Fluidized catalytic cracking catalyst with high rare earth content, preparation method of fluidized catalytic cracking catalyst and application of fluidized catalytic cracking catalyst in catalytic cracking process of high-iron vanadium-nickel feedstock

Abstract

The invention provides a fluidized catalytic cracking catalyst with high rare earth content, a preparation method and application of the fluidized catalytic cracking catalyst in a high-iron vanadium-nickel feed catalytic cracking process, the preparation method comprises the following steps: step 1, mixing and stirring clay, pseudo-boehmite, cerium chloride, alumina sol, silica sol and water to obtain a first mixed solution; step 2, adding a P modified USY molecular sieve, cerium chloride and a silicon-containing macroporous bauxite slurry into the first mixed solution in the step 1, pulping, homogenizing, forming, roasting, washing and drying to obtain the fluidized catalytic cracking catalyst with high rare earth content. At present, the conventional rare earth content in the industry is less than 3.5% and is not more than 5% at most, while the catalyst disclosed by the invention adopts the design of high rare earth content and low molecular sieve content, iron, vanadium and nickel are passivated by the high rare earth content, and the structural stability of the catalyst is guaranteed.

Description

Technical Field

[0001] The present invention relates to the technical field of fluidized catalytic cracking catalysts, and in particular to a high rare earth content fluidized catalytic cracking catalyst, a preparation method and application thereof in a high iron, vanadium and nickel feed catalytic cracking process. Background Art

[0002] In the fluid catalytic cracking (FCC) sector of the petrochemical industry, as crude oil quality gradually deteriorates, the use of high-iron, vanadium, and nickel feedstocks in FCC processes is increasing. However, the iron, vanadium, and nickel in these feedstocks can severely toxicize FCC catalysts, severely impacting their activity, selectivity, and stability. This leads to reduced light oil yields and increased coke and gaseous products, significantly limiting the economic benefits and sustainable development of the FCC process.

[0003] Heavy metals in feedstock can be toxic to FCC catalysts, significantly reducing their activity and selectivity. For example, iron deposition can affect the catalyst's pore structure. When iron levels reach a certain level, it can form nodules on the catalyst surface, severely hindering the diffusion of reactants and products and reducing catalytic efficiency. Vanadium undergoes a redox reaction in the high-temperature environment of the regenerator to produce vanadium pentoxide. In the presence of water vapor, vanadium pentoxide can degrade FCC catalyst activity. Its high volatility also causes vanadium to be distributed over a large area on the catalyst particles, further reducing reaction selectivity, increasing thermal cracking reactions, and significantly increasing coke yields. Furthermore, the dehydrogenation of feedstock molecules on heavy metal vanadium can contribute to the formation of coke as a byproduct. Nickel can also negatively impact catalysts, altering the catalyst's active centers, leading to increased hydrogen and coke yields and reduced light oil yields.

[0004] To address these issues, numerous researchers and companies have conducted extensive research and applied for related patents. For example, the patent "A Heavy Oil Catalytic Cracking Catalyst and Its Preparation Method" (CN 2011104199222) describes rare earth modification of Y-type zeolites, aiming to improve their cracking activity and stability. This patent utilizes a specific rare earth exchange and dispersed pre-exchange process to localize rare earth ions within sodalite cages, partially inhibiting dealumination of the zeolite framework during water vapor aging and improving the catalyst's heavy oil conversion capacity. However, this method has several drawbacks. For example, the addition of large amounts of ammonium ions during the preparation process can cause ammonia nitrogen pollution and increase pollution control costs. It also fails to effectively address the problem of zeolite particle agglomeration, reduces the specific surface area and pore volume of the zeolite, increases the resistance of the modifying elements to the zeolite cages, and results in low rare earth ion utilization. CN1334314A and CN104923282B disclose high-rare-earth-content catalysts and additives, which offer advantages such as high cracking activity, strong vanadium resistance, and stable structure, making them suitable for catalytic cracking units with high-vanadium feeds. While these patents improve the catalyst's tolerance to vanadium and iron to a certain extent, their high molecular sieve content leads to high catalyst costs. Furthermore, when processing high-vanadium iron feeds, the molecular sieves readily react with vanadium, leading to structural collapse and rapid activity degradation, making it difficult to achieve high catalytic efficiency.

[0005] Regarding heavy metal pollution resistance, Exxon's US4824815 and US4944864 mention that catalysts containing strontium carbonate and calcium carbonate have good resistance to vanadium pollution. Phillips' vanadium scavengers (US4750988) using MgO as the active vanadium scavenger, as well as barium compounds (US4377494 and US4473463), have improved feed conversion and selectivity to a certain extent. However, these patents primarily focus on the addition of functional components such as magnesium and aluminum, lacking significant results in modifying the catalyst's pore structure. Furthermore, they fail to fully consider the role of high rare earth content in heavy metal resistance and catalytic performance. In summary, it is difficult for existing FCC catalysts to achieve an ideal balance in terms of heavy metal resistance, activity stability, selectivity, and coke yield control when processing high-iron, vanadium, and nickel feeds. Therefore, there is an urgent need to find and prepare a new catalyst that can achieve an ideal balance in terms of heavy metal resistance, activity stability, selectivity, and coke yield control when processing high-iron, vanadium, and nickel feeds. Summary of the Invention

[0006] The present invention aims to solve the problem that the existing FCC catalyst is difficult to achieve an ideal balance in heavy metal resistance, activity, stability, selectivity and coke yield control when processing high iron, vanadium and nickel feed, and provides a.

[0007] In order to achieve the above technical objectives, the technical solution provided by the present invention is: A high rare earth content fluid catalytic cracking catalyst, wherein the molecular sieve content is 18-23%, the rare earth content is 8-15%, and the rare earth content / molecular sieve content ratio is 35%-52%.

[0008] Furthermore, the rare earth is CeO2.

[0009] Furthermore, the molecular sieve is a P-modified USY molecular sieve.

[0010] Furthermore, it also includes aluminum sol, the aluminum sol content is 4-8%; the silicon modified matrix content is 4-8%, and the SiO2 content in the silicon modified matrix is ​​5-15%.

[0011] Specifically, the silicon-modified matrix is ​​silicon-containing macroporous aluminum oxide.

[0012] The present invention also provides a method for preparing a fluidized catalytic cracking catalyst with a high rare earth content, comprising the following steps: Step 1: mixing clay, pseudo-boehmite, cerium chloride, aluminum sol, silica sol, and water to obtain a first mixed solution; Step 2: Add P-modified USY molecular sieve, cerium chloride, and silicon-containing macroporous aluminum stone slurry to the first mixed solution in step 1, beat, homogenize, shape, calcine, wash, and dry to obtain a high rare earth content fluidized catalytic cracking catalyst.

[0013] Among them, adding cerium chloride in step 1 improves the thermal stability and hydrothermal stability of aluminum oxide and aluminum hydroxide in the matrix, and plays a role in resistance to iron, vanadium and nickel; adding cerium chloride in step 2 improves the stability of the molecular sieve, increases the cracking activity of the molecular sieve, and plays a certain role in resistance to iron, vanadium and nickel.

[0014] Among them, cerium chloride is calcined to generate cerium oxide.

[0015] Furthermore, the clay is kaolin and / or halloysite.

[0016] Furthermore, the preparation method of the silicon-containing macroporous boehmite slurry in step 2 includes the following steps: adding water to the macroporous boehmite and stirring, adding water glass and stirring at a certain temperature, filtering, washing, and then adding water to obtain the silicon-containing macroporous boehmite slurry.

[0017] The present invention also discloses an application of a high rare earth content fluidized catalytic cracking catalyst in a high iron, vanadium and nickel feed catalytic cracking process.

[0018] The present invention has the following beneficial effects: 1. The conventional rare earth content in the current industry is below 3.5%, and no more than 5%. The catalyst of the present invention is designed with a high rare earth content and a low molecular sieve content. The molecular sieve content is 18-23%, the rare earth content is 8-15%, and the rare earth content / molecular sieve content ratio is 35%-52%. The high rare earth content passivates iron, vanadium and nickel, ensuring the stability of the catalyst structure.

[0019] 2. The rare earth in the present invention is preferably CeO2. Part of the rare earth exists in the molecular sieve, and part forms nano rare earth oxides. This unique distribution method can give full play to the role of rare earth in stabilizing the molecular sieve structure, neutralizing the toxicity of heavy metals, and significantly improving the catalyst activity.

[0020] 3. The P-modified USY molecular sieve for molecular screening of the present invention improves the iron resistance of the catalyst. P can passivate the iron element, accurately control the acidity, and optimize the reaction path.

[0021] 4. The matrix of the present invention is modified with silicon, which enhances the mechanical strength and wear resistance of the catalyst and provides a basis for high replacement efficiency. In addition, the combination of high matrix content and low aluminum sol content, with an aluminum sol content of 4-8% and a silicon-modified matrix content of 4-8%, forms a catalyst structure with a high specific surface area, further improving the catalytic efficiency.

[0022] 5. The molecular sieve content of the present invention is 18-23%, the aluminum sol content is 4-8%, the silicon modified matrix content is 4-8%, and the rest is clay, thereby achieving low-cost preparation of the catalyst.

[0023] 6. The low-cost, high-activity, iron-vanadium-nickel resistant inferior oil catalytic cracking catalyst developed by the present invention has low production cost. In the case of high iron, vanadium and nickel, the catalyst has high activity, low coke and oil slurry yields, and improved total yields of gasoline + diesel + liquefied gas. DETAILED DESCRIPTION

[0024] The following is a clear and complete description of the technical solution of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0025] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0026] In each embodiment, the specific surface area of ​​the sample is measured by BET low-temperature nitrogen adsorption method, the elemental composition of the sample is measured by X-ray fluorescence spectrometer, and the wear index of the sample is measured by wear index analyzer.

[0027] The catalytic cracking reactions in the Examples and Comparative Examples were evaluated in a microfluidized bed reactor (ACE) and a gas chromatograph. The catalytic cracking performance of the catalysts in the Examples and Comparative Examples is shown in Table 1.

[0028] For other tests, please refer to (National Standard for Testing Methods for Petroleum and Petroleum Products, published by China Standards Press in 1989).

[0029] Example 1 0.5 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g) was added to 2 kg of water, and 0.043 kg (SiO2 dry weight) of water glass was added under stirring. The mixture was stirred at 80°C for 1 hour, filtered, washed, and then added to 1.5 kg of water to obtain silicon-containing macroporous aluminum stone slurry 1.

[0030] Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 1, and 2.5 kg of deionized water was added. The mixture was beaten for another 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-1.

[0031] The wear index of HCF-1 is 1.6 wt% / h and the BET surface area is 214 m 2 / g, and the pore volume is 0.39 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0032] Example 2: 0.5 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g) was added to 2 kg of water, and 0.068 kg (SiO2 dry weight) of water glass was added under stirring. The mixture was stirred at 80°C for 1 hour, filtered, washed, and then added to 1.5 kg of water to obtain silicon-containing macroporous aluminum stone slurry 2.

[0033] Under stirring conditions, 2.4 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.3 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.8 kg (based on dry weight of CeO2) of cerium chloride, 0.5 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 2, and 2.5 kg of deionized water was added. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-2.

[0034] The wear index of HCF-2 is 2.2 wt% / h, the BET surface area is 211 m2 / g, and the pore volume is 0.38 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0035] Example 3: 0.5 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g) was added to 2 kg of water, and 0.056 kg (SiO2 dry weight) of water glass was added under stirring. The mixture was stirred at 80°C for 1 hour, filtered, washed, and then added to 1.5 kg of water to obtain silicon-containing macroporous aluminum stone slurry 3.

[0036] Under stirring conditions, 2.8 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.3 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 3, and 2.5 kg of deionized water was added. The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-3.

[0037] The wear index of HCF-3 is 1.3 wt% / h and the BET specific surface area is 218 m 2 / g, and the pore volume is 0.39 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0038] Example 4: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 2.0%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 1 from Example 1, and 2.5 kg of deionized water was added. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-4.

[0039] The wear index of HCF-4 is 1.6 wt% / h and the BET specific surface area is 220 m 2 / g, and the pore volume is 0.39 cm 3After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0040] Example 5: 0.7 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g) was added to 2 kg of water, and 0.061 kg (SiO 2 The water glass (based on dry weight) was stirred at 80° C. for 1 hour, filtered, washed, and then added to 2.0 kg of water to obtain a silicon-containing macroporous aluminum stone slurry 5.

[0041] Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.3 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 5, and 2.5 kg of deionized water was added. The mixture was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-5.

[0042] The wear index of HCF-5 is 2.8 wt% / h and the BET specific surface area is 218 m 2 / g, pore volume is 0.41cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0043] Example 6: Under stirring conditions, 2.9 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.4 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 1 from Example 1, and 2.5 kg of deionized water was added. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-6.

[0044] The wear index of HCF-6 is 2.9 wt% / h and the BET specific surface area is 221 m 2 / g, pore volume is 0.40 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0045] Example 7: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.7 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of aluminum sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.1 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), cerium chloride, the silicon-containing macroporous aluminum slurry 1 described in Example 1, and 2.5 kg of deionized water was added. The mixture was further slurried for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-7.

[0046] The wear index of HCF-7 is 1.6 wt% / h and the BET specific surface area is 202 m 2 / g, and the pore volume is 0.39 cm 3After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0047] Example 8: 0.6 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m 2 / g, pore volume 0.97 cm 3 / g) was added to 2 kg of water, and 0.032 kg (SiO2 dry weight) of water glass was added under stirring. The mixture was stirred at 80°C for 1 hour, filtered, washed, and then added to 1.8 kg of water to obtain silicon-containing macroporous aluminum stone slurry 8.

[0048] Under stirring conditions, 2 kg (dry weight) of kaolin, 1.8 kg (dry weight) of halloysite, 2.3 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.5 kg (based on dry weight of Al2O3) of aluminum sol, and 0.2 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 1.8 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of CeO2), siliceous macroporous boehmite slurry 8, and 2.5 kg of deionized water was added. The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst HCF-8.

[0049] The wear index of HCF-8 is 1.9 wt% / h, the BET surface area is 196 m2 / g, and the pore volume is 0.39 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0050] Comparative Example 1: 3.2 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.1 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. A mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.1 kg (based on dry weight of CeO2), slurry 1 of the silicon-containing macroporous alumina from Example 1, and 2.5 kg of deionized water was then added. The mixture was beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst REF-1.

[0051] The wear index of REF-1 is 1.6 wt% / h and the BET surface area is 218 m 2 / g, and the pore volume is 0.39 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0052] Comparative Example 2: 4.1 kg (dry weight) of kaolin, 1.5 kg (dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (dry weight of CeO2) of cerium chloride, 0.7 kg (dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. A mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (dry weight of CeO2) of cerium chloride, the silicon-containing macroporous boehmite slurry 1 from Example 1, and 2.5 kg of deionized water was then added. The mixture was beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst REF-2.

[0053] The wear index of REF-2 is 0.8 wt% / h and the BET surface area is 209 m 2 / g, and the pore volume is 0.34 cm 3After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0054] Comparative Example 3: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 2 kg (dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (dry weight of CeO2) of cerium chloride, 0.7 kg (dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 7 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (dry weight of CeO2) of cerium chloride, and 2.5 kg of deionized water was added. The slurry was further beaten for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst REF-3.

[0055] The wear index of REF-3 is 1.2 wt% / h and the BET surface area is 220 m 2 / g, and the pore volume is 0.32 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0056] Comparative Example 4: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.6 kg (dry weight) of halloysite, 1.5 kg (al2O3 dry weight) of pseudo-boehmite, 0.4 kg (CeO2 dry weight) of cerium chloride, and 0.7 kg (al2O3 dry weight) of aluminum sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (CeO2 dry weight) of cerium chloride, 0.5 kg (al2O3 dry weight) of macroporous boehmite (specific surface area 237 m2) were added. 2 / g, pore volume 0.97 cm 3A mixed slurry consisting of 100 g of 0.5% tantalum (0.1%) and 4 kg of deionized water was prepared. The slurry was then beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia (10 times the catalyst weight) and dried to obtain the high-rare-earth FCC catalyst REF-4.

[0057] The wear index of REF-4 is 1.5 wt% / h and the BET surface area is 213 m 2 / g, pore volume of 0.35 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0058] Comparative Example 5: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of CeO2) of cerium chloride, 0.7 kg (based on dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 0%), 0.4 kg (based on dry weight of CeO2) of cerium chloride, the silicon-containing macroporous alumina slurry 1 from Example 1, and 2.5 kg of deionized water was added. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst REF-5.

[0059] The wear index of REF-5 is 1.7 wt% / h and the BET surface area is 211 m 2 / g, and the pore volume is 0.38 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0060] Comparative Example 6: Under stirring conditions, 2.6 kg (dry weight) of kaolin, 1.5 kg (dry weight) of halloysite, 1.5 kg (based on dry weight of Al2O3) of pseudo-boehmite, 0.4 kg (based on dry weight of La2O3) of lanthanum chloride, 0.7 kg (based on dry weight of Al2O3) of alumina sol, and 0.1 kg of silica sol were added to 6 kg of deionized water and stirred at high speed for 2 hours. Then, a mixed slurry consisting of 2.3 kg (dry weight) of P-modified USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1 and a P2O5 content of 3.8%), 0.4 kg (based on dry weight of La2O3) of lanthanum chloride, the silicon-containing macroporous alumina slurry 1 from Example 1, and 2.5 kg of deionized water was added. Beating was continued for 30 minutes. After homogenization, the slurry was spray-formed and then calcined at 550°C for 2 hours. The calcined catalyst was washed with 0.1% dilute ammonia water in an amount 10 times the weight of the catalyst and dried to obtain a high rare earth FCC catalyst REF-6.

[0061] The wear index of REF-6 is 1.9 wt% / h and the BET surface area is 211 m 2 / g, and the pore volume is 0.38 cm 3 After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0062] Comparative Example 7: Under stirring conditions, 3.4 kg (dry weight) of kaolin, 1.9 kg (dry weight of Al2O3) of pseudo-boehmite, 0.07 kg (dry weight of La2O3) of lanthanum chloride, and 1 kg (dry weight of Al2O3) of alumina sol were added to 7 kg of deionized water and stirred at high speed for 2 hours. A mixed slurry consisting of 3.56 kg (dry weight) of USY molecular sieve (produced by Runhe Catalyst Co., Ltd., with a SiO2 / Al2O3 molar ratio of 5.1), 0.07 kg (dry weight of La2O3) of lanthanum chloride, and 4 kg of deionized water was then added. The mixture was beaten for 30 minutes. After homogenization, the slurry was spray-formed and calcined at 550°C for 2 hours. The calcined catalyst was washed with 10 times the catalyst weight of 0.1% dilute ammonia and dried to obtain the high-rare-earth FCC catalyst REF-7.

[0063] The wear index of REF-7 is 2.4 wt% / h and the BET surface area is 288 m 2 / g, and the pore volume is 0.39 cm 3After the sample was introduced with 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni and aged at 800°C with 100% steam for 10 hours, the cracking performance of the catalyst in the catalytic cracking process is shown in Table 1.

[0064] Table 1 shows the distribution of catalytic cracking products of the examples and comparative examples. The catalysts used in the comparative examples and examples, containing 6000 ppm Fe, 3000 ppm V, and 3000 ppm Ni, were aged at 800°C in 100% steam for 10 hours before being evaluated for catalytic cracking performance on an ACE unit. The reaction feed was hydrotreated residual oil, the reaction temperature was 530°C, the catalyst-to-oil ratio was 7.5, 9 grams of catalyst was added, the oil feed rate was 1.2 grams / minute, and the oil feed time was 60 seconds.

[0065] Coke index = coke yield / conversion rate*(100%-conversion rate) The sample of the embodiment has low content of molecular sieve and aluminum sol, and low raw material cost, but it contains high CeO2 content, silicon-containing macroporous aluminum stone, macroporous clay halloysite, and the Y-type molecular sieve is modified with P element. Under the conditions of high iron, vanadium and nickel, the catalyst has a high conversion rate and a high total yield of liquefied gas + gasoline + diesel.

[0066] Comparing HCF-1 and REF-1, when the CeO2 content in the catalyst was reduced from 8% to 2%, the conversion rate dropped significantly, the total yield of liquefied gas + gasoline + diesel decreased significantly, the coke index increased, and the diesel / oil slurry ratio decreased.

[0067] Comparing HCF-1 and REF-2, reducing the halloysite content in the catalyst from 15% to 0% significantly reduced the catalyst pore volume. This also resulted in a decrease in reaction conversion, a significant drop in the total yield of LPG, gasoline, and diesel, an increase in the coke index, and a decrease in the diesel / slurry oil ratio.

[0068] Comparing HCF-1 and REF-3, reducing the macroporous aluminum content in the catalyst from 5% to 0% significantly reduced the catalyst pore volume. This also resulted in a decrease in reaction conversion, a significant drop in the total yield of liquefied gas, gasoline, and diesel, an increase in the coke index, and a decrease in the diesel / slurry oil ratio.

[0069] Comparing HCF-1 and REF-4, the catalyst's pore volume decreased slightly by replacing silicon-containing macroporous alumina with silicon-free macroporous diaspore and reducing the silica sol content in the binder from 1% to 0%. This reduced the reaction conversion rate, the total yield of liquefied gas, gasoline, and diesel significantly decreased, and the coke index increased.

[0070] Comparing HCF-1 and REF-5, when the P2O5 content in the catalyst raw material Y-type molecular sieve was reduced from 3.8% to 0%, the catalyst conversion rate decreased, the total yield of liquefied gas + gasoline + diesel decreased, and the coke index increased.

[0071] Comparing HCF-1 and REF-6, when CeO2 in the catalyst was replaced by La2O3, the catalyst conversion rate decreased, the total yield of liquefied gas + gasoline + diesel decreased, and the coke index increased.

[0072] Comparing HCF-1 and REF-7, HCF-1 has a 23% molecular sieve content and an 8% rare earth content, while REF-7 has a 35.6% molecular sieve content and a 1.4% rare earth content. HCF-1 exhibits higher conversion, lower coke and slurry oil yields, and a higher total yield of liquefied gas, gasoline, and diesel. HCF-1 offers lower production costs and better reaction performance.

[0073] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0074] The above specific implementation methods are detailed descriptions of the present invention. It cannot be considered that the specific implementation methods of the present invention are limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, they can make several simple deductions and substitutions without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. A high rare earth content fluid catalytic cracking catalyst, characterized in that: The molecular sieve content is 18~23%, the rare earth content is 8~15%, and the ratio of rare earth content to molecular sieve content is 35%~52%.

2. The high rare earth content fluid catalytic cracking catalyst according to claim 1, characterized in that: The rare earth is CeO2.

3. The high rare earth content fluid catalytic cracking catalyst according to claim 1, characterized in that: The molecular sieve is P-modified USY molecular sieve.

4. The high rare earth content fluid catalytic cracking catalyst according to claim 1, characterized in that: It also includes aluminum sol, with an aluminum sol content of 4-8%; a silicon-modified matrix content of 4-8%, and a SiO2 content of 5-15% in the silicon-modified matrix.

5. A method for preparing a high rare earth content fluid catalytic cracking catalyst according to any one of claims 1 to 4, characterized in that: The steps include: Step 1: mixing clay, pseudo-boehmite, cerium chloride, aluminum sol, silica sol, and water to obtain a first mixed solution; Step 2: Add P-modified USY molecular sieve, cerium chloride, and silicon-containing macroporous aluminum stone slurry to the first mixed solution in step 1, beat, homogenize, shape, calcine, wash, and dry to obtain a high rare earth content fluidized catalytic cracking catalyst.

6. The method for preparing a high rare earth content fluid catalytic cracking catalyst according to claim 5, characterized in that: The clay is kaolin and / or halloysite.

7. The method for preparing a high rare earth content fluid catalytic cracking catalyst according to claim 5, characterized in that: The preparation method of silicon-containing macroporous boehmite slurry in step 2 comprises the following steps: adding water to macroporous boehmite and stirring, adding water glass and stirring at a certain temperature, filtering, washing, and then adding water to obtain silicon-containing macroporous boehmite slurry.

8. Use of a high rare earth content fluid catalytic cracking catalyst according to any one of claims 1 to 4 in a catalytic cracking process of high iron, vanadium and nickel feed.

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