Preparation method and application of a catalytic cracking catalyst

Abstract

This invention discloses a method for preparing and applying a catalytic cracking catalyst. The preparation method includes the following steps: Step 1, using SiCl4 as a dealuminizer and silicate supplement, performing gas-phase ultrastabilization treatment on NaY molecular sieve to obtain a gas-phase ultrastabilized Y molecular sieve; Step 2, modifying the gas-phase ultrastabilized Y molecular sieve with zirconium hydrogen phosphate; Step 3, mixing the modified gas-phase ultrastabilized Y molecular sieve obtained in Step 2 with a binder, slurrying, and calcining to obtain the catalytic cracking catalyst. The catalyst obtained by the method of this invention can be used for the direct catalytic cracking of crude oil to produce low-carbon olefins, exhibiting high ethylene and propylene yields and low coke production.

Description

Technical Field

[0001] This invention belongs to the field of oil refining catalysts, specifically relating to a method for preparing and applying a catalytic cracking catalyst. Background Technology

[0002] There are two technologies for the direct production of low-carbon olefins from crude oil: steam cracking and catalytic cracking. Steam cracking suffers from the drawbacks of high plant construction costs, high energy consumption, and high carbon emissions, and also has poor feedstock adaptability and inflexible product distribution control. In contrast, catalytic cracking involves lower reaction temperatures, lower plant construction costs, and a reaction mechanism that combines carbocation and free radical mechanisms, allowing for flexible control of product distribution, making it a popular choice for researchers. The core technology for the direct catalytic cracking of crude oil to produce low-carbon olefins lies in the development of highly efficient catalysts.

[0003] CN115869995A discloses a catalyst for the catalytic cracking of crude oil to produce low-carbon olefins, which has the following components: 5~20wt% high silica-alumina ratio Y-type molecular sieve, 20~60wt% modified ZSM-5 molecular sieve, 0.5~25wt% macroporous matrix material, 0.5~15wt% hydrogen transfer inhibitory component, 15~60wt% clay, and 2~20wt% binder.

[0004] CN116099570A discloses a catalytic cracking catalyst and its application in the catalytic cracking of Dushanzi wax oil. The catalyst preparation method is as follows: based on 100 parts by dry weight of the catalyst, 15-40 parts of ZSM-11 molecular sieve, 5-15 parts of Y-type molecular sieve, 5-15 parts of binder, and 35-75 parts of clay are mixed with water to form a slurry, spray-molded, and calcined to obtain the catalytic cracking catalyst.

[0005] CN116174024A discloses a catalytic cracking catalyst that exhibits the advantage of high and low carbon olefin yield in the catalytic cracking process of naphtha. It has the following components: the content of phosphorus-containing hollow hierarchical ZSM-5 molecular sieve is 15-50wt%, and the support content is 50-85wt%.

[0006] TW202315930A discloses a catalytic cracking catalyst with abundant mesoporous structure and its preparation method, which exhibits advantages of high conversion rate and low coke selectivity in heavy oil catalytic cracking. The catalyst composition is as follows: on a dry basis, it comprises: 10-35 wt% mesoporous and macroporous alumina, with a total pore volume of 0.5-2.0 mL / g, of which pores of 5-100 nm account for more than 80% of the total pore volume; 5-3 wt% acidifying binder, 2-20 wt% secondary binder, 20-60 wt% molecular sieve, and 5-50 wt% clay.

[0007] CN115212915A discloses a method for preparing a catalytic cracking catalyst and applies it to the diesel catalytic cracking process, showing high LPG and propylene yields. The catalyst preparation steps are as follows: Molecular sieves are mixed with an alkaline aqueous solution and treated at 150–200°C for 12–96 hours. After drying and calcination, modified molecular sieves are obtained. Then, kaolin, alumina sol, and phosphoric acid are mixed with water to obtain slurry A. The modified molecular sieve is added to slurry A to obtain slurry B. Silica sol is then added to slurry B to obtain slurry C. Next, a thickener is added to slurry C, and the mixture is ball-milled. The ball-milled slurry is spray-dried to obtain catalyst microspheres. Finally, the catalyst microspheres are calcined to obtain the diesel catalytic cracking catalyst.

[0008] The aforementioned catalytic cracking catalysts, as well as most existing catalytic cracking catalysts, use naphtha, wax oil, and heavy oil from crude oil processing as raw materials, resulting in lengthy process flows. Furthermore, current catalytic cracking catalyst technology focuses on adding functional components such as ZSM-5 shape-selective molecular sieves and hydrogen transfer inhibitors during catalyst preparation, with limited research on further exploring and expanding the catalytic cracking performance of Y-type molecular sieves. The reaction conditions for crude oil catalytic cracking are harsh, requiring catalysts with suitable acid strength and density, as well as good hydrothermal stability. This places higher demands on the Y-type molecular sieve as the main component of catalytic cracking catalysts. Summary of the Invention

[0009] The main objective of this invention is to provide a catalytic cracking catalyst and its application. The catalyst of this invention can be used for the direct catalytic cracking of crude oil to produce low-carbon olefins, with a high ethylene and propylene yield and a low coke production. It can reduce or even eliminate the need for the addition of selective molecular sieves and additives in existing catalytic cracking catalyst technologies.

[0010] To achieve the above objectives, the present invention provides a method for preparing a catalytic cracking catalyst, comprising the following steps:

[0011] Step 1: Using SiCl4 as a dealuminating and silicon replenishing agent, the NaY molecular sieve is subjected to gas-phase ultrastabilization treatment to obtain a gas-phase ultrastabilized Y molecular sieve.

[0012] Step 2: Modify the gas-phase ultrastable Y molecular sieve using zirconium hydrogen phosphate;

[0013] Step 3: Mix the modified gas-phase ultrastable Y molecular sieve obtained in Step 2 with the binder, slurry, and calcine to obtain the catalytic cracking catalyst.

[0014] The preparation method of the catalytic cracking catalyst of the present invention further includes, in step 1, gas-phase ultrastabilization treatment of NaY molecular sieve, ammonium ion exchange and calcination steps.

[0015] The preparation method of the catalytic cracking catalyst of the present invention includes step 2, which further includes placing the modified gas-phase ultrastable Y molecular sieve in a sealed device for a certain period of time, wherein the temperature of the sealed device is 100℃-200℃.

[0016] The method for preparing the catalytic cracking catalyst of the present invention includes a SiCl4 mass of 10-40 wt% of the dry NaY molecular sieve and a gas-phase ultrastability treatment temperature of 320-420 °C.

[0017] The preparation method of the catalytic cracking catalyst of the present invention includes ammonium ion exchange, wherein ammonium salt is mixed and exchanged with gas-phase ultrastable Y molecular sieve, the exchange temperature is 80~93℃, the exchange time is 1~2h, the pH of the system is controlled at 3.0~3.3 during the exchange process, and the mass ratio of ammonium salt to gas-phase ultrastable Y molecular sieve is 0.5~1.0.

[0018] The preparation method of the catalytic cracking catalyst of the present invention includes step 2 modification, which involves: ultrasonically treating a mixture of zirconium hydrogen phosphate and water to obtain zirconium hydrogen phosphate colloid, and then impregnating the gas-phase ultrastable Y molecular sieve with an equal volume of the zirconium hydrogen phosphate colloid.

[0019] In the preparation method of the catalytic cracking catalyst of the present invention, the modified gas-phase ultrastable Y molecular sieve obtained in step 2 contains zirconium (calculated as ZrO2) of 0.1~7.5 wt% and phosphorus (calculated as P2O5) of 0.1~8.6 wt%.

[0020] The method for preparing the catalytic cracking catalyst of the present invention includes adding clay during the mixing process in step 3, spray drying the slurry, and then calcining it to obtain the catalytic cracking catalyst.

[0021] The method for preparing the catalytic cracking catalyst of the present invention includes the following steps: the total mass of the catalytic cracking catalyst is 100%, the dry basis addition of the modified gas-phase ultrastable Y molecular sieve obtained in step 2 is 30-38 wt%, the dry basis addition of the clay is 45-53 wt%, and the dry basis addition of the binder is 10-17 wt%.

[0022] To achieve the above objectives, the present invention also provides a catalytic cracking catalyst obtained by the above preparation method for use in crude oil catalytic cracking reactions.

[0023] The beneficial effects of this invention are:

[0024] This invention uses zirconium hydrogen phosphate to modify gas-phase ultrastable Y molecular sieves, which can simultaneously modify both phosphorus and zirconium. This avoids the problem of loss of the first modified element caused by sequential modification of the two elements, and also avoids the problem of excessive zirconium and phosphorus species in the Y molecular sieve caused by simultaneous modification of the two elements with different donors, which makes it difficult to control experimental variables.

[0025] The catalyst obtained by the method of this invention can be used for the direct catalytic cracking of crude oil to produce low-carbon olefins, with high ethylene and propylene yields and low coke production. Detailed Implementation

[0026] The technical solution of the present invention will be described in detail below. The following embodiments are implemented under the premise of the technical solution of the present invention and a detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. Structures or experimental methods that do not specify specific conditions in the following embodiments are generally performed under conventional conditions.

[0027] This invention provides a method for preparing a catalytic cracking catalyst, comprising the following steps:

[0028] Step 1: Using SiCl4 as a dealuminating and silicon replenishing agent, the NaY molecular sieve is subjected to gas-phase ultrastabilization treatment to obtain a gas-phase ultrastabilized Y molecular sieve.

[0029] Step 2: Modify the gas-phase ultrastable Y molecular sieve using zirconium hydrogen phosphate;

[0030] Step 3: Mix the modified gas-phase ultrastable Y molecular sieve obtained in Step 2 with the binder, slurry, and calcine to obtain the catalytic cracking catalyst.

[0031] This invention improves the acid strength of the catalyst and reduces its acid density and coke selectivity by modifying the Y-type molecular sieve, the main component of the catalytic cracking catalyst.

[0032] This invention does not specifically limit the NaY molecular sieve; commercially available NaY molecular sieves can be used. In one embodiment, the gas-phase ultrastable treatment is as follows: SiCl4 gas is mixed with NaY molecular sieve, reacted at a temperature of 320~420℃, and then filtered, washed, and dried to obtain a gas-phase ultrastable Y molecular sieve (i.e., GUSY). The mass of SiCl4 is 10~40 wt% of the dry basis mass of the NaY molecular sieve.

[0033] In one embodiment, the relative crystallinity of the gas-phase ultrastable Y molecular sieve of the present invention is maintained above 80%, the silica-alumina ratio is 10.0-12.0, and the total specific surface area is 620-680 m². 2 ·g -1 The total pore volume is 0.35-0.37 cm³. 3 ·g -1 .

[0034] In one embodiment, after the gas-phase ultrastabilization treatment of NaY molecular sieve in step 1 of the present invention, the method further includes ammonium ion exchange and calcination. The ammonium ion exchange is, for example, mixing and exchanging ammonium salt with the gas-phase ultrastabilized Y molecular sieve, at an exchange temperature of 80-93°C, for an exchange time of 1-2 hours, controlling the pH of the system at 3.0-3.3 during the exchange process, and maintaining a ratio of ammonium salt to the gas-phase ultrastabilized Y molecular sieve of 0.5-1.0. The ammonium salt is, for example, ammonium chloride. The Na₂O content of the gas-phase ultrastabilized Y molecular sieve (HGUSY) after ammonium exchange according to the present invention can be reduced to below 1 wt%.

[0035] In one embodiment, the present invention performs dealuminization and silicon replenishment at a high SiCl4 to NaY molecular sieve mass ratio. Since sodium is also removed during dealuminization and silicon replenishment, the ammonium exchange step mentioned above for reducing the sodium content of the molecular sieve can be omitted.

[0036] Step 2 of this invention is: modifying the gas-phase ultrastable Y molecular sieve with zirconium hydrogen phosphate.

[0037] In one embodiment, step 2 modification includes: ultrasonically treating a mixture of zirconium hydrogen phosphate and water to obtain zirconium hydrogen phosphate colloid, and then impregnating the gas-phase ultrastable Y molecular sieve with the zirconium hydrogen phosphate colloid.

[0038] Zirconium hydrogen phosphate (Zr(HPO4)2) is a two-dimensional layered material with three structural types: α, γ, and τ. It is a white powder, insoluble in water and common organic solvents, and possesses a strong cation exchange capacity. This invention uses zirconium hydrogen phosphate as a co-donor for zirconium and phosphorus, avoiding the problem of donor-to-donor reactions that can introduce multiple zirconium and phosphorus species, making experimental variables difficult to control, when different donors are used. Furthermore, by using zirconium hydrogen phosphate as a co-donor for zirconium and phosphorus, this invention allows for the modification of Y-zeolite with zirconium and phosphorus in a specific ratio.

[0039] In one embodiment, the ultrasonic treatment temperature is 45-65°C, and the ultrasonic treatment time is 1-2 hours. In another embodiment, the present invention uses a gas-phase ultrastable Y molecular sieve impregnated with an equal volume of zirconium hydrogen phosphate colloid.

[0040] In one embodiment, the impregnated gas-phase ultrastable Y molecular sieve is placed in a sealed device for a certain period of time. The temperature of the sealed device is 100℃-250℃, preferably 100℃-200℃, and the placement time is, for example, 12-30 hours, preferably 18-24 hours. The sealed device is, for example, a high-pressure reactor. This promotes the solid-phase migration of Zr and P elements to the molecular sieve channels and even the framework, preventing the enrichment and blockage of Zr and P species, which would otherwise lead to a loss of the molecular sieve's specific surface area and pore volume, and further reduce the accessibility of reactants in catalytic cracking reactions.

[0041] The modified gas-phase ultrastable Y molecular sieve of this invention can be gently dried at 50-70℃ without high-temperature calcination, thus minimizing P loss.

[0042] In one embodiment, the modified gas-phase ultrastable Y molecular sieve obtained by the present invention contains zirconium (calculated as ZrO2) of 0.1-7.5 wt%, preferably 0.1-5 wt%, more preferably 0.1-4 wt% or 0.1-3.5 wt%, and phosphorus (calculated as P2O5) of 0.1-8.6 wt%, preferably 0.1-5.8 wt%, more preferably 0.1-4.6 wt% or 0.1-4.0 wt%.

[0043] Step 3 of this invention involves mixing the modified gas-phase ultrastable Y molecular sieve obtained in step 2 with a binder, slurrying the mixture, and then calcining it to obtain a catalytic cracking catalyst. In one embodiment, clay is also added during the mixing process, the slurry is spray-dried, and then calcined to obtain the catalytic cracking catalyst.

[0044] Specifically, water, binder, and clay are slurried and stirred evenly to obtain a matrix slurry; modified gas-phase ultrastable Y molecular sieve (Zr-P / HGUSY) is slurried to obtain a molecular sieve slurry; then the matrix slurry and molecular sieve slurry are mixed evenly, spray-dried, and calcined to form a catalytic cracking catalyst. In one embodiment, the calcination temperature is 400-550℃, and the calcination time is 0.5-2 hours. The calcination here serves three purposes: first, it solidifies the catalyst, making it stronger; second, it releases residual hydrochloric acid from the catalyst; and third, it allows Zr and P species to further migrate into the molecular sieve channels. Since the entire preparation process only involves one calcination process, P loss is minimized throughout the entire preparation process.

[0045] In one embodiment, the clay is one or more of kaolin, montmorillonite, and halloysite, and the binder is one or more of alumina sol, silica alumina sol, and highly concentrated acid-acidified pseudoboehmite.

[0046] In one embodiment, with the total mass of the catalytic cracking catalyst being 100%, the dry basis addition of the modified gas-phase ultrastable Y molecular sieve obtained in step 2 is 30-38 wt%, the dry basis addition of the clay is 45-53 wt%, and the dry basis addition of the binder is 10-17 wt%.

[0047] The catalytic cracking catalyst of the present invention undergoes hydrothermal aging treatment before use, for example, hydrothermal aging at 750℃~850℃ for 8~12h in a 100% water vapor atmosphere.

[0048] The catalytic cracking catalyst of this invention can be used in the catalytic cracking reaction of crude oil to produce low-carbon olefins, with high ethylene and propylene yields and low coke production. In one embodiment, when the catalytic cracking catalyst of this invention is used for the catalytic cracking of crude oil, the reaction temperature is 600℃~680℃, and the catalyst-to-oil weight ratio is 4~15, preferably 4~8.

[0049] In addition, this invention performs three steps on NaY molecular sieve: gas-phase ultrastabilization, Zr-P impregnation, and catalyst preparation, to obtain a direct catalytic cracking catalyst for crude oil, which greatly simplifies the catalyst preparation steps and reduces process and energy consumption costs.

[0050] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0051] Source of raw materials or equipment:

[0052] In the examples and comparative examples, the unmodified NaY molecular sieve was provided by Sinopec Catalyst to the Catalyst Plant of Lanzhou Petrochemical Company of China National Petroleum Corporation. The sodium oxide content was 14.6 wt%, the framework silicon-aluminum ratio (SiO2 / Al2O3 molar ratio) was 5.0, and the relative crystallinity was 93%.

[0053] Silicon tetrachloride was supplied by Aladdin Reagents.

[0054] Zirconium hydrogen phosphate was supplied by Sigma-Aldrich.

[0055] Ammonium chloride was provided by Tianjin Guangfu Technology Development Co., Ltd.

[0056] The kaolin is a special kaolin for cracking catalysts produced by Suzhou China Kaolin Company, with a solid content of 76 wt%.

[0057] The aluminum sol was provided by Lanzhou Petrochemical Company of China National Petroleum Corporation, with an alumina content of 21 wt%.

[0058] The Chunlin CR-020S ultrasonic cleaner is manufactured by Shenzhen Chunlin Ultrasonic Technology Co., Ltd.

[0059] Evaluation and analysis methods:

[0060] The elemental content of molecular sieves was determined by X-ray fluorescence spectrometry, and the method standard was Q / SY LS10500-2014.

[0061] The crystallinity of molecular sieves was tested using X-ray powder diffraction, with the standard method being Q / SYLS0596-2002.

[0062] The molecular sieve cell constant (silicon-to-aluminum ratio) was tested using X-ray powder diffraction, and the standard method is SH / T 0339-92.

[0063] Example 1

[0064] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. ZrO2:(ZrO2+HGUSY (dry basis)) = 1 wt% was used. Zr(HPO4)2 was dispersed in the measured volume of deionized water. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃, and ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY to obtain HGUSY with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 1-Zr-P / HGUSY.

[0065] Following a dry weight ratio of 35:50:15 (1-Zr-P / HGUSY:kaolin:aluminum sol), water, binder, and aluminum sol were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Then, 1-Zr-P / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-1. Cat-1 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5 (by weight).

[0066] Example 2

[0067] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. ZrO2:(ZrO2+HGUSY (dry basis)) = 2% was used. Zr(HPO4)2 was dispersed in a measured volume of deionized water. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner, and the water bath temperature was set to 55℃. The mixture was ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY to obtain HGUSY with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 2-Zr-P / HGUSY.

[0068] Following a dry basis mass ratio of 35:50:15 for 2-Zr-P / HGUSY:kaolin:aluminum sol, water, binder, and aluminum sol were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 2-Zr-P / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-2. Cat-2 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5 (by weight).

[0069] Example 3

[0070] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. Zr(HPO4)2 was dispersed in a measured volume of deionized water at a concentration of ZrO2:(ZrO2 + HGUSY (dry basis)) = 3%. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃ and ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY to obtain HGUSY with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3-Zr-P / HGUSY.

[0071] Following a dry weight ratio of 3-Zr-P / HGUSY:kaolin:aluminum sol = 35:50:15, water, binder, and aluminum sol were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3-Zr-P / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-3. Cat-3 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5.

[0072] Example 4

[0073] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. Zr(HPO4)2 was dispersed in a measured volume of deionized water at a concentration of ZrO2:(ZrO2 + HGUSY (dry basis)) = 4%. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃ and ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY to obtain HGUSY with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 4-Zr-P / HGUSY.

[0074] Following a dry weight ratio of 35:50:15 (4-Zr-P / HGUSY:kaolin:aluminum sol), water, binder, and aluminum sol were first added to a container and stirred until homogeneous. The pH was then adjusted to 4.0-5.3 to form a matrix slurry. Next, 4-Zr-P / HGUSY was added to the container and stirred to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-4. Cat-4 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5.

[0075] Example 5

[0076] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.38:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY-1. Due to the high SiCl4 to NaY molecular sieve ratio in this experiment, both aluminum and sodium were removed during the gas-phase ultrastability process. The resulting product had a sodium oxide content below 0.5wt%, eliminating the need for ammonium exchange and directly naming it HGUSY-1. The saturated water absorption of HGUSY-1 (dry basis) was determined. ZrO2:(ZrO2+HGUSY-1 (dry basis)) = 3% was used. Zr(HPO4)2 was dispersed in the measured volume of deionized water. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃ and ultrasonicated and bathed in water for 1.5 hours to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, zirconium hydrogen phosphate colloid was impregnated onto HGUSY-1 to obtain HGUSY-1 with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160°C for 24 hours. The resulting sample was then gently dried at 60°C for 12 hours, and named 3-Zr-P / HGUSY-1.

[0077] Following the ratio of HGUSY-1:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Then, HGUSY-1 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-5. Cat-5 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0078] Example 6

[0079] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.35:1, preheated vaporized SiCl4 gas was introduced and reacted at 400℃ for 40 minutes. The product was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY-3. Because the SiCl4 to NaY molecular sieve ratio was high in this experiment, both aluminum and sodium were removed during the gas-phase ultrastable process. The resulting product had a sodium oxide content below 0.5wt%, eliminating the need for ammonium exchange, and was directly named HGUSY-3. The saturated water absorption of HGUSY-3 (dry basis) was determined. ZrO2:(ZrO2+HGUSY-3 (dry basis)) = 3%, Zr(HPO4)2 was dispersed in the measured volume of deionized water. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner, with the water bath temperature set to 55℃, and ultrasonicated and bathed in the water for 1.5 hours to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, zirconium hydrogen phosphate colloid was impregnated onto HGUSY-3 to obtain HGUSY-3 with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160°C for 24 hours. The resulting sample was then gently dried at 60°C for 12 hours, and named 3-Zr-P / HGUSY-3.

[0080] Following a dry basis mass ratio of 3-Zr-P / HGUSY-3:kaolin:aluminum sol = 35:50:15, water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3-Zr-P / HGUSY-3 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-6. Cat-6 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0081] Example 7

[0082] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.35:1, preheated vaporized SiCl4 gas was introduced and reacted at 400℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product, named GUSY-4. Because the SiCl4 to NaY molecular sieve ratio was high in this experiment, both aluminum and sodium were removed during the ultrastable gas-phase process. The resulting product had a sodium oxide content below 0.5wt%, eliminating the need for further ammonium exchange. Therefore, it was directly named HGUSY-4. The saturated water absorption of HGUSY-4 (dry basis) was determined. Zr(HPO4)2 was dispersed in a measured volume of deionized water at a concentration of ZrO2:(ZrO2 + HGUSY-4 (dry basis)) = 3%. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃ and ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY-4 to obtain HGUSY-4 with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3-Zr-P / HGUSY-4.

[0083] Following a dry basis mass ratio of 3-Zr-P / HGUSY-4:kaolin:aluminum sol = 35:50:15, water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3-Zr-P / HGUSY-4 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-7. Cat-7 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0084] Example 8

[0085] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.35:1, preheated vaporized SiCl4 gas was introduced and reacted at 400℃ for 20 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product, named GUSY-5. Because the SiCl4 to NaY molecular sieve ratio was high in this experiment, both aluminum and sodium were removed during the ultrastable gas-phase process. The resulting product had a sodium oxide content below 0.5wt%, eliminating the need for further ammonium exchange. Therefore, it was directly named HGUSY-5. The saturated water absorption of HGUSY-5 (dry basis) was determined. Zr(HPO4)2 was dispersed in a measured volume of deionized water at a concentration of ZrO2:(ZrO2 + HGUSY-5 (dry basis)) = 3%. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner with a water bath temperature of 55℃ and ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY-5 to obtain HGUSY-5 with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3-Zr-P / HGUSY-5.

[0086] Following a dry basis mass ratio of 3-Zr-P / HGUSY-5:kaolin:aluminum sol = 35:50:15, water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3-Zr-P / HGUSY-5 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-7. Cat-7 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0087] Example 9

[0088] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. ZrO2:(ZrO2+HGUSY (dry basis)) = 3% was used. Zr(HPO4)2 was dispersed in the measured volume of deionized water. The Zr(HPO4)2 dispersion was placed in an ultrasonic cleaner, and the water bath temperature was set to 55℃. The mixture was ultrasonicated and water bathed for 1.5 h to obtain zirconium hydrogen phosphate colloid. Using an equal-volume impregnation method, the zirconium hydrogen phosphate colloid was impregnated onto HGUSY to obtain HGUSY with a fixed Zr and P loading ratio. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 16 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3-Zr-P-1 / HGUSY.

[0089] Following a dry weight ratio of 3-Zr-P-1 / HGUSY:kaolin:aluminum sol = 35:50:15, water, binder, and aluminum sol were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3-Zr-P-1 / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated Cat-9. Cat-9 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5.

[0090] Comparative Example 1

[0091] NaY molecular sieve (dry basis), NH4Cl solid, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, and then dried at 120℃ for 12 hours. After drying, the sample was placed in a muffle furnace and subjected to hydrothermal treatment at 650℃ for 2 hours with 100% steam. After this "two-exchange, two-hydrothermal" process, the desired sample was obtained and named USY.

[0092] Following a ratio of USY:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Next, USY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated DB-Cat-1. DB-Cat-1 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5 (by weight).

[0093] Comparative Example 2

[0094] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY.

[0095] Following the ratio of HGUSY:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Then, HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated DB-Cat-2. DB-Cat-2 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0096] Comparative Example 3

[0097] Following a SiCl4:NaY molecular sieve (dry basis) weight ratio of 0.38:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was then washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain a product named GUSY-1. Due to the high SiCl4 to NaY molecular sieve ratio in this experiment, both aluminum and sodium were removed during the ultrastable gas-phase process. The resulting product had a sodium oxide content below 0.5wt%, eliminating the need for further ammonium exchange, and was named HGUSY-1.

[0098] Following the ratio of HGUSY-1:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Then, HGUSY-1 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated DB-Cat-3. DB-Cat-3 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0099] Comparative Example 4

[0100] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.11:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY-2. GUSY-2, NH4Cl solid, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then subjected to ion exchange in a 90℃ water bath for 1 hour. The mixture was filtered, repeatedly washed until the filtrate was neutral, dried at 120℃ for 12 hours, and calcined in a muffle furnace at 550℃ for 4 hours. The sample was then subjected to another ammonium exchange and calcination to obtain the product named HGUSY-2.

[0101] Following the ratio of HGUSY-2:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, aluminum sol, and kaolin were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0-5.3 to form a matrix slurry. Then, HGUSY-2 was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated DB-Cat-4. DB-Cat-4 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38-212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃.

[0102] Comparative Example 5

[0103] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. Zr(NO3)4·5H2O was dissolved in a measured volume of deionized water according to a ZrO2:(ZrO2+HGUSY (dry basis)) = 3%. The system was placed in an ultrasonic cleaner with a water bath temperature of 55℃, and ultrasonicated and water bathed for 0.5 h to obtain a zirconium nitrate solution. Using an equal-volume impregnation method, the zirconium nitrate solution was impregnated onto the HGUSY to obtain Zr-loaded HGUSY. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3Zr / HGUSY. It should be noted that the obtained sample easily agglomerates into small lumps, is very hard, and is not easily broken into powder.

[0104] Following a dry weight ratio of 3Zr / HGUSY:kaolin:aluminum sol = 35:50:15, water, binder, and aluminum sol were first added to a container and slurried. The mixture was stirred until homogeneous, and the pH was adjusted to 4.0–5.3 to form a matrix slurry. Then, 3Zr / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and molecular sieve slurry were mixed and spray-dried to form a catalytic cracking catalyst, designated DB-Cat-5. DB-Cat-5 was hydrothermally aged at 800℃ for 10 hours in a 100% steam atmosphere. Microspheres with a particle size of 38–212 μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5.

[0105] Comparative Example 6

[0106] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. Zr(NO3)4·5H2O was dissolved in a measured volume of deionized water according to a ZrO2:(ZrO2+HGUSY (dry basis)) = 3%. The system was placed in an ultrasonic cleaner with a water bath temperature of 55℃, and ultrasonicated and water bathed for 0.5 h to obtain a zirconium nitrate solution. Using an equal-volume impregnation method, the zirconium nitrate solution was impregnated onto the HGUSY to obtain Zr-loaded HGUSY. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160℃ for 24 h. The resulting sample was then gently dried at 60℃ for 12 h, and named 3Zr / HGUSY. It should be noted that the obtained sample easily agglomerates into small lumps, is very hard, and is not easily broken into powder. The saturated water absorption of 3Zr / HGUSY (dry basis) was measured using an equal-volume impregnation method. The impregnation amount was P2O5:(P2O5+HGUSY (dry basis)) = 3.45% (comparative to ZrO2:P2O5 in Example 3). Ammonium dihydrogen phosphate solution was uniformly mixed with Zr / HGUSY (dry basis). The resulting sample was further dried using the ultrasonic + two-stage drying method described above, and then calcined at 500℃ for 3 hours to obtain 3Zr+3.45P / HGUSY.

[0107] According to the ratio of 3Zr / HGUSY:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, binder, and aluminum sol were first added to a container and slurried. After stirring evenly and adjusting the pH to 4.0~5.3, a matrix slurry was formed. Then, 3Zr + 3.45P / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and the molecular sieve slurry were mixed evenly and spray-dried to form a catalytic cracking catalyst, denoted as DB-Cat-6. DB-Cat-6 was hydrothermally aged at 800℃ for 10 hours in a 100% water vapor atmosphere. Microspheres with a particle size of 38-212μm were sieved and placed in an ACE reactor for catalytic cracking of Daqing paraffin-based crude oil at a reaction temperature of 650℃ and a catalyst-to-oil ratio of 7.5.

[0108] Comparative Example 7

[0109] According to the weight ratio of SiCl4:NaY molecular sieve (dry basis) = 0.20:1, preheated vaporized SiCl4 gas was introduced and reacted at 350℃ for 30 minutes. The mixture was washed with 5L of deionized water, filtered, and dried overnight at 120℃ to obtain the product named GUSY. GUSY, solid NH4Cl, and deionized water were mixed in a mass ratio of 1:1:10. The pH of the system was adjusted to 3.0-3.3 with hydrochloric acid, and then placed in a 90℃ water bath for ion exchange for 1 hour. The mixture was filtered and repeatedly washed until the filtrate was neutral, then dried at 120℃ for 12 hours. Finally, it was calcined in a muffle furnace at 550℃ for 4 hours to obtain the product named HGUSY. The saturated water absorption of HGUSY (dry basis) was determined. Using a ZrO2:(ZrO2+HGUSY (dry basis)) = 3% and a P2O5:(P2O5+HGUSY (dry basis)) = 3.45% impregnation amount (comparative to ZrO2:P2O5 in Example 3), Zr(NO3)4·5H2O and ammonium dihydrogen phosphate were dissolved in a measured volume of deionized water. The system was placed in an ultrasonic cleaner, with the water bath temperature set at 55°C, and ultrasonicated and water bathed for 0.5 h to obtain a zirconium nitrate solution. Using an equal-volume impregnation method, the zirconium nitrate solution was impregnated onto the HGUSY to obtain Zr and P-loaded HGUSY. The wet sample was transferred to a high-pressure reactor and placed in an oven at 160°C for 24 h. The resulting sample was then gently dried at 60°C for 12 h, and named 3Zr-3.45P / HGUSY.

[0110] According to the ratio of 3Zr-3.45P / HGUSY:kaolin:aluminum sol = 35:50:15 (dry basis mass ratio), water, binder, and aluminum sol were first added to a container and slurried. After stirring evenly and adjusting the pH to 4.0~5.3, a matrix slurry was formed. Then, 3Zr-3.45P / HGUSY was added to the container and slurried to form a molecular sieve slurry. Finally, the matrix slurry and the molecular sieve slurry were mixed evenly and spray-dried to form a catalytic cracking catalyst, denoted as DY-Cat-7. DY-Cat-7 was hydrothermally aged at 800℃ for 10 hours in a 100% water vapor atmosphere. Microspheres with a particle size of 38-212μm were sieved and placed in an ACE reactor for the catalytic cracking reaction of Daqing paraffin-based crude oil. The reaction temperature was 650℃ and the catalyst-to-oil ratio was 7.5.

[0111] The physical properties and chemical composition of the modified Y molecular sieves obtained in the examples and comparative examples are shown in Table 1, the texture properties are shown in Table 2, and the evaluation results of the catalysts obtained in the examples and comparative examples are shown in Table 3.

[0112] Table 1. Physical properties and chemical composition of Zr-P / HGUSY molecular sieves with different impregnation amounts

[0113] sample <![CDATA[C / C0(%)]]> <![CDATA[Si / Al2 (a) ]]> <![CDATA[UCC (a) / nm]]> <![CDATA[Na2Owt% (b) ]]> <![CDATA[ZrO2wt% (b) ]]> <![CDATA[P2O5wt% (b) ]]> USY (Comparative Example 1) 72 10.9 2.445 0.74 0 0 HGUSY (Comparative Example 2) 76 10.6 2.446 0.85 0 0 HGUSY-1 (Comparative Example 3) 70 14.2 2.440 0.46 0 0 HGUSY-2 (Comparative Example 4) 80 8.5 2.451 0.90 0 0 3Zr / HGUSY (Comparative Example 5) 71 11.6 2.444 0.82 2.69 0 3Zr + 3.45P / HGUSY (Comparative Example 6) 70 12.2 2.442 0.70 2.48 3.12 3Zr-3.45P / HGUSY (Comparative Example 7) 71 12.2 2.442 0.73 2.58 3.09 1-Zr-P / HGUSY (Example 1) 73 10.6 2.444 0.85 0.94 1.05 2-Zr-P / HGUSY (Example 2) 72 10.6 2.446 0.89 2.12 2.40 3-Zr-P / HGUSY (Example 3) 70 11.6 2.444 0.82 3.19 3.54 4-Zr-P / HGUSY (Example 4) 67 11.6 2.444 0.73 4.08 4.71 3-Zr-P / HGUSY-1 (Example 5) 63 15.6 24.38 0.43 3.05 3.48 3-Zr-P / HGUSY-3 (Example 6) 70 16.6 24.37 0.40 3.07 3.50 3-Zr-P / HGUSY-4 (Example 7) 67 15.6 24.38 0.41 3.04 3.50 3-Zr-P / HGUSY-5 (Example 8) 63 14.8 2.439 0.43 3.13 3.58 3-Zr-P-1 / HGUSY (Example 9) 68 11.6 2.444 0.81 2.85 3.25

[0114] Note: C / C0 represents relative crystallinity; Si / Al2 (a) The skeletal silicon-to-aluminum ratio is determined by XRD; UCC (a) The unit cell constant determined by XRD

[0115] (a): XRD measurement; (b): XRF measurement

[0116] Table 2. Texture properties of Zr-P / HGUSY with different impregnation amounts

[0117] sample <![CDATA[S BET (m 2 ·g -1 )]]> <![CDATA[S mic (m 2 ·g -1 )]]> <![CDATA[S mesc (m 2 ·g -1 )]]> <![CDATA[V pore (cm 3 ·g -1 )]]> <![CDATA[V mic (cm 3 ·g -1 )]]> <![CDATA[V mes (cm 3 ·g -1 )]]> USY (Comparative Example 1) 582 418 164 0.402 0.190 0.212 HGUSY (Comparative Example 2) 637 568 70 0.357 0.278 0.079 HGUSY-1 (Comparative Example 3) 484 399 85 0.286 0.194 0.092 HGUSY-2 (Comparative Example 4) 629 523 106 0.346 0.254 0.092 3Zr / HGUSY (Comparative Example 5) 615 538 79 0.339 0.261 0.080 3Zr + 3.45P / HGUSY (Comparative Example 6) 576 496 80 0.321 0.239 0.082 3Zr-3.45P / HGUSY (Comparative Example 7) 595 520 75 0.330 0.252 0.078 1Zr-P / HGUSY (Example 1) 623 557 66 0.344 0.272 0.072 2Zr-P / HGUSY (Example 2) 620 543 77 0.343 0. 265 0.078 3Zr-P / HGUSY (Example 3) 618 540 78 0.341 0.264 0.077 4Zr-P / HGUSY (Example 4) 613 535 78 0.339 0.260 0.079 3-Zr-P / HGUSY-1 (Example 5) 470 379 91 0.273 0.184 0.089 3-Zr-P / HGUSY-3 (Example 6) 490 402 88 0.290 0.197 0.093 3-Zr-P / HGUSY-4 (Example 7) 478 395 83 0.281 0.190 0.091 3-Zr-P / HGUSY-5 (Example 8) 472 380 92 0.275 0.185 0.090 3-Zr-P-1 / HGUSY (Example 9) 609 533 76 0.338 0.263 0.075

[0118] Note: S BET : Total specific surface area of ​​the sample calculated by the BET method; S mic : Microporous specific surface area; S mesc : Mesoporous specific surface area calculated by the t-plot method; V pore Total pore volume; V mic : Micropore volume; V mes Mesoporous volume

[0119] As shown in Tables 1 and 2, compared with Example 3, the total specific surface area of ​​Comparative Example 6 decreased by 6.8%, and the pore volume decreased by 5.9%. This may be because the Zr-impregnated sample is prone to agglomeration into small lumps, making it difficult to grind into powder. Compared with the two-step impregnation operation, one-step impregnation not only has the advantages of shorter process and simpler operation, but also avoids pore blockage of molecular sieve samples. More importantly, the designed impregnation amount and the ZrO2 content and P2O5 content measured by XRF in Comparative Example 6 differed by 0.52% and 0.33%, respectively, while the designed impregnation amount and the ZrO2 content and P2O5 content measured by XRF in Example 3 obtained by one-step impregnation with zirconium hydrogen phosphate differed by 0.19% and 0.09%, respectively. This indicates that Example 3 has a more uniform loading and does not exhibit the Zr loss phenomenon that occurs in two-step impregnation. Comparative Example 6 used a calcination method to treat the P-loaded sample, resulting in P loss.

[0120] Examples 1-4 are samples impregnated with different concentrations of zirconium hydrogen phosphate. The crystallization loss of Example 4 with the maximum loading was only 18.4% compared to the sample before loading, and the total specific surface area decreased by less than 5%. Furthermore, the designed impregnation amount and the ZrO2 content and P2O5 content measured by XRF in Examples 1-4 were very similar.

[0121] Table 3. Distribution of partial reaction products from the catalytic cracking of Daqing paraffin-based crude oil over a catalyst.

[0122] catalyst Conversion rate (wt%) Coke (wt%) C2=+C3=(wt%) DY-Cat-1 90.34 11.46 21.27 DY-Cat-2 87.22 12.63 21.89 DY-Cat-3 86.34 10.24 21.28 DY-Cat-4 91.52 13.12 21.65 DY-Cat-5 90.01 12.15 23.19 DY-Cat-6 88.67 10.01 22.97 DY-Cat-7 89.34 11.45 22.74 Cat-1 87.96 9.66 22.82 Cat-2 89.55 9.53 23.41 Cat-3 91.03 8.59 24.02 Cat-4 90.53 8.96 22.99 Cat-5 86.48 8.12 23.57 Cat-6 88.29 7.98 23.54 Cat-7 88.01 7.74 23.24 Cat-8 86.35 7.69 22.77 Cat-9 90.59 8.89 23.48

[0123] As shown in Table 3, compared with Comparative Example 2, the catalysts prepared by Zr-P modified gas-phase ultrastable Y molecular sieves in Examples 1-4, when used for crude oil conversion, showed a 3.21 wt% increase in ethylene + propylene single-pass yield and a 2.68 wt% decrease in coke yield, while maintaining comparable crude oil conversion rates. This is likely because the gas-phase ultrastable Y was modified with Zr and P, resulting in a synergistic effect between Zr and P and the gas-phase ultrastable Y. This further modulates the acidity of the gas-phase ultrastable Y, increasing the proportion of strong acid in the total acid content and the B / L value of the strong acid, making it more suitable as an active component in the catalytic cracking reaction of crude oil with complex group composition and a wide distillation range. In the direct catalytic cracking of crude oil, it exhibits a high ethylene and propylene yield and a low coke content. Compared with Comparative Examples 6 and 7, Example 3 showed a higher ethylene and propylene yield, higher conversion rate, and lower coke content. This is likely because the Zr and P active species in Example 3 are more uniformly distributed, and the Zr and P active species generated from zirconium hydrogen phosphate are more conducive to the reaction of producing low-carbon olefins from the direct catalytic cracking of crude oil.

[0124] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a catalytic cracking catalyst, characterized in that, Includes the following steps: Step 1: Using SiCl4 as a dealuminating and silicon replenishing agent, the NaY molecular sieve is subjected to gas-phase ultrastabilization treatment to obtain a gas-phase ultrastabilized Y molecular sieve. Step 2: Modify the gas-phase ultrastable Y molecular sieve using zirconium hydrogen phosphate; Step 3: Mix the modified gas-phase ultrastable Y molecular sieve obtained in Step 2 with the binder, slurry, and calcine to obtain the catalytic cracking catalyst.

2. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, Step 1, after subjecting the NaY molecular sieve to gas-phase ultrastabilization, also includes steps of ammonium ion exchange and calcination.

3. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, Step 2 also includes placing the modified gas-phase ultrastable Y molecular sieve in a sealed device for a certain period of time, with the temperature of the sealed device being 100℃-200℃.

4. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, The mass of SiCl4 is 10~40wt% of the dry basis mass of NaY molecular sieve, and the temperature of gas phase ultrastabilization treatment is 320~420℃.

5. The method for preparing the catalytic cracking catalyst according to claim 2, characterized in that, Ammonium ion exchange is performed by mixing and exchanging ammonium salt with gas-phase ultrastabilized Y molecular sieve at an exchange temperature of 80-93℃ for 1-2 hours. During the exchange, the pH of the system is controlled at 3.0-3.3, and the mass ratio of ammonium salt to gas-phase ultrastabilized Y molecular sieve is 0.5-1.

0.

6. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, Step 2 modification includes: ultrasonically treating a mixture of zirconium hydrogen phosphate and water to obtain zirconium hydrogen phosphate colloid, and then impregnating the gas-phase ultrastable Y molecular sieve with an equal volume of the zirconium hydrogen phosphate colloid.

7. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, In the modified gas-phase ultrastable Y molecular sieve obtained in step 2, the content of zirconium (calculated as ZrO2) is 0.1~7.5wt%, and the content of phosphorus (calculated as P2O5) is 0.1~8.6wt%.

8. The method for preparing the catalytic cracking catalyst according to claim 1, characterized in that, In step 3, clay was added during the mixing process. The slurry was then spray-dried and calcined to obtain the catalytic cracking catalyst.

9. The method for preparing the catalytic cracking catalyst according to claim 8, characterized in that, With the total mass of the catalytic cracking catalyst as 100%, the dry basis addition of the modified gas-phase ultrastable Y molecular sieve obtained in step 2 is 30-38 wt%, the dry basis addition of clay is 45-53 wt%, and the dry basis addition of binder is 10-17 wt%.

10. The catalytic cracking catalyst obtained by the preparation method according to any one of claims 1-9 is used in the catalytic cracking reaction of crude oil.