Mesoporous in-situ crystallized fcc catalyst and method for preparing the same

Abstract

The application discloses a mesoporous in-situ crystallization FCC catalyst and a preparation method thereof. In one aspect, the application provides a preparation method of a mesoporous in-situ crystallization FCC catalyst, comprising the following steps: S1, microwave expansion treatment of vermiculite to obtain expanded vermiculite powder; S2, acid treatment and modification treatment of the vermiculite powder to obtain modified vermiculite powder; S3, high-temperature calcination and grinding of kaolin to obtain kaolin powder; S4, acid treatment and modification treatment of the kaolin powder to obtain modified kaolin; S5, preparation of the modified kaolin into microspheres; and S6, slurry preparation of the microspheres, and preparation of the mesoporous in-situ crystallization FCC catalyst after aging treatment and in-situ crystallization treatment. In another aspect, the application provides the mesoporous in-situ crystallization FCC catalyst prepared by the preparation method. The application has excellent stability, an ideal pore structure, excellent catalytic activity for heavy oil, high gasoline yield and low coke yield.

Description

Technical Field

[0001] This application relates to the field of petroleum refining technology, and in particular to a mesoporous in-situ crystallization FCC catalyst and its preparation method. Background Technology

[0002] The petrochemical industry is the foundation of modern industry, providing the vast majority of transportation fuels and chemical production raw materials, making it one of the largest and most important industries in modern times. In my country's petroleum refining process, catalytic cracking (FCC) technology is the most basic and crucial method for processing heavy oil into lighter forms. It is also one of the most flexible, efficient, and economical key technologies for the efficient conversion and clean utilization of crude oil, holding a core position in the crude oil processing flow. FCC catalysts are the key core technology of catalytic cracking, directly affecting the catalytic cracking process and determining the outcome of crude oil processing. From a preparation process perspective, FCC catalysts are mainly divided into two types: semi-synthetic catalysts and in-situ crystallization catalysts. Semi-synthetic catalysts utilize industrial raw materials such as silicon and aluminum sources to first synthesize molecular sieves, which are then mixed with binders and kaolin to prepare the catalyst. In-situ crystallization catalysts are prepared by first spraying kaolin and binders into balls, then synthesizing molecular sieves, and finally modifying them to prepare the catalyst.

[0003] As oil resources are consumed at an ever-increasing rate, global oil reserves are declining, and crude oil quality is deteriorating. The proportion of heavy oil (high in oil content) and high-sulfur oil (high in sulfur content), which are difficult to refine, is steadily increasing. In-situ crystallization catalysts, due to their high stability and strong ability to crack heavy oil molecules, are gradually becoming dominant in FCC processes. However, as the proportion of heavy oil in crude oil continues to rise, higher demands are being placed on the performance of FCC catalysts. Heavy oil contains relatively high levels of macromolecular compounds such as gums and asphaltenes. These compounds have extremely high gasification temperatures and are difficult to gasify under conventional cracking conditions. They are easily converted into coke during catalyst regeneration, leading to reduced conversion rates and the generation of large amounts of coke and dry gas. Existing technologies improve in-situ crystallization catalysts by modifying the kaolin matrix and optimizing the preparation process to improve pore structure, in order to meet the needs of heavy oil processing. However, the existing in-situ crystallization catalysts are still not ideal for the catalytic cracking of heavy oil, and have problems such as easy metal poisoning, insufficient catalytic cracking conversion rate, and excessively high coke yield. Summary of the Invention

[0004] To address at least one of the aforementioned technical problems and develop an FCC catalyst with excellent stability, a relatively ideal pore structure, superior heavy oil catalytic activity, high gasoline yield, and low coke yield, this application provides a mesoporous in-situ crystallization FCC catalyst and its preparation method.

[0005] On the one hand, this application provides a method for preparing a mesoporous in-situ crystallized FCC catalyst, comprising the following steps:

[0006] S1. After washing and drying the vermiculite, microwave expansion treatment is performed. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite powder.

[0007] S2. The vermiculite powder obtained in step S1 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50 and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate and aluminum chloride and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours and then ground to a particle size of 5-50 μm to obtain modified vermiculite powder.

[0008] S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder;

[0009] S4. The kaolin powder from step S3 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50, and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours to obtain modified kaolin.

[0010] S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.15~0.25:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture to form a slurry at a mass ratio of 1:0.1~0.15:0.2~0.25:15~30, and then spray-dried to granulate the mixture to form microparticles with a particle size of 50~100μm. The microparticles are then calcined at 550~600℃ for more than 2 hours to obtain microspheres.

[0011] S6. Take the microspheres obtained in step S5, and mix them thoroughly with sodium aluminate, water glass, sodium hydroxide and deionized water according to the mass ratio of microspheres:sodium oxide:alumina:silicon oxide:deionized water of 1:0.1~0.18:0.01~0.02:0.18~0.24:20~30. After aging and in-situ crystallization, filter out the solid product, wash and dry it to obtain the mesoporous in-situ crystallized FCC catalyst.

[0012] Optionally, in step S1, the microwave power of the microwave expansion treatment is 400~450W, and the treatment time is 2~8min.

[0013] Optionally, in step S2, the ultrasonic acid treatment temperature is 80~85℃.

[0014] Optionally, in step S2, the concentrations of bismuth nitrate and antimony nitrate in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride are 0.2~0.3 g / mL and 0.1~0.2 g / mL, respectively.

[0015] Optionally, in step S2, the concentration of aluminum chloride in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride is 1~1.5 g / mL.

[0016] Optionally, in step S4, the ultrasonic acid treatment temperature is 80~85℃.

[0017] Optionally, in step S4, the concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution prepared from yttrium chloride and zirconium sulfate are 0.04~0.6 g / mL and 0.04~0.6 g / mL, respectively.

[0018] Optionally, in step S6, the aging process is carried out at a temperature of 75~80℃ for at least 24 hours.

[0019] Optionally, in step S6, the in-situ crystallization treatment is carried out by dynamic crystallization at a temperature of 100~110℃ for 10~12h.

[0020] On the other hand, this application provides a method for preparing the above-mentioned mesoporous in-situ crystallized FCC catalyst, and the resulting mesoporous in-situ crystallized FCC catalyst.

[0021] In summary, the present invention has at least one of the following beneficial technical effects:

[0022] 1. This application, by adding a specific amount of specially treated and modified vermiculite to kaolin and combining it with special process steps, produces an FCC catalyst with a relatively more ideal pore structure. The resulting matrix has abundant macroporous channels, the embedded vermiculite has suitable mesoporous channels, and the molecular sieve formed by in-situ crystallization has an abundant microporous pore structure. This facilitates the contact between heavy oil macromolecules and active components, promotes molecular diffusion, reduces deep cracking reactions, significantly improves the catalytic activity of the FCC catalyst for heavy oil, thereby reducing coke and dry gas yields and effectively improving conversion rate.

[0023] 2. The FCC catalyst of this application, through modification of the kaolin matrix and the use of specially modified vermiculite, can effectively capture heavy metals such as nickel and vanadium, avoid their coverage of catalytic active sites, and greatly improve the catalyst's resistance to heavy metal pollution.

[0024] 3. The FCC catalyst of this application has undergone acidification and specific modification treatments on vermiculite to give it certain catalytic activity; at the same time, the kaolin in this application has undergone specific modification treatments to increase the acid content and give it high catalytic activity; the above modifications, combined with the pore structure formed in this application, enable the FCC catalyst of this application to form a catalytic chain of macroporous and mesoporous pre-catalytic cracking followed by microporous high-efficiency catalytic cracking, with excellent catalytic effect and the ability to significantly improve gasoline yield. Attached Figure Description

[0025] Figure 1 This is an electron micrograph of the catalyst in Example 1 of this application. Detailed Implementation

[0026] The present application will be further described in detail below with reference to the embodiments.

[0027] This application provides a method for preparing a mesoporous in-situ crystallized FCC catalyst, comprising the following steps:

[0028] S1. After washing and drying the vermiculite, microwave expansion treatment is performed. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite powder.

[0029] S2. The vermiculite powder obtained in step S1 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50 and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate and aluminum chloride and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours and then ground to a particle size of 5-50 μm to obtain modified vermiculite powder.

[0030] S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder;

[0031] S4. The kaolin powder from step S3 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50, and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours to obtain modified kaolin.

[0032] S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.15~0.25:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture to form a slurry at a mass ratio of 1:0.1~0.15:0.2~0.25:15~30, and then spray-dried to granulate the mixture to form microparticles with a particle size of 50~100μm. The microparticles are then calcined at 550~600℃ for more than 2 hours to obtain microspheres.

[0033] S6. Take the microspheres obtained in step S5, and mix them thoroughly with sodium aluminate, water glass, sodium hydroxide and deionized water according to the mass ratio of microspheres:sodium oxide:alumina:silicon oxide:deionized water of 1:0.1~0.18:0.01~0.02:0.18~0.24:20~30. After aging and in-situ crystallization, filter out the solid product, wash and dry it to obtain the mesoporous in-situ crystallized FCC catalyst.

[0034] Prior to this application, existing in-situ crystallization-type FCC catalysts primarily used kaolin as the main raw material. Impurity metals were removed through acid treatment, and the acid strength and quantity were increased through modification treatment. Then, in-situ crystallization was performed to produce NaY molecular sieves, which were then used to prepare the catalyst. These catalysts mainly utilize the crystalline structure formed by calcining kaolin to capture heavy metals, and the resulting porous structure ensures sufficient contact between the catalytically active material and crude oil components. Combined with the high catalytic activity resulting from the high acid content, this achieves highly efficient catalysis. However, these catalysts are not ideal for heavy oil. Analysis of existing catalyst preparation methods revealed that in-situ crystallization treatment reduces the number and volume of pores in the catalyst, thus affecting the contact between the large molecular components of heavy oil and the catalytically active material. Furthermore, these catalysts have poor heavy metal capture efficiency, easily leading to the coverage of catalytic active sites by heavy metals such as nickel and vanadium, resulting in catalyst contamination and failure. Furthermore, heavy oil contains a significant amount of macromolecular compounds such as gums and asphaltenes. The pore structure of existing catalysts is not ideal, affecting the catalytic cracking effect on these macromolecular compounds. Therefore, existing catalysts are not ideal for heavy oil, resulting in low gasoline yield, high coke yield, and relatively low overall conversion rate.

[0035] This application designs a composite catalyst by introducing modified vermiculite. Through microwave expansion and modification treatment, it can be endowed with a mesoporous structure and certain catalytic effects. This design, combined with pore-expanding treatment of cellulose, enables the prepared catalyst to form a relatively ideal pore structure from macropores to mesopores to micropores, facilitating the entry and catalysis of large molecular compounds in heavy oil. Furthermore, through modification treatment, this application can form a catalytic chain of macroporous and mesoporous pre-catalytic cracking followed by high-efficiency microporous catalytic cracking, achieving efficient catalytic cracking of large molecular compounds in heavy oil. In addition, this application modifies kaolinite with yttrium chloride and zirconium sulfate, giving the molecular sieve formed by catalyst crystallization excellent catalytic activity. This promotes the formation of saturated alkanes as much as possible from the large molecular compounds in heavy oil after catalytic cracking, thereby effectively improving gasoline yield, reducing coke yield, and significantly improving conversion rate.

[0036] The design of this application, with its macroporous-mesoporous-microporous channel structure, allows large molecular compounds from heavy oil to enter the catalyst's pores, ensuring sufficient contact between the catalytic active sites and the various components of the heavy oil. The addition of cellulose enables kaolin to form larger pores during calcination, effectively expanding the pores. Even after in-situ crystallization, which reduces the number and volume of pores, the catalyst still maintains abundant macroporous channels.

[0037] This application modifies kaolin by composite impregnation with yttrium chloride and zirconium sulfate. After sintering, the kaolin is uniformly loaded with strongly acidic zirconium compounds and moderately acidic yttrium compounds. This ensures that the macroporous surface of the catalyst after calcination and in-situ crystallization is loaded with the aforementioned composite acidic active sites of strong and moderate acids. The microporous surface of the molecular sieve formed by in-situ crystallization is also loaded with the aforementioned composite acidic active sites of strong and moderate acids. The loading modification of mesoporous vermiculite in this application involves loading bismuth nitrate, antimony nitrate, and aluminum chloride. After calcination, bismuth nitrate and antimony nitrate form bismuth and antimony oxides loaded on the mesoporous surface of vermiculite. This effectively captures heavy metals from heavy oil entering the macropores, effectively preventing contamination of the molecular sieve. The loading of acidic aluminum allows the formation of moderately acidic active catalytic sites on the vermiculite surface. This design allows the large molecular compounds in the heavy oil entering the macropores of the catalyst to first contact the complex acidic active sites within the macropores during catalytic cracking. These compounds undergo preliminary catalytic cracking into smaller molecules, then enter the mesopores to capture heavy metals and continue the cracking reaction under the catalysis of acidic aluminum active sites, completing the pre-catalytic cracking. The smaller molecular components, after pre-catalytic cracking, can then smoothly enter the pores of the molecular sieve, where they are catalyzed by the active sites to generate even smaller hydrocarbon molecules. This loading modification design, combined with the pore design, can form a strong-medium-strong-strong catalytic chain, effectively promoting the catalytic cracking of heavy oil, avoiding the surge in coke yield caused by over-catalysis, significantly increasing the formation rate of small molecule hydrocarbons, and thus significantly increasing gasoline yield and reducing coke yield.

[0038] Furthermore, this application uses a composite raw material of kaolin and vermiculite powder as a matrix, and prepares microspheres through a multi-calcination process, followed by in-situ crystallization treatment to prepare the catalyst. Expanded vermiculite possesses excellent heat resistance, and the multi-calcination process allows the formation of kaolinite and quartz phases in the microspheres of this application, effectively improving the strength and wear resistance of the catalyst, compensating for the insufficient strength of vermiculite, and giving the catalyst excellent stability.

[0039] The following are embodiments of this application.

[0040] Example 1

[0041] The preparation of the mesoporous in-situ crystallized FCC catalyst in this embodiment includes the following steps:

[0042] S1. After ultrasonically cleaning the vermiculite with deionized water for 30 minutes and vacuum drying, it is microwave expanded for 1.5 minutes at 500W. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite micro powder.

[0043] S2. The vermiculite powder obtained in step S1 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. After ultrasonic acid treatment at 65°C for 6 hours, it is washed with deionized water, vacuum dried, and then placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate, and aluminum chloride. After ultrasonic impregnation for 1 hour, it is filtered out and calcined at 550~600°C for 2 hours. Then it is ground to a particle size of 5~50 μm to obtain modified vermiculite powder. The concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution are 0.5 g / mL, 0.3 g / mL, and 2 g / mL, respectively.

[0044] S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder;

[0045] S4. The kaolin powder from step S3 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. It is then ultrasonically treated at 65°C for 6 hours. After washing with deionized water and vacuum drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for 1 hour. After filtration, it is calcined at 550-600°C for 2 hours to obtain modified kaolin. The concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution are 0.03 g / mL and 0.03 g / mL, respectively.

[0046] S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.15:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture at a mass ratio of 1:0.1:0.2:15 to form a slurry. Then, the mixture is spray-dried and granulated to form microparticles with a particle size of 50~100μm. Finally, the microspheres are calcined at 550~600℃ for 2h.

[0047] S6. Take the microspheres obtained in step S5, and mix sodium aluminate, water glass, sodium hydroxide and deionized water with the microspheres in a mass ratio of 1:0.1:0.01:0.18:20. After standing and aging at 75~80℃ for 24h, the mixture is dynamically crystallized at 100~110℃ for 10h. The solid product is filtered out, washed with deionized water and vacuum dried to obtain the mesoporous in-situ crystallized FCC catalyst.

[0048] Example 2

[0049] The preparation of the mesoporous in-situ crystallized FCC catalyst in this embodiment includes the following steps:

[0050] S1. After ultrasonically cleaning the vermiculite with deionized water for 30 minutes and vacuum drying, it is microwave expanded for 1.5 minutes at 500W. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite micro powder.

[0051] S2. The vermiculite powder obtained in step S1 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. After ultrasonic acid treatment at 65°C for 6 hours, it is washed with deionized water, vacuum dried, and then placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate, and aluminum chloride. After ultrasonic impregnation for 1 hour, it is filtered out and calcined at 550~600°C for 2 hours. Then it is ground to a particle size of 5~50 μm to obtain modified vermiculite powder. The concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution are 0.5 g / mL, 0.3 g / mL, and 2 g / mL, respectively.

[0052] S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder;

[0053] S4. The kaolin powder from step S3 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. It is then ultrasonically treated at 65°C for 6 hours. After washing with deionized water and vacuum drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for 1 hour. After filtration, it is calcined at 550-600°C for 2 hours to obtain modified kaolin. The concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution are 0.03 g / mL and 0.03 g / mL, respectively.

[0054] S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.25:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture to form a slurry at a mass ratio of 1:0.15:0.25:30, and then spray-dried to granulate to produce microparticles with a particle size of 50~100μm. The microparticles are then calcined at 550~600℃ for 2h to obtain microspheres.

[0055] S6. Take the microspheres obtained in step S5, and mix sodium aluminate, water glass, sodium hydroxide and deionized water with the microspheres in a mass ratio of 1:0.18:0.02:0.24:30. After standing and aging at 75~80℃ for 24h, the mixture is dynamically crystallized at 100~110℃ for 10h. The solid product is filtered out, washed with deionized water and vacuum dried to obtain the mesoporous in-situ crystallized FCC catalyst.

[0056] Example 3

[0057] The preparation of the mesoporous in-situ crystallized FCC catalyst in this embodiment includes the following steps:

[0058] S1. After ultrasonically cleaning the vermiculite with deionized water for 30 minutes and vacuum drying, it is microwave expanded for 1.5 minutes at 500W. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite micro powder.

[0059] S2. The vermiculite powder obtained in step S1 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. After ultrasonic acid treatment at 65°C for 6 hours, it is washed with deionized water, vacuum dried, and then placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate, and aluminum chloride. After ultrasonic impregnation for 1 hour, it is filtered out and calcined at 550~600°C for 2 hours. Then it is ground to a particle size of 5~50 μm to obtain modified vermiculite powder. The concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution are 0.5 g / mL, 0.3 g / mL, and 2 g / mL, respectively.

[0060] S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder;

[0061] S4. The kaolin powder from step S3 is placed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10. It is then ultrasonically treated at 65°C for 6 hours. After washing with deionized water and vacuum drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for 1 hour. After filtration, it is calcined at 550-600°C for 2 hours to obtain modified kaolin. The concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution are 0.03 g / mL and 0.03 g / mL, respectively.

[0062] S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.2:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture to form a slurry according to a mass ratio of 1:0.3:0.22:24 of mixture:alumina:cellulose:deionized water. Then, the mixture is spray-dried and granulated to form microparticles with a particle size of 50~100μm. Finally, the microspheres are calcined at 550~600℃ for 2h.

[0063] S6. Take the microspheres obtained in step S5, and mix sodium aluminate, water glass, sodium hydroxide and deionized water with the microspheres in a mass ratio of 1:0.15:0.014:0.21:26. Let the mixture stand at 75~80℃ for 24h, and then dynamically crystallize it at 100~110℃ for 12h. Filter out the solid product, wash it with deionized water and vacuum dry it to obtain the mesoporous in-situ crystallized FCC catalyst.

[0064] Example 4

[0065] The difference between this embodiment and embodiment 3 is that in step S1, the microwave power of the microwave expansion treatment is 400W and the processing time is 8min.

[0066] Example 5

[0067] The difference between this embodiment and embodiment 3 is that in step S1, the microwave power of the microwave expansion treatment is 450W and the processing time is 2min.

[0068] Example 6

[0069] The difference between this embodiment and embodiment 3 is that in step S1, the microwave power of the microwave expansion treatment is 400W and the processing time is 5min.

[0070] Example 7

[0071] The difference between this embodiment and embodiment 6 is that the ultrasonic acid treatment temperature in steps S2 and S4 is 80~85℃.

[0072] Example 8

[0073] The difference between this embodiment and Embodiment 7 is that, in step S2, the concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride are 0.2 g / mL, 0.1 g / mL, and 1 g / mL, respectively; and in step S4, the concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution prepared from yttrium chloride and zirconium sulfate are 0.04 g / mL and 0.04 g / mL, respectively.

[0074] Example 9

[0075] The difference between this embodiment and Embodiment 7 is that, in step S2, the concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride are 0.3 g / mL, 0.2 g / mL, and 1.5 g / mL, respectively; and in step S4, the concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution prepared from yttrium chloride and zirconium sulfate are 0.06 g / mL and 0.06 g / mL, respectively.

[0076] Example 10

[0077] The difference between this embodiment and Embodiment 7 is that, in step S2, the concentrations of bismuth nitrate, antimony nitrate, and aluminum chloride in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride are 0.24 g / mL, 0.16 g / mL, and 1.2 g / mL, respectively; and in step S4, the concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution prepared from yttrium chloride and zirconium sulfate are 0.05 g / mL and 0.05 g / mL, respectively.

[0078] Comparative Example 1

[0079] This application uses NaY molecular sieve catalyst produced by Zhuoran Environmental Protection Technology (Dalian) Co., Ltd. as comparative example 1.

[0080] Comparative Example 2

[0081] This application selects Example 2 of the invention patent with publication number CN116328821A and invention title "A Mesoporous In-situ Crystallization FCC Catalyst and Its Preparation Method" as Comparative Example 2 of this application.

[0082] The catalytic cracking effect of the products from Examples 1-10 and Comparative Examples 1-2 was tested.

[0083] The sample crude oil was heavy crude oil purchased from a certain company. The properties of the crude oil are shown in Table 1 below.

[0084] Table 1 Crude Oil Properties

[0085]

[0086] The catalysts prepared in Examples 1-10 of this application and the catalysts in Comparative Examples 1-2 were installed in a catalytic cracking unit. The reaction temperature was 500-540°C, and the mass ratio of catalyst to feedstock was 4:1. The catalytic cracking effect was then tested. The results are shown in Table 2.

[0087] Table 2. Test results of Examples 1-10 and Comparative Examples 1-2

[0088] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Dry gas (%) 2.82 2.85 2.78 2.72 2.74 2.66 Liquefied petroleum gas (%) 20.90 20.85 20.97 21.07 21.08 21.16 gasoline(%) 56.86 56.81 56.93 56.98 56.96 57.12 diesel fuel(%) 11.79 11.83 11.77 11.74 11.75 11.71 heavy oil(%) 3.40 3.41 3.35 3.31 3.28 3.22 Coke (%) 4.21 4.23 4.18 4.16 4.17 4.11 Total liquid yield (%) 89.55 89.49 89.73 89.79 89.79 89.99 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Dry gas (%) 2.63 2.52 2.49 2.47 6.81 3.32 Liquefied petroleum gas (%) 21.29 21.31 21.39 21.39 18.12 22.36 gasoline(%) 57.17 57.28 57.33 57.37 47.92 50.09 diesel fuel(%) 11.62 11.66 11.63 11.65 12.48 11.64 heavy oil(%) 3.18 3.19 3.13 3.12 7.26 5.81 Coke (%) 4.09 4.02 4.01 3.98 7.29 6.58 Total liquid yield (%) 90.08 90.25 90.35 90.41 76.53 84.09

[0089] As can be seen from the data in Table 2, the combined catalysts prepared in Examples 1-10 of this application exhibit significantly better total liquid phase yield and gasoline yield in the catalytic cracking of heavy oil compared to the catalysts in Comparative Examples 1 and 2, while the coke yield is significantly lower. This demonstrates that the mesoporous in-situ crystallized FCC catalyst of this application, with its more ideal pore structure and specifically designed catalytic pathway, significantly improves the catalytic cracking effect of heavy oil, demonstrating a significantly superior catalytic performance compared to existing catalysts.

[0090] The data in Table 1, comparing the data from Examples 1-10 of this application, shows that the catalytic effect of the catalyst is further improved after optimizing the catalyst ratio. Furthermore, the catalytic effect is also further improved after optimizing the preparation process. The applicant believes that using specific microwave treatment parameters can achieve better expansion effects, making the mesoporous pores of the expanded vermiculite more compatible with the catalyst of this application. Optimizing the acid treatment process parameters can more effectively remove metal impurities from the raw materials, effectively improving the catalytic activity of the catalyst. Optimizing the concentration ratio of the modified solution can give the supported modified components a better ratio, allowing the formed bismuth and antimony oxide components to achieve better resistance to heavy metal contamination, while making the acid strength and amount of the acid supported on vermiculite and kaolin more suitable, resulting in better pre-catalytic and final catalytic effects. Furthermore, using the specific aging and in-situ crystallization parameters of this application can effectively improve the crystallization rate, thereby improving the catalytic activity of the catalyst.

[0091] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A method for preparing a mesoporous in-situ crystallized FCC catalyst, characterized in that, Includes the following steps: S1. After washing and drying the vermiculite, microwave expansion treatment is performed. After sieving out the unexpanded vermiculite, the expanded vermiculite is ground to a particle size of 5~50μm to obtain expanded vermiculite powder. S2. The vermiculite powder obtained in step S1 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50 and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of bismuth nitrate, antimony nitrate and aluminum chloride and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours and then ground to a particle size of 5-50 μm to obtain modified vermiculite powder. S3. Calcine the kaolin at 700~750℃ for more than 2 hours, and grind it to a particle size of 5~50μm to obtain kaolin micro powder; S4. The kaolin powder from step S3 is placed in a 0.5-1 mol / L hydrochloric acid solution at a solid-liquid mass ratio of 1:10-50, and ultrasonically acid-treated for more than 6 hours. After washing and drying, it is placed in a mixed aqueous solution of yttrium chloride and zirconium sulfate and ultrasonically impregnated for more than 1 hour. After filtration, it is calcined at 550-600℃ for more than 2 hours to obtain modified kaolin. S5. The modified vermiculite powder obtained in step S2 and the modified kaolin obtained in step S4 are mixed at a mass ratio of 0.15~0.25:1 to obtain a mixture. The aluminum sol, cellulose and deionized water are mixed with the mixture to form a slurry at a mass ratio of 1:0.1~0.15:0.2~0.25:15~30, and then spray-dried to granulate the mixture to form microparticles with a particle size of 50~100μm. The microparticles are then calcined at 550~600℃ for more than 2 hours to obtain microspheres. S6. Take the microspheres obtained in step S5, and mix them thoroughly with sodium aluminate, water glass, sodium hydroxide and deionized water according to the mass ratio of microspheres:sodium oxide:alumina:silicon oxide:deionized water of 1:0.1~0.18:0.01~0.02:0.18~0.24:20~30. After aging and in-situ crystallization, filter out the solid product, wash and dry it to obtain the mesoporous in-situ crystallized FCC catalyst.

2. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S1, the microwave power of the microwave expansion treatment is 400~450W, and the treatment time is 2~8min.

3. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S2, the ultrasonic acid treatment temperature is 80~85℃.

4. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S2, the concentrations of bismuth nitrate and antimony nitrate in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride are 0.2~0.3 g / mL and 0.1~0.2 g / mL, respectively.

5. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S2, the concentration of aluminum chloride in the mixed aqueous solution prepared from bismuth nitrate, antimony nitrate, and aluminum chloride is 1~1.5 g / mL.

6. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S4, the ultrasonic acid treatment temperature is 80~85℃.

7. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S4, the concentrations of yttrium chloride and zirconium sulfate in the mixed aqueous solution prepared from yttrium chloride and zirconium sulfate are 0.04~0.6 g / mL and 0.04~0.6 g / mL, respectively.

8. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S6, the aging process involves standing at 75-80°C for at least 24 hours.

9. The method for preparing the mesoporous in-situ crystallized FCC catalyst according to claim 1, characterized in that, In step S6, the in-situ crystallization treatment is carried out by dynamic crystallization at a temperature of 100~110℃ for 10~12h.

10. A method for preparing the mesoporous in-situ crystallized FCC catalyst according to any one of claims 1 to 9, wherein the mesoporous in-situ crystallized FCC catalyst is obtained.

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