CN110193376B

CN110193376B - Petroleum hydrocarbon catalytic cracking catalyst

Info

Publication number: CN110193376B
Application number: CN201810159587.9A
Authority: CN
Inventors: 王鹏; 周灵萍; 姜秋桥; 宋海涛; 孙言; 严加松; 田辉平; 张久顺
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: 2018-02-26
Filing date: 2018-02-26
Publication date: 2021-09-07
Anticipated expiration: 2038-02-26
Also published as: CN110193376A

Abstract

A petroleum hydrocarbon catalytic cracking catalyst comprises a carrier, a Y-type molecular sieve, a mesoporous molecular sieve with an M41S structure and a molecular sieve with a pore opening diameter of 0.59-0.73 nm; the Y-type molecular sieve comprises an ultra-stable Y-type molecular sieve containing phosphorus and rare earth, the total pore volume of the Y-type molecular sieve is 0.33-0.39 mL/g, the pore volume of secondary pores with the diameter of 2-100 nm accounts for 10-25% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the proportion of non-framework aluminum content to total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of B acid content to L acid content measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 2.50. The catalyst has high heavy oil converting activity, high coke selectivity, high gasoline yield, high liquefied gas yield, high light oil yield and high total liquid yield.

Description

Petroleum hydrocarbon catalytic cracking catalyst

Technical Field

The present invention relates to a catalytic cracking catalyst for petroleum hydrocarbon.

Background

Catalytic cracking is an important means for processing hydrocarbon oil, the amount of slag doped in a catalytic cracking raw material is increased in recent years, and as the proportion of residual oil macromolecules is large, the content of aromatic hydrocarbon is high, coking is easy to occur in the reaction process, and higher requirements are provided for the heavy oil cracking activity of a cracking catalyst. In order to improve the processability of the residual oil, the residual oil is hydrogenated and then catalytically cracked in the prior art to produce fuels such as gasoline, diesel oil and the like.

At present, the cracking catalyst for improving the conversion depth of heavy oil uses an ultra-stable Y-shaped molecular sieve in the catalyst. For example, CN1060976, CN1060977, CN1128673, CN1005405, CN1119206, CN1065844, US5340957, US5206194, US4273753, US4438178, US4584287 and US4429053 provide hydrothermal preparation methods of ultrastable Y-type molecular sieves, but the above methods are easy to cause defects in the crystal structure of the molecular sieves, and the obtained ultrastable Y-type molecular sieves have low heavy oil cracking activity and poor coke selectivity.

CN1382525A, CN1194941A, CN1683244A disclose the use of SiCl₄A method for preparing an ultra-stable Y-type molecular sieve by gas-phase chemical dealumination. However, the existing gas-phase ultrastable molecular sieve still has the problem of low activity when used for heavy oil cracking, can not meet the processing requirements of heavy oil and poor oil, and influences the product distribution and economic benefit of a catalytic cracking device.

CN1330981A, CN1353086A, CN1506161A, CN1317547A and CN1436727A introduce phosphorus and rare earth into Y-type zeolite. However, the cracking catalyst prepared by using these zeolites in the prior art is used for hydrocracking the hydrogenated residual oil, and the activity and selectivity of heavy oil cracking are poor.

CN106268932A provides a catalytic cracking catalyst, a preparation method and application thereof. The catalyst contains a substrate, a super-stabilized USY molecular sieve and a super-stabilized IM-5 molecular sieve, wherein the weight of the catalyst is taken as a reference, the total weight content of the super-stabilized USY molecular sieve and the super-stabilized IM-5 molecular sieve is 50 wt% -90 wt%, and the weight ratio of the super-stabilized IM-5 molecular sieve to the super-stabilized USY molecular sieve is (0.01-0.25): 1. the catalyst is suitable for hydrogenation wax oil conversion and hydrogenation residual oil conversion, and has low cracking activity, low gasoline yield and poor coke selectivity.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a petroleum hydrocarbon catalytic cracking catalyst which has higher heavy oil cracking activity and better coke selectivity when being used for heavy oil cracking. The second technical problem to be solved by the invention is to provide a preparation method and an application method of the catalyst.

The invention provides a petroleum hydrocarbon catalytic cracking catalyst, which comprises, by weight based on dry basis, 40-80 wt% of a carrier, such as 50-70 wt%, 10-50 wt% of a Y-type molecular sieve, such as 20-50 wt%, 5-15 wt% of a mesoporous molecular sieve with an M41S structure, 5-15 wt% of a molecular sieve with a pore opening diameter of 0.59-0.73 nm, wherein the Y-type molecular sieve comprises a phosphorus and rare earth-containing ultrastable Y-type molecular sieve (the modified Y-type molecular sieve for short), the content of rare earth oxide in the phosphorus and rare earth-containing ultrastable Y-type molecular sieve is 4-11 wt%, and the phosphorus content is P₂O₅The content is 0.05-10 wt%, the content of sodium oxide is 0.1-0.7 wt%, the total pore volume is 0.33-0.39 mL/g, the percentage of the pore volume of the secondary pores with the aperture of 2-100 nm of the super-stable Y-type molecular sieve containing phosphorus and rare earth in the total pore volume of the super-stable Y-type molecular sieve containing phosphorus and rare earth is 10-25%, the unit cell constant is 2.440-2.455 nm, and the framework silicon-aluminum ratio (SiO is)₂/Al₂O₃Molar ratio) may be 7.3 to 14.0: 1, the percentage of non-framework aluminum content in the molecular sieve to the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the phosphorus and rare earth-containing ultrastable Y-type molecular sieve measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 2.50.

The lattice collapse temperature of the ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention is not lower than 1050 ℃, preferably, the lattice collapse temperature of the molecular sieve is 1055-1080 ℃, for example, 1057-1075 ℃.

The phosphorus and rare earth containing ultrastable Y-type molecular sieve used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has the advantages that the ratio of the B acid amount to the L acid amount in the total acid amount of the phosphorus and rare earth containing ultrastable Y-type molecular sieve measured at 200 ℃ by a pyridine adsorption infrared method is preferably 2.6-4.0, for example, 2.7-3.3.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has a unit cell constant of 2.440-2.455 nm, such as 2.442-2.450 nm.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention is a high-silicon Y-type molecular sieve, and the framework silicon-aluminum ratio (SiO) of the molecular sieve is₂/Al₂O₃Molar ratio) of 7.3 to 14.0, for example 8.5 to 12.6.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the catalyst provided by the invention has the non-framework aluminum content accounting for not more than 20 wt% of the total aluminum content, for example 13-19 wt%.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has a crystal retention of 38% or more, for example, 38-48% or 39-45% after aging for 17 hours at 800 ℃ under normal pressure and 100 volume% of steam atmosphere. The normal pressure is 1 atm.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has a relative crystallinity of not less than 60%, preferably, the ultrastable Y-type molecular sieve containing phosphorus and rare earth has a relative crystallinity of 60-70%, for example, 60-66%. The method for measuring the relative crystallinity (referred to as crystallinity for short) in the present invention is referred to RIPP146-90 standard method in "analytical methods of petrochemical industry (RIPP test method)", (compiled by Yangshui et al, published by scientific Press, 1990).

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has an implementation mode that the specific surface area is 620-670 m²The/g is, for example, 630 to 660m²/g。

The phosphorus and rare earth containing ultrastable Y-type molecular sieve used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has the preferable total pore volume of 0.35-0.39 mL/g, for example, 0.36-0.375 mL/g.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention has the pore volume of secondary pores with the pore diameter (diameter) of 2.0-100 nm accounting for 10-25% of the total pore volume, and the optimal pore volume is 15-21%.

The ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst contains rare earth elements, and RE is used in the ultrastable Y-type molecular sieve containing phosphorus and rare earth₂O₃The content of the rare earth oxide is 4-11 wt%, preferably 4.5-10 wt%.

In the petroleum hydrocarbon catalytic cracking catalyst provided by the invention, the ultrastable Y-shaped molecular sieve containing the phosphorus and the rare earth contains a phosphorus modified element, and P in the ultrastable Y-shaped molecular sieve containing the phosphorus and the rare earth₂O₅(i.e. with P)₂O₅The phosphorus content) is 0.05 to 10 wt%, for example 0.1 to 6 wt%, preferably 0.1 to 5 wt%.

The content of sodium oxide in the ultrastable Y-type molecular sieve containing phosphorus and rare earth used in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention is not more than 0.7%, and can be 0.3-0.7 wt%, for example, 0.35-0.60 wt% or 0.4-0.55 wt%.

In the petroleum hydrocarbon catalytic cracking catalyst provided by the invention, the preparation method of the ultrastable Y-shaped molecular sieve containing phosphorus and rare earth comprises the following steps:

(1) contacting the NaY molecular sieve with a rare earth solution to perform an ion exchange reaction, filtering and washing to obtain a Y-type molecular sieve containing rare earth with a conventional unit cell size and reduced sodium oxide content; wherein the rare earth solution is also called rare earth salt solution;

(2) modifying the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size, and optionally drying to obtain a Y-type molecular sieve with a reduced unit cell constant, wherein the modifying is to roast the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size at the temperature of 350-480 ℃ in an atmosphere containing 30-90 vol% of water vapor (also called 30-90 vol% of water vapor atmosphere or 30-90 vol% of water vapor) for 4.5-7 hours;

(3) carrying out phosphorus modification treatment on the obtained Y-shaped molecular sieve with the reduced unit cell constant by using a phosphorus compound, and drying to obtain the Y-shaped molecular sieve with the reduced unit cell constant containing phosphorus; wherein the water content of the Y-type molecular sieve with reduced phosphorus unit cell constant is preferably not more than 1 wt%;

(4) reducing the unit cell constant of the phosphorus-containing Y-type molecular sieve obtained in the step (3) and SiCl₄Gas is contacted and reacted at the temperature of 200-650 ℃, wherein SiCl is contained₄: the weight ratio of the Y-type molecular sieve with reduced unit cell constant containing phosphorus obtained in the step (3) on a dry basis is 0.1-0.7: 1, reacting for 10 minutes to 5 hours, and then washing and filtering to obtain the ultrastable Y-type molecular sieve containing phosphorus and rare earth.

The petroleum hydrocarbon catalytic cracking catalyst provided by the invention contains a carrier, wherein the carrier can be a conventional carrier used in the existing catalytic cracking catalyst, and the invention has no particular limitation, and the carrier can be one or more of clay, alumina carrier, silica carrier and silica-alumina carrier. Such as one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. The alumina carrier can be one or more of alumina, hydrated alumina and alumina sol in various forms; for example, one or more selected from gamma-alumina, eta-alumina, theta-alumina, chi-alumina, hydrated alumina such as one or more of pseudo Boehmite (Pseudoboehmite), diaspore (Boehmite), Gibbsite (Gibbsite), and Bayer stone (Bayerite), or alumina sol. The alumina carrier is preferably selected from pseudo-boehmite and alumina sol. In one embodiment, the catalytic cracking catalyst comprises 2 to 15 wt%, preferably 3 to 10 wt%, based on the weight of the catalyst, of alumina sol, and 5 to 40 wt%, or 10 to 30 wt%, preferably 15 to 25 wt%, based on the weight of the alumina solAmount% pseudoboehmite. The silica carrier can be silica gel, water glass and/or silica sol, and preferably, the silica carrier comprises silica sol, based on the weight of the catalyst, and SiO is used as the standard₂The content of the silica sol is 1-30 wt% or 0.5-25 wt%, for example 0.5-20 wt% or 1-15 wt%, and the silica sol can be neutral silica sol, acidic silica sol or alkaline silica sol. Silica-alumina supports such as one or more of silica-alumina sol, silica-alumina gel, amorphous silica-alumina.

The petroleum hydrocarbon catalytic cracking catalyst provided by the invention contains a mesoporous molecular sieve with an M41S structure, and the content of the mesoporous molecular sieve with the M41S structure is 5-15 wt% on a dry basis based on the weight of the petroleum hydrocarbon catalytic cracking catalyst. The mesoporous molecular sieve with the M41S structure is one or more of MCM-41, MCM-48 and MCM-50. Generally, the molar ratio of silicon atoms to aluminum atoms of the molecular sieve with the M41S structure is 10-400: 1, for example, 50 to 350: 1 or 100-300: 1 or 10-200: 1 or 10 to 100: 1 or 20-80: 1 or 15-50: 1. the content of sodium oxide in the molecular sieve with the M41S structure is not more than 0.1 weight percent, and the molecular sieve with the M41S structure can be a hydrogen-type molecular sieve with the M41S structure, such as one or more of HMCM-41, H-Al-MCM-48 and HMCM-50. The hydrogen M41S molecular sieve can be obtained by acid and/or ammonium exchange and calcination of a sodium M41S molecular sieve obtained by synthesis, which is well known to those skilled in the art.

The petroleum hydrocarbon catalytic cracking catalyst provided by the invention contains 5-15 wt% of molecular sieve with pore opening diameter of 0.59-0.73 nm based on the weight of the petroleum hydrocarbon catalytic cracking catalyst. The molecular sieve with the pore opening diameter of 0.59-0.73 nm is selected from at least one of a molecular sieve with an AFR structure, a molecular sieve with an AFS structure, a molecular sieve with an AFI structure, a molecular sieve with a BEA structure, a molecular sieve with a BOG structure, a molecular sieve with a CON structure, a molecular sieve with a GME structure, a molecular sieve with an LTL structure, a molecular sieve with an MEI structure, a molecular sieve with an MOR structure and a molecular sieve with an OFF structure. Preferably: at least one of Beta molecular sieve, SAPO-5 molecular sieve, SAPO-40 molecular sieve, SSZ-24 molecular sieve, CIT-1 molecular sieve, ZSM-18 molecular sieve, mordenite, gmelinite and offretite. Preferably, the molecular sieve with the opening diameter of the pore canal of 0.59-0.73 nm comprises one or more of ZSM-18 molecular sieve, SAPO-5 molecular sieve and Beta molecular sieve. The molecular sieve with the pore opening diameter of 0.59-0.73 nm is preferably a molecular sieve with the hydrogen type pore opening diameter of 0.59-0.73 nm, the sodium oxide content of the molecular sieve is not more than 1.5 wt%, for example, 0.01-1.5 wt%, or 0.1-1 wt%, or 0.2-0.5 wt%, and the molar ratio of silicon to aluminum atoms is 0.1-500, for example, 0.1-300: 1 or 0.5-200: 1 or 1 to 100: 1. for example, preferred molecular sieves having pore opening diameters of 0.59 to 0.73 nanometers are silicalites, such as one or more of Beta, SAPO-40, SSZ-24, CIT-1, ZSM-18, mordenite, gmelinite and offretite, each having a silica to alumina atomic molar ratio of 0.1 to 100 or 1 to 100: 1 or 5-80: 1 or 10 to 50: 1 or 20-40: 1.

in the petroleum hydrocarbon catalytic cracking catalyst provided by the invention, the Y-type molecular sieve comprises the ultrastable Y-type molecular sieve containing phosphorus and rare earth, and the content of the ultrastable Y-type molecular sieve containing phosphorus and rare earth is 10-50 wt%, preferably 20-40 wt% based on the weight of the petroleum hydrocarbon catalytic cracking catalyst. The Y-type molecular sieve may also include other types of Y-type molecular sieves, such as those obtained by prior methods, preferably having a content of no more than 30 wt%, such as from 0 to 20 wt% or from 0 to 10 wt%. Preferably, the Y-type molecular sieve is the ultrastable Y-type molecular sieve containing phosphorus and rare earth.

The invention also provides a preparation method of the petroleum hydrocarbon catalytic cracking catalyst, which comprises the following steps: forming slurry of a carrier, a Y-type molecular sieve, a mesoporous molecular sieve with an M41S structure, a molecular sieve with a pore opening diameter of 0.59-0.73 nm and water, and drying; the Y-type molecular sieve preferably comprises or is the ultrastable Y-type molecular sieve containing the phosphorus and the rare earth, and the preparation method of the ultrastable Y-type molecular sieve containing the phosphorus and the rare earth comprises the following steps:

(1) contacting the NaY molecular sieve with a rare earth salt solution to perform an ion exchange reaction, filtering, washing, and optionally drying to obtain a rare earth-containing Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content;

(2) roasting the rare earth-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere of 30-90 vol% of water vapor, and optionally drying to obtain the Y-type molecular sieve with the reduced unit cell constant;

(3) carrying out phosphorus modification treatment on the Y-type molecular sieve with the reduced unit cell constant obtained in the step (2) by using a phosphorus compound, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant containing phosphorus;

(4) contacting the phosphorus-containing Y-type molecular sieve with reduced unit cell constant with silicon tetrachloride gas for reaction, washing and filtering, preferably according to SiCl₄: the Y-type molecular sieve with reduced unit cell constant of phosphorus is 0.1-0.7: 1, the Y-shaped molecular sieve with the reduced unit cell constant containing phosphorus is contacted and reacted with silicon tetrachloride gas at the reaction temperature of 200-650 ℃ for 10 minutes to 5 hours, and the Y-shaped molecular sieve containing phosphorus and rare earth is obtained by washing and filtering. Wherein the water content of the Y-type molecular sieve having a reduced phosphorus-containing unit cell constant is preferably not more than 1% by weight.

The preparation method of the petroleum hydrocarbon catalytic cracking catalyst provided by the invention optionally further comprises the steps of washing and drying the catalyst microspheres obtained by drying, such as spray drying. The slurry formation, spray drying, washing and drying are prior art and the present invention has no special requirements.

The carrier of the petroleum hydrocarbon catalytic cracking catalyst provided by the invention can contain or not contain rare earth elements, and the catalyst carrier can contain 0-5 wt% of rare earth (based on RE) based on the weight of the petroleum hydrocarbon catalytic cracking catalyst₂O₃In terms of lanthanum and/or cerium, wherein the lanthanum and/or cerium is present in an amount of 50 wt.% or more, for example 60 wt.% or more, based on the total rare earth. The addition of rare earth elements to the support can improve the stability of the catalyst. When the carrier contains rare earth elements, the rare earth compound is added in the process of forming the catalyst slurry, and the rare earth can be firstly changed into rare earthThe compound is mixed with the carrier and then mixed with the molecular sieve, or the carrier and the molecular sieve are mixed to form slurry, and then the rare earth compound is added, or the rare earth compound and part of the carrier are mixed to form mixture, and then the mixture is added into the slurry formed by part of the carrier and the molecular sieve.

The petroleum hydrocarbon catalytic cracking catalyst is suitable for catalytic cracking conversion of hydrocarbon oil, and is particularly suitable for catalytic cracking of heavy oil. Therefore, the invention provides a heavy oil conversion method, which comprises the step of carrying out contact reaction on heavy oil and the petroleum hydrocarbon catalytic cracking catalyst under catalytic cracking conditions, wherein the reaction temperature is 400-600 ℃, and the weight hourly space velocity is 5-30 h^-1The agent-oil ratio is 1-10 (weight ratio); the reaction temperature is preferably 450-550 ℃ or 480-530 ℃, and the weight hourly space velocity is preferably 8-25 h^-1The ratio of solvent to oil is preferably 2-7. Such as one or more of atmospheric residue, vacuum residue, coker gas oil, deasphalted oil, or hydrotreated oil obtained by hydrotreating the above hydrocarbon oil. The heavy oil conversion method provided by the invention is particularly suitable for hydrogenation residue catalytic conversion. In one embodiment, the heavy oil is a hydrogenated residue having an aromatic hydrocarbon content of 40 to 75 wt%, such as 45 to 65 wt% or 50 to 70 wt%, a paraffin hydrocarbon content of 1 to 25 wt%, such as 5 to 20 wt% or 8 to 15 wt%, a naphthene hydrocarbon content of 15 to 45 wt%, such as 20 to 45 wt% or 25 to 35 wt%, and a specific gravity of 0.92 to 0.95g/cm³For example, 0.925 to 0.945g/cm³Or 0.93 to 0.942g/cm³The catalyst-to-oil ratio refers to the weight ratio of the catalyst to the raw oil.

The catalyst provided by the invention contains the ultrastable Y-type molecular sieve containing phosphorus and rare earth, the mesoporous molecular sieve with the M41S structure and the molecular sieve with the pore opening diameter of 0.59-0.73 nanometer, has excellent heavy oil macromolecule cracking capability, good product selectivity, high heavy oil conversion rate and light oil yield and good coke selectivity, can have higher heavy oil conversion activity and lower coke selectivity compared with a catalytic cracking catalyst obtained by the conventional method, is used for hydrogenation residual oil conversion with higher aromatic hydrocarbon content, and can have higher gasoline yield, liquefied gas yield, light oil yield and total liquid yield.

The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of preparing a stable Y-shaped molecular sieve containing phosphorus and rare earth, forming slurry by the ultra-stable Y-shaped molecular sieve containing phosphorus and rare earth, a carrier, a mesoporous molecular sieve with an M41S structure, a molecular sieve with a pore opening diameter of 0.59-0.73 nm and water, and drying to prepare the petroleum hydrocarbon catalytic cracking catalyst provided by the invention.

The heavy oil conversion method provided by the invention has the advantages of high heavy oil conversion rate, low coke yield, high light oil yield, and higher gasoline yield, liquefied gas yield and total liquid yield compared with the conventional heavy oil conversion method.

Detailed Description

The invention provides a petroleum hydrocarbon catalytic cracking catalyst, which takes the dry weight of the petroleum hydrocarbon catalytic cracking catalyst as a reference, and comprises 40-80 wt% of a carrier, 10-50 wt% of a Y-type molecular sieve, 5-15 wt% of a mesoporous molecular sieve with an M41S structure and 5-15 wt% of a molecular sieve with a pore opening diameter of 0.59-0.73 nm, wherein the molecular sieve comprises the following components in percentage by weight: 50-75 wt% of carrier is preferably 50-70 or 55-75 wt%, 15-50 wt% of Y-type molecular sieve is preferably 20-40 wt% or 25-45 wt%, 5-15 wt% of mesoporous molecular sieve with M41S structure is preferably 5-10 wt%, and 5-15 wt% of molecular sieve with pore opening diameter of 0.59-0.73 nm (also called shape-selective molecular sieve in the invention) is preferably 5-10 wt%.

In the petroleum hydrocarbon catalytic cracking catalyst provided by the invention, the content of the rare earth oxide in the phosphorus and rare earth containing ultrastable Y-type molecular sieve is 4-11 wt%, preferably 4.5-10 wt%; p in the ultrastable Y-type molecular sieve containing phosphorus and rare earth₂O₅(i.e. with P)₂O₅The phosphorus content) is 0.05 to 10 wt.%, for example 0.1 to 6 wt.%, preferably 0.1 to 5 wt.%; the content of sodium oxide is 0.1-0.7 wt%, preferably 0.3-0.7 wt%, the total pore volume is 0.33-0.39 mL/g, and the pore diameter is 2The pore volume of the secondary pores with the nm-100 nm accounts for 10-25 percent, preferably 15-21 percent of the total pore volume, the unit cell constant is 2.440-2.455 nm, and the framework silicon-aluminum ratio (SiO2/Al2O3 molar ratio) is as follows: 7.3-14.0, the percentage of non-framework aluminum content in the molecular sieve in the total aluminum content is not higher than 20%, preferably 13-19, the relative crystallinity is not lower than 60%, the lattice collapse temperature is 1055-1080 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the phosphorus and rare earth containing ultrastable Y-type molecular sieve measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 2.50, preferably 2.6-4.0.

In the petroleum hydrocarbon catalytic cracking catalyst provided by the invention, the ultrastable Y-type molecular sieve containing phosphorus and rare earth is a gas-phase ultrastable modified Y-type molecular sieve containing phosphorus and rare earth, and the preparation process comprises the step of contacting the Y-type molecular sieve with silicon tetrachloride to carry out dealuminization and silicon supplementation reaction. The molecular sieve has high crystallinity, secondary pore structure and high thermal and hydrothermal stability.

In the preparation method of the catalytic cracking catalyst, in the preparation method of the ultrastable Y-shaped molecular sieve containing the phosphorus and the rare earth, the NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction in the step (1) to obtain the Y-shaped molecular sieve containing the rare earth and having the conventional unit cell size and the reduced sodium oxide content. The NaY molecular sieve can be purchased commercially or prepared according to the existing method, and in one embodiment, the unit cell constant of the NaY molecular sieve is 2.465-2.472 nm, and the framework silicon-aluminum ratio (SiO)₂/Al₂O₃Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85 to 95%, and a sodium oxide content of 13.0 to 13.8% by weight. The NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction, the exchange temperature is preferably 15-95 ℃, for example 65-95 ℃, and the exchange time is preferably 30-120 minutes, for example 45-90 minutes. NaY molecular sieve (dry basis) rare earth salt (RE)₂O₃Meter) H₂O is 1:0.01 to 0.18:5 to 15 by weight. In one embodiment, the ion exchange reaction of the NaY molecular sieve and the rare earth solution comprises the following steps of mixing the NaY molecular sieve, rare earth salt and H₂Forming NaY molecular sieve (also called NaY zeolite), rare earth salt and water according to the weight ratio of 1: 0.01-0.18: 5-15And stirring the mixture at 15-95 ℃, for example, 65-95 ℃, preferably stirring for 30-120 minutes to exchange rare earth ions and sodium ions, wherein the water is decationized water, deionized water or a mixture thereof. The NaY molecular sieve, rare earth salt and water are mixed to form a mixture, the NaY molecular sieve and the water can be formed into slurry, and then rare earth salt and/or aqueous solution of rare earth salt are added into the slurry, wherein the rare earth solution is solution of rare earth salt, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate. The rare earth such as one or more of La, Ce, Pr, Nd and misch metal, preferably, the misch metal contains one or more of La, Ce, Pr and Nd, or further contains at least one of rare earth other than La, Ce, Pr and Nd. In one embodiment, the rare earth is a misch metal. The washing in step (1) is intended to wash out exchanged sodium ions, and for example, deionized water or decationized water may be used for washing. Preferably, the rare earth content of the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content obtained in step (1) and the conventional unit cell size is calculated as RE₂O₃5.5 to 14 wt%, for example, 7 to 14 wt% or 5.5 to 12 wt%, sodium oxide content of not more than 9 wt%, for example, 5.5 to 8.5 wt% or 5.5 to 7.5 wt%, and unit cell constant of 2.465nm to 2.472 nm.

In the preparation method of the catalytic cracking catalyst, the preparation method of the ultrastable Y-shaped molecular sieve containing the phosphorus and the rare earth comprises the step (2) of roasting the Y-shaped molecular sieve containing the rare earth and having the conventional unit cell size for 4.5 to 7 hours at the temperature of 350 to 480 ℃ under the atmosphere of 30 to 90 volume percent of water vapor, preferably, the roasting temperature in the step (2) is 380 to 460 ℃, the roasting atmosphere is 40 to 80 volume percent of water vapor, and the roasting time is 5 to 6 hours. The water vapor atmosphere contains 30-90% by volume of water vapor and also contains other gases, such as one or more of air, helium or nitrogen. The Y-type molecular sieve with the reduced unit cell constant in the step (2) has the unit cell constant of 2.450 nm-2.462 nm.

In the preparation method of the catalytic cracking catalyst, the preparation method of the ultrastable Y-shaped molecular sieve containing phosphorus and rare earth comprises the step (3) of obtaining the molecular sieve in the step (2)The Y-type molecular sieve with the reduced unit cell constant is subjected to phosphorus modification treatment by using a phosphorus compound to introduce phosphorus into the molecular sieve, wherein the phosphorus modification treatment generally comprises the step of contacting the Y-type molecular sieve with the reduced unit cell constant obtained in the step (2) with an exchange solution, wherein the exchange solution contains the phosphorus compound, and the contacting is generally carried out for 10-100 minutes at 15-100 ℃, preferably 30-95 ℃, and then the filtering and washing are carried out. Wherein the weight ratio of water to molecular sieve in the exchange liquid is 2-5, preferably 3-4, phosphorus (as P)₂O₅Calculated) and the weight ratio of the molecular sieve is as follows: 0.0005 to 0.10, preferably 0.001 to 0.05. The phosphorus compound can be one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate. The washing is performed by using water with the weight 5-15 times of that of the molecular sieve, such as decationized or deionized water. The calcined molecular sieve is also dried in step (3) so that the water content in the Y-type molecular sieve having a reduced unit cell constant containing phosphorus is preferably not more than 1% by weight. The drying can be carried out by conventional methods, such as pneumatic drying, oven drying, and flash drying.

In the preparation method of the catalytic cracking catalyst provided by the invention, one embodiment of the preparation method of the ultrastable Y-type molecular sieve containing phosphorus and rare earth is that the phosphorus modification treatment conditions are as follows: adding the Y-type molecular sieve powder sample with the reduced unit cell constant into an exchange solution containing a phosphorus compound, carrying out exchange reaction for 10-100 minutes at 15-100 ℃, filtering and washing; wherein the weight ratio of water to molecular sieve in the exchange liquid is 2-5, preferably 3-4, phosphorus (as P)₂O₅Calculated) and the weight ratio of the molecular sieve is as follows: 0.0005 to 0.10, preferably 0.001 to 0.05.

In the preparation method of the catalytic cracking catalyst, the preparation method of the ultrastable Y-shaped molecular sieve containing the phosphorus and the rare earth comprises the step (4) of SiCl₄: the weight ratio of the Y-type molecular sieve (calculated on a dry basis) is preferably 0.3-0.6: 1, the reaction temperature is preferably 350-500 ℃, and the washing method in the step (4) can adopt a conventional washing method, and can be washed by water, such as decationized water or deionized water, so as to remove Na remained in the zeolite⁺，Cl^-And Al³⁺Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h₂The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, and the washing temperature is 30-60 ℃. Preferably, the washing is performed such that no free Na is detected in the washing solution after washing⁺，Cl^-And Al³⁺Plasma, usually Na in washed molecular sieve samples⁺，Cl^-And Al³⁺The respective contents of ions do not exceed 0.05 wt.%.

In the preparation method of the catalytic cracking catalyst provided by the invention, one embodiment of the preparation method of the ultrastable Y-type molecular sieve containing phosphorus and rare earth comprises the following steps:

(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a rare earth solution, filtering and washing to obtain a Y-type molecular sieve containing rare earth and having a conventional unit cell size and reduced sodium oxide content; the ion exchange is carried out for 30-120 minutes under the conditions of stirring and the temperature of 15-95 ℃, preferably 65-95 ℃;

(2) roasting the rare earth-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere containing 30-90 vol% of water vapor, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant; the unit cell constant of the Y-type molecular sieve with the reduced unit cell constant is 2.450 nm-2.462 nm;

(3) adding the Y-type molecular sieve with the reduced unit cell constant into an exchange solution containing a phosphorus compound, carrying out exchange reaction for 10-100 minutes at 15-100 ℃, filtering and washing; wherein the weight ratio of water to molecular sieve in the exchange liquid is 2-5, preferably 3-4, phosphorus (as P)₂O₅Calculated) to the molecular sieve in a weight ratio of 0.0005 to 0.10, preferably 0.001 to 0.05, and drying to obtain a phosphorus-containing Y-type molecular sieve with a reduced unit cell constant and a water content of less than 1 wt%;

(4) mixing the phosphorus-containing Y-type molecular sieve with SiCl vaporized by heating, wherein the water content of the Y-type molecular sieve is less than 1 wt%₄Gas contact of SiCl₄: phosphorus-containing Y with a reduced unit cell constant and a water content of less than 1 wt.%The weight ratio of the type molecular sieve (calculated on a dry basis) is 0.1-0.7: 1, carrying out contact reaction for 10 minutes to 5 hours at the temperature of 200-650 ℃, and washing and filtering to obtain the ultrastable Y-type molecular sieve containing phosphorus and rare earth.

The method for preparing the stable Y-shaped molecular sieve containing the phosphorus and the rare earth can obtain the high-silicon Y-shaped molecular sieve with a certain secondary pore structure, high crystallinity, high thermal stability and high hydrothermal stability, and the molecular sieve has uniform aluminum distribution and less non-framework aluminum content.

In the preparation method of the chemical cracking catalyst provided by the invention, the carrier can be one or more of clay, alumina carrier, silica carrier and silica-alumina carrier. The alumina carrier is one or more of gamma-alumina, eta-alumina, theta-alumina, chi-alumina, pseudo-Boehmite (Pseudoboemite), Boehmite (Boehmite), Gibbsite (Gibbsite), Bayer (Bayerite) or alumina sol; the silica carrier is one or more of silica gel, silica sol and water glass; the silica-alumina carrier is one or more of silica-alumina gel, amorphous silica-alumina and silica-alumina sol, the clay is one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, preferably one or more of kaolin, halloysite, montmorillonite, diatomite and rectorite, and more preferably the kaolin. Preferably, the support comprises a material commonly referred to as a binder, such as an aluminium binder and/or a silica binder, the aluminium binder may be selected from hydrated alumina such as one or more of pseudo-Boehmite (pseudoboehmite), diaspore (Boehmite), Gibbsite (Gibbsite), and Bayerite (bayer), and/or an aluminium sol, the hydrated alumina as a binder typically being subjected to acidification (the acidification product is also referred to as acidified hydrated alumina), wherein the acidification comprises a step of contacting the hydrated alumina with an acid, wherein the preferred acidified acid to aluminium ratio (weight ratio of 36 wt% hydrochloric acid to hydrated alumina, calculated as alumina) is in the range of 0.15 to 0.25: 1, preferably 0.18 to 0.22: 1; the silica binder is one or more of silica sol and water glass, preferably silica sol, and the silica sol is one or more of acidic silica sol (usually with a pH value of 2-4), neutral silica sol (usually with a pH value of 6-8) and alkaline silica sol (usually with a pH value of 9-10.5).

In the preparation method of the chemical cracking catalyst, the proportion of the silicon binder in the total dry basis weight (referred to as the dry basis weight of the catalyst slurry in the invention) of the carrier, the Y-type molecular sieve, the mesoporous molecular sieve (mesoporous molecular sieve for short) with the M41S structure and the molecular sieve (shape-selecting molecular sieve for short) with the pore opening diameter of 0.59-0.73 nm is not more than 30 wt%, for example, 0-15 wt% or 1-15 wt%, preferably 5-15 wt%; the proportion of the aluminum binder in terms of oxides in the total dry basis weight of the support, the Y-type molecular sieve, the mesoporous molecular sieve having the M41S structure, and the molecular sieve having a pore opening diameter of 0.59 to 0.73 nm is not more than 40 wt%, for example, 0 to 40 wt% or 12 to 35 wt%. In one embodiment, the binder is one or more of pseudo-boehmite, alumina sol and silica sol, and the proportion of the binder in terms of oxide to the total dry basis weight of the carrier, the Y-type molecular sieve, the mesoporous molecular sieve with the M41S structure and the molecular sieve with the pore opening diameter of 0.59-0.73 nm is 12-35 wt%, preferably 15-30 wt% or 18-28 wt% or 20-25 wt%. In general, the support other than the binder, referred to herein as the inorganic oxide matrix, is present in a proportion of from 0 to 80 wt%, such as from 10 to 70 wt% or from 20 to 50 wt% or from 25 to 45 wt%, based on the dry weight of the catalyst slurry, and is selected from one or more of the inorganic oxide matrices commonly used in cracking catalysts, with preferred inorganic oxide matrices being clays, for example, from the kaolin family of clays, preferably kaolin, and with preferred clays being present in a proportion of from 10 to 60 wt%, such as from 20 to 50 wt% or from 30 to 45 wt%, based on the dry weight of the catalyst slurry.

The preparation method of the petroleum hydrocarbon catalytic cracking catalyst provided by the invention comprises the following steps: mixing and pulping the Y-type molecular sieve, the mesoporous molecular sieve, the shape-selective molecular sieve, the inorganic oxide matrix, the binder and deionized water of the ultrastable Y-type molecular sieve containing the phosphorus and the rare earth to form catalyst slurry, and drying to obtain the catalytic cracking catalyst. The solids content of the catalyst slurry formed by beating is generally from 10 to 50% by weight, preferably from 15 to 30% by weight. The drying condition after pulping is the drying condition which is commonly used in the preparation process of the catalytic cracking catalyst. Generally, the drying temperature is 100-350 ℃, preferably 200-300 ℃. The drying may be by oven drying, air drying or spray drying, preferably by spray drying.

The invention will be further illustrated by the following examples, which are not to be construed as limiting the invention.

In the examples and comparative examples, the NaY molecular sieve (also called NaY zeolite) was supplied by the chinese petrochemical catalyst co, zeuginese, inc, and had a sodium oxide content of 13.5 wt% and a framework silica to alumina ratio (SiO) of₂/Al₂O₃Molar ratio) of 4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; the chlorinated rare earth and the nitric acid rare earth are chemical pure reagents produced by Beijing chemical plants.

The analysis method comprises the following steps: in each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy; the unit cell constant and relative crystallinity (crystallinity) of the zeolite were measured by X-ray powder diffraction (XRD) using RIPP145-90 and RIPP146-90 standard methods (see the compilation of petrochemical analysis methods (RIPP test methods), Yangchun et al, published by scientific publishers, 1990), and the framework silicon-aluminum ratio of the zeolite was calculated from the following formula: SiO2₂/Al₂O₃＝(2.5858-a₀)×2/(a₀-2.4191)]Wherein, a₀Is the unit cell constant in nm; the total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated. The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).

In each comparative example and example, the acid center type of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption. An experimental instrument: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. By using pyridine to suckThe experimental method for measuring the acid amount at 200 ℃ by an infrared method comprises the following steps: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C^-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 200 ℃, and vacuumizing to 10 DEG C^-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400cm^-1～1700cm^-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 200 ℃. According to pyridine absorption infrared spectrogram of 1540cm^-1And 1450cm^-1The strength of the adsorption peak is characterized to obtain the total content in the molecular sieve

Relative amount of acid center (B acid center) to Lewis acid center (L acid center).

In each of the comparative examples and examples, the secondary pore volume was determined as follows: measuring total pore volume of the molecular sieve according to adsorption isotherm, measuring micropore volume of the molecular sieve according to T mapping method from adsorption isotherm, subtracting micropore volume from total pore volume to obtain secondary pore volume,

the chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.

Example 1

2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized water and stirred to be mixed evenly, 600ml of RE (NO) is added₃)₃Solution (rare earth solution concentration in RE)₂O₃319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying filter cake at 120 ℃, obtaining crystal cell constant of 2.471nm, sodium oxide content of 7.0 wt%, RE₂O₃Calculating Y-type molecular sieve with rare earth content of 8.8 wt%, and calcining at 390 deg.C in the atmosphere containing 50 vol% of water vapor and 50 vol% of air for 6 hr to obtain Y-type molecular sieve with unit cell constant of 2.455nmSieving, cooling, adding molecular sieve into 6L aqueous solution containing 35 g phosphoric acid, heating to 90 deg.C, performing phosphorus modification for 30min, filtering, washing, drying to water content below 1 wt%, and adding SiCl₄: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating₄Reacting gas at 400 ℃ for 2 hours, washing with 20 liters of decationized water, and filtering to obtain the ultrastable Y-type molecular sieve containing phosphorus and rare earth, which is marked as SZ1 and has the physicochemical properties shown in Table 1, wherein the relative crystallinity of the molecular sieve before and after the aging of SZ1 is analyzed by an XRD method after the exposed SZ1 is aged for 17 hours at 800 ℃, 1atm and 100% of water vapor, and the relative crystallinity retention after the aging is calculated, and the result is shown in Table 2, wherein:

example 2

2000 g of NaY molecular sieve (dry basis) is added into 25L of decationized water and stirred to be mixed evenly, 800ml of RECl is added₃Solutions (with RE)₂O₃The solution concentration is measured as: 319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying the filter cake at 120 ℃, and obtaining the crystal cell with the constant of 2.471nm, the content of sodium oxide of 5.5 weight percent and RE₂O₃Measuring a Y-type molecular sieve with the rare earth content of 11.3 weight percent, roasting for 5.5 hours at the temperature of 450 ℃ and under the condition of 80 percent water vapor to obtain the Y-type molecular sieve with the unit cell constant of 2.461nm, cooling, adding the molecular sieve into 6 liters of aqueous solution dissolved with 268 grams of ammonium phosphate, heating to 60 ℃, carrying out phosphorus modification treatment for 50 minutes, filtering and washing the molecular sieve, drying a filter cake to ensure that the water content is lower than 1 weight percent, and then carrying out SiCl treatment according to the weight percent₄: y-type zeolite 0.6: 1, by weight, introducing SiCl vaporized by heating₄The gas was reacted at 480 ℃ for 1.5 hours, and then washed with 20 liters of decationized water, followed by filtration,obtaining the ultrastable Y-type molecular sieve containing phosphorus and rare earth, and recording the molecular sieve as SZ 2. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ2 is analyzed by XRD method after aging of SZ2 in an exposed state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.

Example 3

2000 g of NaY molecular sieve (dry basis) is added into 22L of decationized water and stirred to be mixed evenly, and 570ml of RECl is added₃Solutions (with RE)₂O₃The calculated concentration of the rare earth solution is 319g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and obtaining the rare earth solution with the unit cell constant of 2.471nm, the sodium oxide content of 7.5 weight percent and the RE content₂O₃Metering a Y-type molecular sieve with the rare earth content of 8.5 weight percent, roasting for 5 hours at the temperature of 470 ℃ and under the condition of 70 volume percent of water vapor to obtain the Y-type molecular sieve with the unit cell constant of 2.458nm, cooling, adding the molecular sieve into 6 liters of aqueous solution dissolved with 95g of diammonium hydrogen phosphate, heating to 40 ℃, carrying out phosphorus modification treatment for 80 minutes, filtering and washing the molecular sieve, drying a filter cake to ensure that the water content is lower than 1 weight percent, and then carrying out SiCl treatment according to the weight percent₄: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating₄The gas was reacted at 500 ℃ for 1 hour, then washed with 20 liters of decationized water and filtered to obtain the ultrastable Y-type molecular sieve containing phosphorus and rare earths, noted as SZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ3 is analyzed by XRD method after aging of SZ3 in a naked state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.

Comparative example 1

2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized water and stirred to be mixed evenly, 1000 g of (NH) is added₄)₂SO₄Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification (at 650 deg.C, calcining with 100% steam for 5 hr), and addingAdding into 20L of decationized aqueous solution, stirring to mix well, adding 1000 g (NH)₄)₂SO₄Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment, wherein the hydrothermal treatment conditions are 650 ℃ and roasting for 5 hours under 100% of water vapor, so as to obtain the rare earth-free hydrothermal ultrastable Y-shaped molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and is marked as DZ 1. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ1 is analyzed by XRD method after aging DZ1 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.

Comparative example 2

2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized water and stirred to be mixed evenly, 1000 g of (NH) is added₄)₂SO₄Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification treatment, calcining at 650 deg.C under 100% steam for 5 hr, adding into 20L of decationized aqueous solution, stirring, mixing, adding 200ml RE (NO)₃)₃Solutions (with RE)₂O₃The concentration of the rare earth solution is measured as follows: 319g/L) and 900 g (NH)₄)₂SO₄Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then performing second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-containing hydrothermal ultrastable Y-type molecular sieve marked as DZ2, wherein the hydrothermal ultrastable Y-type molecular sieve is hydrothermally ultrastable twice through ion exchange twice. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ2 is analyzed by XRD method after aging DZ2 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.

Comparative example 3

2000 g of NaY molecular sieve (dry basis) is added into 22L of decationized water and stirred to be mixed evenly, and 570ml of RECl is added₃Solutions (with RE)₂O₃Rare earth solution for measuringThe concentration of the solution is 319g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, drying the filter cake at 120 ℃, and obtaining the crystal cell constant of 2.471nm, the content of sodium oxide of 7.5 weight percent and RE₂O₃Measuring Y-type molecular sieve with 8.5 wt% of rare earth, adding the molecular sieve into 6L of aqueous solution dissolved with 95g of diammonium hydrogen phosphate, heating to 40 ℃, carrying out phosphorus modification treatment for 80 minutes, filtering and washing the molecular sieve, drying a filter cake, drying the filter cake until the water content is lower than 1 wt%, and then carrying out SiCl-based treatment₄: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating₄The gas was reacted at 580 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to obtain the ultrastable Y-type molecular sieve containing phosphorus and rare earths, noted as DZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of zeolite before and after aging of SZ3 is analyzed by XRD method after aging DZ3 in naked state with 100% steam at 800 deg.C for 17 hr, and the relative crystal retention after aging is calculated.

Examples 4 to 7

Examples 4-7 illustrate the preparation and stability of the catalysts provided by the present invention.

The ultra-stable Y-type molecular sieves containing phosphorus and rare earth prepared in the embodiments 1-3 are respectively prepared into catalysts SZ1, SZ2 and SZ3, and the serial numbers of the catalysts are as follows: a1, a2, A3 and a 4.

The kaolin in examples 4-7 was an industrial product of China Kaolin corporation having a solids content of 84% by weight; the pseudoboehmite is produced by Shandong division of China aluminum industry Co., Ltd, and the content of alumina is 35 wt%; the alumina sol is produced by Qilu division of China petrochemical catalyst Limited, the alumina content of the alumina sol is 21 weight percent, the MCM-41 molecular sieve and the MCM-48 molecular sieve are products of Nanjing Gibbs nanotechnology Limited, the silica-alumina ratio of the MCM-41 molecular sieve is 300 (the molar ratio of silicon to aluminum atoms), the crystallinity is 90 percent, the sodium oxide content is 0.1 weight percent, and the hydrogen type is adopted; the Al-MCM-48 molecular sieve has the advantages of 100 silica-alumina ratio (silicon-aluminum atom mole ratio), 91 percent of crystallinity, 0.08 weight t percent of sodium oxide and hydrogen type; beta zeolite and mordenite are commercial products of Qilu Branch of China petrochemical catalyst, Inc., and Beta (Beta) molecular sieves are prepared by the following steps: the product of Qilu division of China petrochemical catalyst, Inc., the molar ratio of silicon to aluminum atoms is 20, and the content of sodium oxide is 0.02 percent by weight; hydrogen mordenite: the new environment-friendly material is produced by Shanghai Shenbroad-leaved epiphyllum, and the molar ratio of silicon to aluminum atoms is 10; sodium oxide content 0.05 wt%, hydrogen form.

The acidic silica sol was obtained from Beijing chemical plant and had a silica content of 25% by weight.

The preparation method of the catalyst comprises the following steps:

(1) weighing quantitative pseudoboehmite (referred to as alundum) and quantitative water, uniformly mixing, adding quantitative concentrated hydrochloric acid (chemical purity, produced by Beijing chemical plant) with the concentration of 36 wt% under stirring, wherein the acid-aluminum ratio is 0.18 (the weight ratio of 36 wt% hydrochloric acid to alundum (calculated by alumina)), heating the obtained mixture to 70 ℃, and aging for 1.5 hours to obtain aged pseudoboehmite, wherein the alumina content of the aged pseudoboehmite is 12 wt%.

(2) Quantitative ultrastable Y-type molecular sieves SZ1, SZ2 and SZ3 containing phosphorus and rare earth, quantitative alumina sol and/or silica sol, quantitative mesoporous molecular sieve (i.e. mesoporous molecular sieve with M41S structure), shape-selective molecular sieve (i.e. molecular sieve with pore opening diameter of 0.59-0.73 nm), quantitative kaolin, aged pseudo-boehmite and deionized water are mixed uniformly to obtain slurry with solid content of 30 wt%, and the slurry is sprayed and dried.

The kind and amount of Y-type zeolite used in step (2), and the amounts of alumina sol, silica sol and kaolin are shown in Table 3. The compositions of catalysts A1 to A4 are given in Table 4. The contents of Y-type zeolite, binder, mesoporous molecular sieve, shape-selective molecular sieve and kaolin in the catalyst composition are calculated by the feeding amount, and the content of rare earth oxide is determined by adopting an X-ray fluorescence spectrometry.

The light oil micro-reactivity of the catalyst was evaluated after aging the catalyst with 100% steam at 800 ℃ for 4 hours or 17 hours, and the evaluation results are shown in Table 5.

TABLE 1

As can be seen from Table 1, the high-stability ultrastable Y-type molecular sieve containing phosphorus and rare earth provided by the invention has the following advantages: the content of sodium oxide is low, the non-framework aluminum content is low when the silicon-aluminum content of the molecular sieve is high, the pore volume of secondary pores with the pore diameter of 2.0-100 nm in the molecular sieve accounts for higher percentage of the total pore volume, the ratio of the total B acid content to the L acid content is high, the crystallinity value measured when the content of rare earth in the molecular sieve with small unit cell constant is high, and the thermal stability is high.

TABLE 2

As can be seen from Table 2, the ultrastable Y-type molecular sieve containing phosphorus and rare earth provided by the invention has higher relative crystallization retention after being aged under the harsh conditions of 800 ℃ and 17 hours in the exposed state of the molecular sieve sample, which indicates that the ultrastable Y-type molecular sieve containing phosphorus and rare earth provided by the invention has high hydrothermal stability.

TABLE 3

TABLE 4

The catalyst composition in percent by weight in Table 4

Evaluation method of light oil micro-inverse activity:

the light oil micro-reverse activity of the sample is evaluated by adopting a standard method of RIPP92-90 (see the edition of petrochemical analysis method (RIPP test method), Yangcui et al, scientific publishing company, published in 1990), the catalyst loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is Hongkong light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the light oil micro-reverse activity is calculated according to the product composition.

Light oil micro-inversion activity (MA) (gasoline yield with boiling point lower than 216 ℃ in product + gas yield + coke yield)/total feed × 100%.

Comparative examples 4 to 6

Comparative examples 4-6 illustrate the activity and stability of petroleum hydrocarbon cracking catalysts prepared using the ultrastable Y-type molecular sieves provided in comparative examples 1-3.

Respectively mixing the ultrastable Y-type molecular sieves DZ1, DZ2 and DZ3 (which respectively replace an SZ1 molecular sieve) prepared in comparative examples 1-3 with pseudo-boehmite, kaolin, a mesoporous molecular sieve, a shape-selective molecular sieve, water and alumina sol according to the preparation method of the catalyst in example 4, and performing spray drying to prepare the microspherical catalyst, wherein the catalyst is sequentially numbered as follows: b1, B2 and B3, the content of Y-type molecular sieve (also called Y-type zeolite) in each catalyst is 30 wt%, and the composition of the rest components is the same as that in example 4. The light oil micro-reactivity of the catalyst was evaluated after aging the catalyst at 800 ℃ for 4 hours or 17 hours with 100% steam. The evaluation methods are shown in examples 4 to 7, and the evaluation results are shown in Table 5.

TABLE 5

Examples 8 to 11

Examples 8 to 11 illustrate the cracking reaction performance of the catalyst provided by the present invention.

The catalytic cracking performance of catalysts A1, A2, A3 and A4 after aging at 800 deg.C for 17 hours with 100% steam was evaluated in a small fixed fluidized bed reactor (ACE), and cracked gas and product oil were collected separately and analyzed by gas chromatography. The catalyst loading is 9g, the reaction temperature is 500 ℃, and the weight hourly space velocity is 16h^-1The oil-to-agent ratio (weight ratio) is shown in Table 7, the properties of the raw oil in the ACE test are shown in Table 6, and the evaluation results are shown in Table 7.

Comparative examples 7 to 9

Comparative examples 7-9 show that catalysts B1, B2, and B3 were aged with 100% steam at 800 ℃ for 17 hours and then evaluated for catalytic cracking reaction performance in a small fixed fluidized bed reactor (ACE), the evaluation method is shown in example 7, the properties of the raw materials for the ACE experiment are shown in Table 6, and the evaluation results are shown in Table 7.

TABLE 6

TABLE 7

As can be seen from tables 5 and 7, the catalytic cracking catalyst provided by the present invention has high hydrothermal stability, is used for heavy oil conversion such as hydrogenation residue oil conversion with high aromatic content, has significantly lower coke selectivity, has significantly higher total liquid yield, has significantly higher light oil yield, significantly improves gasoline yield, and has higher heavy oil conversion activity.

Claims

1. A petroleum hydrocarbon catalytic cracking catalyst comprises, on a dry basis weight, 40-80 wt% of a carrier, 10-50 wt% of a Y-type molecular sieve, 5-15 wt% of a mesoporous molecular sieve having a structure of M41S, and 5-15 wt% of a molecular sieve having a pore opening diameter of 0.59-0.73 nm; the Y-type molecular sieve comprises a phosphorus and rare earth containing ultrastable Y-type molecular sieve, and the rare earth content of the phosphorus and rare earth containing ultrastable Y-type molecular sieve is RE₂O₃4-11 wt.% of phosphorus, calculated as P₂O₅0.05 to 10 wt% of Na₂The content of O is 0.1-0.7 wt%, the total pore volume is 0.33-0.39 mL/g, the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 10-25% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the proportion of non-framework aluminum content in the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of B acid content to L acid content measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.50.

2. The catalytic cracking catalyst for petroleum hydrocarbon according to claim 1, wherein the volume percentage of the pore volume of the secondary pores with the pore diameter of 2nm to 100nm in the ultrastable Y-type molecular sieve containing phosphorus and rare earth in the total pore volume is 15% to 21%.

3. The petroleum hydrocarbon catalytic cracking catalyst of claim 1, wherein the ultrastable Y-type molecular sieve containing phosphorus and rare earth has a non-framework aluminum content of 13-19% of the total aluminum content, and a framework silica-alumina ratio of SiO₂/Al₂O₃The molar ratio is 7.3-14.

4. The catalytic cracking catalyst for petroleum hydrocarbon according to claim 1, wherein the lattice collapse temperature of the phosphorus-and rare earth-containing ultrastable Y-type molecular sieve is 1055-1080 ℃.

5. A petroleum hydrocarbon catalytic cracking catalyst as defined in claim 1, wherein the ratio of the amount of B acid to the amount of L acid in the total acid content of said ultrastable Y-type molecular sieve containing phosphorus and rare earth, as measured by pyridine adsorption infrared method at 200 ℃, is 2.6 to 4.0.

6. The catalytic cracking catalyst for petroleum hydrocarbons according to claim 1, wherein the ultrastable Y-type molecular sieve containing phosphorus and rare earth has a relative crystallinity of 60% to 70%; after aging at 800 ℃ and normal pressure in 100% steam atmosphere for 17 hours, the relative crystallization retention degree of the ultrastable Y-type molecular sieve containing phosphorus and rare earth is more than 38%.

7. The catalytic cracking catalyst for petroleum hydrocarbon according to claim 6, wherein the relative crystal retention of the ultrastable Y-type molecular sieve containing phosphorus and rare earth is 38-48% after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.

8. A petroleum hydrocarbon catalytic cracking catalyst as claimed in any one of claims 1 to 7, wherein the phosphorus and rare earth containing ultrastable Y-type molecular sieve has a rare earth oxide content of 5.5 to 5 ℃10 wt%, sodium oxide content of 0.3-0.7 wt%, and phosphorus content expressed as P₂O₅0.1 to 6 wt%, a cell constant of 2.442 to 2.450nm, and a framework Si/Al ratio of 8.5 to 12.6.

9. A petroleum hydrocarbon catalytic cracking catalyst as recited in claim 1, wherein said mesoporous molecular sieve having the structure of M41S is at least one of MCM-41, MCM-48 and MCM-50.

10. A petroleum hydrocarbon catalytic cracking catalyst as claimed in claim 1, wherein the mesoporous molecular sieve having the structure M41S has a sodium oxide content of not more than 0.1 wt%.

11. The catalytic cracking catalyst for petroleum hydrocarbons according to claim 1, wherein the mesoporous molecular sieve having the structure of M41S has a silicon-aluminum atomic molar ratio of 10 to 400: 1.

12. the catalytic cracking catalyst for petroleum hydrocarbons according to claim 1, wherein the mesoporous molecular sieve having the structure of M41S has a silicon-aluminum atomic molar ratio of 10 to 100: 1.

13. the catalytic cracking catalyst for petroleum hydrocarbons according to claim 9, wherein the mesoporous molecular sieve having the structure of M41S has a molar ratio of silicon to aluminum atoms of 10 to 100: 1.

14. the catalytic cracking catalyst for petroleum hydrocarbons according to claim 1, wherein the molecular sieve having pore opening diameters of 0.59 to 0.73 nm is at least one selected from the group consisting of molecular sieves having structures of AFR, AFS, AFI, BEA, BOG, CON, GME, LTL, MEI, MOR and OFF.

15. The catalyst for catalytic cracking of petroleum hydrocarbons according to claim 1, wherein the molecular sieve having pore opening diameters of 0.59 to 0.73 nm is at least one of Beta, SAPO-5, SAPO-40, SSZ-24, CIT-1, ZSM-18, mordenite, gmelinite and offretite, and the molecular sieve having pore opening diameters of 0.59 to 0.73 nm has a sodium oxide content of 0.01 to 1.5 wt%.

16. The catalytic cracking catalyst for petroleum hydrocarbon according to claim 1, wherein the molecular sieve having pore opening diameters of 0.59 to 0.73 nm has a silicon-aluminum atomic molar ratio of 0.1 to 100.

17. A petroleum hydrocarbon catalytic cracking catalyst as defined in claim 1, wherein said carrier is one or more of clay, alumina carrier, silica carrier, and silica-alumina carrier.

18. The petroleum hydrocarbon catalytic cracking catalyst of claim 1, comprising 50 to 70 wt.% of the carrier on a dry basis, 20 to 40 wt.% of the Y-type molecular sieve on a dry basis, 5 to 15 wt.% of the mesoporous molecular sieve having the structure M41S on a dry basis, and 5 to 15 wt.% of the molecular sieve having a pore opening diameter of 0.59 to 0.73 nm on a dry basis.

19. A preparation method of a catalytic cracking catalyst comprises the steps of forming slurry of a carrier, a Y-type molecular sieve, a mesoporous molecular sieve with an M41S structure, a molecular sieve with a pore opening diameter of 0.59-0.73 nanometers and water, and drying, wherein the Y-type molecular sieve comprises a phosphorus and rare earth containing ultrastable Y-type molecular sieve, and the preparation method of the phosphorus and rare earth containing ultrastable Y-type molecular sieve comprises the following steps:

(4) and (3) carrying out contact reaction on the Y-type molecular sieve with the reduced phosphorus-containing unit cell constant and silicon tetrachloride gas, washing and filtering.

20. The process of claim 19, wherein said rare earth-containing, conventional unit cell size Y-type molecular sieve having a reduced sodium oxide content of step (1) has a unit cell constant of 2.465 to 2.472nm and a sodium oxide content of no more than 9.0 wt.%.

21. The process of claim 19, wherein in step (1), the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content and a conventional unit cell size contains rare earth in an amount of RE₂O₃4.5 to 13 wt%, 4 to 9 wt% of sodium oxide, and 2.465nm to 2.472nm in unit cell constant.

22. The process of claim 19, wherein in step (1), the rare earth-containing conventional unit cell size Y-type molecular sieve having a reduced sodium oxide content has a sodium oxide content of 5.5 to 8.5 wt.%.

23. The method of claim 19, wherein the step (1) of contacting the NaY molecular sieve with the rare earth salt solution to effect the ion exchange reaction comprises contacting the NaY molecular sieve with a solution of a rare earth salt in an amount of, based on the weight of the NaY molecular sieve: rare earth salt: h₂O is 1: 0.01-0.18: 5-15, mixing the NaY molecular sieve, the rare earth salt and water to form a mixture, and stirring.

24. The method of claim 19 or 23, wherein the step (1) of contacting the NaY molecular sieve with the rare earth solution for an ion exchange reaction comprises: mixing NaY molecular sieve with water, adding rare earth salt and/or rare earth salt solution while stirring for ion exchange reaction, filtering and washing; the conditions of the ion exchange reaction are as follows: the exchange temperature is 15-95 ℃, the exchange time is 30-120 minutes, and the rare earth salt solution is a rare earth salt water solution.

25. The method of claim 19, wherein the rare earth salt is a rare earth chloride or a rare earth nitrate and the phosphorus compound is one or more selected from the group consisting of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.

26. The method according to claim 19, wherein the calcination temperature in the step (2) is 380 to 460 ℃, the calcination atmosphere is 40 to 80 vol% of water vapor atmosphere, and the calcination time is 5 to 6 hours.

27. The method according to claim 19, wherein the Y-type molecular sieve having a decreased unit cell constant obtained in step (2) has a unit cell constant of 2.450nm to 2.462 nm.

28. The method of claim 19, wherein the phosphorus modification conditions of step (3) are: contacting the Y-type molecular sieve sample with the reduced unit cell constant with an exchange solution containing a phosphorus compound, carrying out exchange reaction for 10-100 minutes at 15-100 ℃, filtering and washing; wherein the weight ratio of water to the molecular sieve in the exchange liquid is 2-5, and P is used₂O₅The weight ratio of phosphorus to molecular sieve is: 0.0005 to 0.10.

29. The method of claim 28, wherein the weight ratio of water to molecular sieve in the exchange liquid is 3 to 4 in terms of P₂O₅The weight ratio of the phosphorus to the molecular sieve is 0.001-0.05.

30. The process of claim 19, wherein the water content of the phosphorus-containing molecular sieve having a reduced unit cell constant of Y-type in step (3) is not more than 1 wt.%.

31. The method of claim 19, wherein step (4) is performed in accordance with SiCl₄: the Y-type molecular sieve with reduced unit cell constant of phosphorus is 0.1-0.7: 1, the Y-shaped molecular sieve with the reduced unit cell constant containing phosphorus is contacted and reacted with silicon tetrachloride gas at the reaction temperature of 200-650 ℃ for 10 minutes to 5 hours, and the Y-shaped molecular sieve containing phosphorus and rare earth is obtained by washing and filtering.

32. The method according to claim 19, wherein the washing method in the step (4) is washing with water under the following washing conditions:

molecular sieve: h₂The weight ratio of O =1: 6-15, the pH value is 2.5-5.0, and the washing temperature is 30-60 ℃.

33. The method of claim 19, wherein the support is one or more of a clay, an alumina support, a silica support, and a silica-alumina support.

34. The method of claim 33, wherein the silica support is a silica sol comprising SiO₂The content is 1-30 wt%; the alumina carrier is one or more of gamma-alumina, eta-alumina, theta-alumina, chi-alumina, alumina sol and hydrated alumina; the silicon oxide-aluminum oxide carrier is one or more of silicon-aluminum sol, silicon-aluminum gel and amorphous silicon oxide-aluminum oxide.

35. The method of claim 34, wherein the silica sol is a neutral silica sol, an acidic silica sol or an alkaline silica sol, and the hydrated alumina is one or more of pseudoboehmite, diaspore, gibbsite and bayerite.

36. The method according to claim 19, wherein the molecular sieve having a pore opening diameter of 0.59 to 0.73 nm is at least one selected from the group consisting of molecular sieves having structures of AFR, AFS, AFI, BEA, BOG, CON, GME, LTL, MEI, MOR, and OFF.

37. The process of claim 35 wherein the molecular sieve having pore opening diameters of 0.59 to 0.73 nm is at least one of Beta, SAPO-5, SAPO-40, SSZ-24, CIT-1, ZSM-18, mordenite, gmelinite, and offretite.

38. The method of claim 37, wherein the molecular sieve having pore opening diameters of 0.59 to 0.73 nm has a silicon to aluminum atomic mole ratio of 0.1 to 100: 1.

39. a heavy oil conversion method, comprising the step of carrying out contact reaction on heavy oil and the catalyst of any one of claims 1-18 under catalytic cracking conditions, wherein the reaction temperature is 400-^-1The weight ratio of the agent to the oil is 1-10.

40. The process as set forth in claim 39, wherein the reaction temperature is 450 ℃ and 550 ℃, and the weight hourly space velocity is 8-25 hours^-1The weight ratio of the components is 2-7.

41. The method as set forth in claim 40, wherein the reaction temperature is 480 ℃ and 530 ℃.

42. The process of claim 39, wherein the heavy oil is hydrogenated residue having an aromatic hydrocarbon content of 40 to 75 wt%, a paraffin hydrocarbon content of 1 to 25 wt%, a naphthene hydrocarbon content of 15 to 45 wt%, and a specific gravity of 0.92 to 0.95g/cm³。