of a catalytic cracking assistant comprises the steps of mixing and pulping a phosphorus-modified MFI structure molecular sieve, a binder and optionally added second clay, and spray-drying to obtain the catalytic cracking assistant, and is characterized in that the phosphorus-modified MFI structure molecular sieve is prepared by mixing and contacting an aqueous solution of a phosphorus-containing compound with the temperature of 40-150 ℃ and a hydrogen type MFI structure molecular sieve with the temperature of 40-150 ℃ at the basically same temperature for at least 0.1 hour by an impregnation method, drying, and roasting at 200-600 ℃ for at least 0.1 hour in an air or steam atmosphere; or, after mixing and pulping the phosphorus-containing compound, the hydrogen MFI structure molecular sieve and water, heating to 40-150 ℃, keeping for at least 0.1 hour, drying, and roasting for at least 0.1 hour at 200-600 ℃ in the air or steam atmosphere; the basically same temperature means that the temperature difference between the water solution of the phosphorus-containing compound and the hydrogen MFI structure molecular sieve is +/-5 ℃; the phosphorus modified MFI structure molecular sieve has a K value which satisfies: k is more than or equal to 70% and less than or equal to 90%, and K = P1/P2 × 100%, wherein P1 represents the phosphorus content in the area of a 100 square nanometer region within the vertical depth of any crystal face of the molecular sieve crystal grain of 0-2 nm determined by the XPS method, and P2 represents the phosphorus content in the area of a 100 square nanometer region within the thickness interval of 5-10 nm of the vertical depth of any crystal face of the molecular sieve crystal grain determined by the EPMA method.

17. The process of claim 16 wherein the phosphorus modified MFI structure molecular sieve is prepared by contacting an aqueous solution of a phosphorus-containing compound having a temperature of 50 to 150 ℃ with a hydrogen MFI structure molecular sieve having a temperature of 50 to 150 ℃ in a mixing manner at substantially the same temperature by impregnation.

18. The process of claim 16, wherein the phosphorus-modified MFI structure molecular sieve is prepared by contacting an aqueous solution of a phosphorus-containing compound having a temperature of 70 to 130 ℃ with a hydrogen MFI structure molecular sieve having a temperature of 70 to 130 ℃ by an impregnation method under mixing at substantially the same temperature.

19. The method according to claim 16, wherein the phosphorus compound is selected from an organic phosphide and/or an inorganic phosphide.

20. The process according to claim 19, wherein the organophosphate is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

21. The process according to claim 16, wherein the molar ratio of the phosphorus-containing compound to the hydrogen MFI structure molecular sieve is 0.01 to 2.

22. The method of claim 16, wherein the molar ratio of the phosphorus-containing compound calculated as phosphorus to the hydrogen-type MFI structure molecular sieve calculated as aluminum is 0.1-1.5.

23. The process according to claim 16, wherein the molar ratio of the phosphorus-containing compound to the hydrogen MFI structure molecular sieve is 0.2 to 1.5.

24. The method according to claim 16, wherein the phosphorus-containing compound is a mixture of boron phosphate and one or more selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate, and the mixture contains 10 to 80% by weight of boron phosphate.

25. The method according to claim 24, wherein the mixture contains 20 to 40% by weight of boron phosphate.

26. The method of claim 16, wherein the contacting is carried out in a water-sieve weight ratio of 0.5 to 1.

27. The method of claim 16, wherein the firing is performed at 450 to 550 ℃ under an air atmosphere.

28. The method of claim 16, wherein the binder is a phosphor-aluminum inorganic binder.

29. The method of claim 28, 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 clay ₂ O ₃ 15-40% by weight, calculated as P, of an aluminium component ₂ O ₅ 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, wherein the P/Al weight ratio 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.

30. The method according to claim 16, wherein the second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

31. The method of claim 16, wherein the binder comprises 3 to 39 wt% of the aluminophosphate inorganic binder on a dry basis and 1 to 30 wt% of the other inorganic binder on a dry basis, based on the total weight of the catalytic cracking assistant.

32. The method of claim 31, wherein the additional inorganic binder comprises at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass.

33. The method of claim 16, further comprising: performing first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalytic cracking auxiliary agent; wherein the roasting temperature of the first roasting is 300-650 ℃, and the roasting time is 0.5-8 h; the temperature of the drying treatment is 100-200 ℃, and the drying time is 0.5-24 h.

34. The method of claim 29, further comprising: preparing the first clay-containing phosphorus-aluminum inorganic binder by adopting the following steps: pulping and dispersing an alumina source, the first clay and water into slurry with the 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 weight of the alumina source is 15-40 parts by weight of Al ₂ O ₃ (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 =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.

35. A catalytic cracking aid prepared by the method of any one of claims 16 to 34.

36. A method for catalytic cracking of hydrocarbon oil, comprising: a hydrocarbon oil is contacted with the catalytic cracking assistant according to any one of claims 1 to 15 and 35 under catalytic cracking conditions.

37. The method of claim 36, wherein the method comprises: under the catalytic cracking condition, the hydrocarbon oil is in contact reaction with a catalyst mixture containing the catalytic cracking auxiliary agent and a catalytic cracking catalyst; in the catalyst mixture, the content of the catalytic cracking assistant is 0.1-30 wt%.

38. The method of claim 36 or 37, wherein the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiling, coking wax oil and coal liquefaction products.