A catalyst cracking anti-iron-nickel vanadium catcher, its preparation method and application

Abstract

The application relates to the field of heavy oil catalytic cracking, and discloses a catalytic cracking iron-nickel-resistant vanadium capturing agent, a preparation method and application thereof, the preparation method comprises the following steps: S1, mixing water, pseudo-boehmite and acid to obtain a hydrotalcite slurry; S2, mixing water, a metal oxide and acid to obtain a metal oxide slurry; S3, mixing water and a rare earth nitrate to obtain a rare earth solution; S4, mixing yttrium aluminum garnet, the hydrotalcite slurry, the metal oxide slurry and the rare earth solution, performing spray drying, and performing calcination to obtain the catalytic cracking iron-nickel-resistant vanadium capturing agent. Through the technical scheme, the problem of poor iron-nickel-resistant vanadium capturing effect of the catalytic cracking iron-nickel-resistant vanadium capturing agent in the related art is solved, the technical scheme has excellent iron-nickel-resistant vanadium capturing effect, the yield and quality of gasoline, diesel and other products are improved, and the technical scheme is irreplaceable.

Description

Technical Field

[0001] This invention relates to the field of heavy oil catalytic cracking technology, specifically to a catalytic cracking agent for resisting iron-nickel vanadium capture, its preparation method, and its application. Background Technology

[0002] In heavy oil catalytic cracking, as feedstocks become increasingly heavy and of lower quality, they often contain high levels of sulfur and heavy metals such as nickel, vanadium, and iron. Although these heavy metals have different mechanisms of action, their continuous deposition on the catalyst increases catalyst loss, reduces the yield of light and liquid products, and impacts the company's economic efficiency. The continuously increasing sulfur content in catalytic cracking feedstocks leads to higher sulfur oxide content in the regenerated flue gas, severe corrosion of downstream equipment, difficulties in treating high-salinity wastewater, and severe blue smoke or tailing phenomena.

[0003] Therefore, there is a need for a catalytic cracking agent that effectively resists vanadium capture by iron and nickel. Summary of the Invention

[0004] This invention proposes a catalytic cracking agent for resisting vanadium capture by iron and nickel, its preparation method, and its application, which solves the problem of insufficient anti-vanadium capture effect of vanadium capture agents for iron and nickel in related technologies.

[0005] The technical solution of the present invention is as follows:

[0006] This invention proposes a method for preparing an anti-ferro-nickel vanadium-capturing agent for catalytic cracking, comprising the following steps:

[0007] S1. Mix water, boehmite, and acid to obtain boehmite slurry;

[0008] S2. Mix water, metal oxide, and acid to obtain a metal oxide slurry;

[0009] S3. Mix water and rare earth nitrates to obtain a rare earth solution;

[0010] S4. Yttrium aluminum garnet, the boehmite slurry, the metal oxide slurry and the rare earth solution are mixed, spray-dried and calcined to obtain the catalytic cracking anti-iron-nickel vanadium capture agent.

[0011] As a further technical solution, in step S1, the mass ratio of water to acid is 20~25:1; for example, it can be 20:1, 21:1, 22:1, 23:1, 24:1, or 25:1.

[0012] The mass ratio of the pseudoboehmite to the acid is 3~5:1;

[0013] The pH value of the hydrated alumina slurry is 3.5~4.0.

[0014] As a further technical solution, in step S2, the mass ratio of water to acid is 10~13:1, for example, it can be 10:1, 11:1, 12:1, or 13:1;

[0015] The mass ratio of the metal oxide to the acid is 2~3:1;

[0016] The pH of the metal oxide slurry is 11~11.5;

[0017] The metal oxide includes magnesium oxide and component A;

[0018] Component A includes one of gallium oxide, zirconium oxide, molybdenum oxide, calcium oxide, barium oxide, and zinc oxide;

[0019] The mass ratio of magnesium oxide to component A is 4~6:1.

[0020] As a further technical solution, in step S3, the mass ratio of water to rare earth nitrate is 1.2~1.4:1, for example, it can be 1.2:1, 1.25:1, 1.3:1, 1.35:1, or 1.4:1;

[0021] The rare earth nitrates include one of cerium nitrate and lanthanum nitrate;

[0022] The acids in steps S1 and S2 each independently include one of nitric acid, formic acid, acetic acid, oxalic acid, and citric acid.

[0023] As a further technical solution, the mass ratio of yttrium aluminum garnet to rare earth nitrate is 0.5~1:1, for example, it can be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1;

[0024] The mass ratio of the pseudoboehmite, metal oxide, and rare earth nitrate is 1.7~1.8:2~3:1.

[0025] As a further technical solution, the preparation method of yttrium aluminum garnet includes the following steps: mixing alumina and yttrium oxide, then solid-phase sintering and pulverizing to obtain yttrium aluminum garnet.

[0026] In this invention, during the high-temperature solid-state sintering process, alumina and yttrium oxide particles come into contact with each other. The aluminum ions in the alumina and the yttrium ions in the yttrium oxide gradually rearrange and recombine through lattice diffusion and interfacial diffusion, growing according to the crystal structure of yttrium aluminum garnet, and finally forming a dense sintered body, thus forming yttrium aluminum garnet material.

[0027] As a further technical solution, the solid-state sintering temperature is 1500~1600℃, for example, it can be 1500℃, 1520℃, 1540℃, 1560℃, 1580℃, or 1600℃.

[0028] As a further technical solution, the solid-state sintering time is 3~4h, for example, it can be 3h, 3.2h, 3.4h, 3.6h, 3.8h, or 4h.

[0029] As a further technical solution, the mass ratio of alumina to yttrium oxide is 2:1~4.

[0030] In this invention, the yttrium aluminum garnet material prepared by using an alumina to yttrium oxide mass ratio of 2:1~4 during high-temperature solid-state sintering further improves the anti-ferro-nickel vanadium-capturing effect of the catalytic cracking anti-ferro-nickel vanadium-capturing agent.

[0031] As a further technical solution, the yttrium aluminum garnet is an aluminum phosphate composite yttrium aluminum garnet.

[0032] As a further technical solution, the preparation method of the aluminum phosphate composite yttrium aluminum garnet includes the following steps: mixing sodium aluminate, phosphoric acid and water, adding yttrium aluminum garnet, reacting at 80°C, and drying to obtain aluminum phosphate composite yttrium aluminum garnet; wherein, the mass ratio of sodium aluminate to phosphoric acid is 2~4:1, and the mass-volume ratio of sodium aluminate to water is 1g:100~200mL.

[0033] In this invention, aluminum phosphate composite yttrium aluminum garnet is used as the raw material for the anti-iron-nickel vanadium capture agent. The aluminum phosphate composite yttrium aluminum garnet can efficiently capture and stabilize iron and vanadium ions, avoiding the reduction of gasoline, diesel and liquefied gas yields and quality by iron, vanadium and other metal impurities. This allows the catalytic cracking catalyst to significantly improve reaction efficiency and product selectivity, thereby increasing the production of gasoline, diesel and other products.

[0034] This invention proposes a catalytic cracking agent to resist vanadium capture by iron and nickel, which is prepared by the method described above.

[0035] The present invention also proposes the application of a catalytic cracking anti-iron-nickel vanadium-capturing agent prepared by the above preparation method in heavy oil catalytic cracking.

[0036] The working principle and beneficial effects of this invention are as follows:

[0037] In this invention, the catalytic cracking anti-ferrous nickel vanadium ore agent is prepared by mixing yttrium aluminum garnet, boehmite slurry, metal oxide slurry, and rare earth solution, followed by spray drying and calcination. The resulting catalytic cracking anti-ferrous nickel vanadium ore agent exhibits excellent anti-ferrous nickel vanadium ore capture effects, extending catalyst lifespan and improving the yield and quality of gasoline, diesel, and other products. Existing technologies, when preparing catalytic cracking anti-ferrous nickel vanadium ore agents, have limited and singular raw material selection, failing to fully utilize the synergistic effects between various raw materials. For example, they may only use a single type of active ingredient or common additives, failing to comprehensively address the negative impacts of iron, nickel, and vanadium on the catalytic cracking process. The product of this invention is composed of multiple highly efficient active components, possessing strong and large-capacity anti-ferrous nickel vanadium ore capture capabilities. It can selectively capture and passivate heavy metals in feedstock oil, thereby reducing the destructive effects of heavy metals on the catalyst within the system, improving product distribution and product selectivity. In terms of anti-ferrous nickel vanadium ore capture effects, it achieves more effective capture and inhibition of the negative impacts of iron, nickel, and vanadium on catalytic cracking catalysts, and improves the efficiency and stability of the catalytic cracking reaction, making it irreplaceable. Detailed Implementation

[0038] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0041] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0042] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of zirconium oxide, and 568 kg of formic acid were stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) was obtained, a metal oxide slurry was obtained.

[0043] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0044] S4, the alumina slurry and metal oxide slurry are placed in a transfer vessel and heated with steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 95℃, and the time is recorded. The holding time is 4 hours. Cooling begins using circulating water. When the temperature of the material in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (to combine alumina and oxygen) are added to the vessel. Yttrium was mixed at a mass ratio of 3:1, sintered in the solid phase at 1500℃ for 4 hours, pulverized to obtain yttrium aluminum garnet with a particle size of 15 μm; the mass ratio of yttrium aluminum garnet to cerium nitrate was 0.5:1. After stirring for 30 minutes, it was spray-dried (outlet temperature 140℃, inlet temperature 550℃, spray particle size: D50 90 μm, spray pressure: 3.5 MPa), and calcined at 550℃ for 2 hours to obtain a catalytic cracking agent against iron-nickel vanadium capture.

[0045] Example 2

[0046] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0047] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0048] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of calcium oxide, and 568 kg of formic acid are stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) is obtained, a metal oxide slurry is obtained.

[0049] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0050] S4. Alumina slurry and metal oxide slurry are placed in a transfer vessel and heated with steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 98℃, and the time is recorded. The holding time is 3 hours. Cooling then begins using circulating water. When the temperature of the materials in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (to combine alumina and oxygen) are added to the vessel. Yttrium was mixed at a mass ratio of 3:1, sintered in the solid phase at 1600℃ for 3 hours, pulverized to obtain yttrium aluminum garnet with a particle size of 15 μm (mass ratio of yttrium aluminum garnet to cerium nitrate was 0.8:1), stirred for 30 minutes, spray dried (outlet temperature 145℃, inlet temperature 550℃, spray particle size: D50 80 μm, spray pressure: 3.5 MPa), and calcined at 550℃ for 2 hours to obtain a catalytic cracking agent against iron-nickel vanadium capture.

[0051] Example 3

[0052] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0053] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0054] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of zirconium oxide, and 568 kg of formic acid were stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) was obtained, a metal oxide slurry was obtained.

[0055] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0056] S4, hydrated alumina slurry and metal oxide slurry are placed in a transfer vessel and heated by steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 95℃, and the time is recorded. The holding time is 2 hours. Cooling begins using circulating water. When the temperature of the material in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (alumina and yttrium oxide are mixed at a mass ratio of 3:1, sintered in solid phase at 1550℃ for 4 hours, pulverized to obtain yttrium aluminum garnet with a particle size of 15 μm, and the mass ratio of yttrium aluminum garnet to cerium nitrate is 1:1) are added to the vessel. Stirring is performed for 30 minutes, followed by spray drying (outlet temperature 140℃, inlet temperature 550℃, spray particle size: D50 85 μm, spray pressure: 3.5 MPa). The mixture is then calcined at 550℃ for 2 hours to obtain a catalytic cracking agent that resists iron-nickel vanadium capture.

[0057] Example 4

[0058] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0059] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0060] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of zirconium oxide, and 568 kg of formic acid were stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) was obtained, a metal oxide slurry was obtained.

[0061] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0062] S4, the alumina slurry and metal oxide slurry are placed in a transfer vessel and heated with steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 95℃, and the time is recorded. The holding time is 4 hours. Cooling begins using circulating water. When the temperature of the material in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (to combine alumina and oxygen) are added to the vessel. Yttrium was mixed at a mass ratio of 2:5, sintered in the solid phase at 1500℃ for 4 hours, pulverized to obtain yttrium aluminum garnet with a particle size of 15 μm; the mass ratio of yttrium aluminum garnet to cerium nitrate was 0.5:1. After stirring for 30 minutes, it was spray-dried (outlet temperature 140℃, inlet temperature 550℃, spray particle size: D50 90 μm, spray pressure: 3.5 MPa) and calcined at 550℃ for 2 hours to obtain a catalytic cracking agent against iron-nickel vanadium capture.

[0063] Example 5

[0064] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0065] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0066] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of zirconium oxide, and 568 kg of formic acid were stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) was obtained, a metal oxide slurry was obtained.

[0067] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0068] S4, the alumina slurry and metal oxide slurry are placed in a transfer vessel and heated with steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 95℃, and the time is recorded. The holding time is 4 hours. Cooling begins using circulating water. When the temperature of the material in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (to combine alumina and oxygen) are added to the vessel. Yttrium was mixed at a mass ratio of 2:1, sintered in the solid phase at 1500℃ for 4 hours, pulverized, and yttrium aluminum garnet with a particle size of 15 μm was obtained; the mass ratio of yttrium aluminum garnet to cerium nitrate was 0.5:1. After stirring for 30 minutes, spray drying was carried out (outlet temperature 140℃, inlet temperature 550℃, spray particle size: D50 of 90 μm, spray pressure: 3.5 MPa), and calcined at 550℃ for 2 hours to obtain a catalytic cracking agent against iron-nickel vanadium capture.

[0069] Example 6

[0070] A method for preparing an anti-ferro-nickel vanadium scavenging agent for catalytic cracking includes the following steps:

[0071] S1. 5500 kg of primary water, 1140 kg of pseudoboehmite, and 241 kg of formic acid were stirred and mixed for 30 min to obtain a boehmite slurry.

[0072] S2, 7000 kg of primary water, 1300 kg of magnesium oxide, 260 kg of zirconium oxide, and 568 kg of formic acid were stirred and mixed for 30 min. After the slurry D50 (<6.5 μm) was obtained, a metal oxide slurry was obtained.

[0073] S3. Mix 850 kg of primary water and 640 kg of cerium nitrate to obtain a rare earth solution;

[0074] S4, hydrated alumina slurry and metal oxide slurry are placed in a transfer vessel and heated by steam. The steam pressure should not exceed 0.2 MPa, and the stirring current should be kept below 150 A. When the temperature reaches 95℃, the steam valve is closed to maintain the temperature at 95℃, and the time is recorded. The holding time is 4 hours. Cooling begins using circulating water. When the temperature of the material in the vessel drops to 60℃, rare earth solution and yttrium aluminum garnet (alumina and yttrium oxide are mixed at a mass ratio of 2:4, sintered in solid state at 1500℃ for 4 hours, and pulverized to obtain yttrium aluminum garnet with a particle size of 15 μm; the mass ratio of yttrium aluminum garnet to cerium nitrate is 0.5:1) are added to the vessel. The mixture is stirred for 30 minutes and then spray-dried (outlet temperature 140℃, inlet temperature 550℃, spray particle size: D50 90 μm, spray pressure: 3.5 MPa). The mixture is then calcined at 550℃ for 2 hours to obtain a catalytic cracking agent that resists iron-nickel vanadium capture.

[0075] Example 7

[0076] The only difference between this embodiment and Embodiment 5 is that yttrium aluminum garnet is replaced with aluminum phosphate composite yttrium aluminum garnet;

[0077] Preparation method of aluminum phosphate composite yttrium aluminum garnet: Sodium aluminate and phosphoric acid are dissolved in deionized water, mechanically stirred, yttrium aluminum garnet is added, reacted at 80℃, and dried to obtain aluminum phosphate composite yttrium aluminum garnet; wherein, the mass ratio of sodium aluminate to phosphoric acid is 3:1, and the mass-volume ratio of sodium aluminate to deionized water is 1g:150mL.

[0078] Comparative Example 1

[0079] The only difference between this comparative example and Example 1 is that yttrium aluminum garnet is not added.

[0080] Experimental Example

[0081] 1. Evaluation of the effect of iron vanadium capture resistance

[0082] The effect of different addition ratios of the anti-iron-nickel vanadium-capturing agent in catalytic cracking was investigated using the FFB-II fixed fluidized bed catalyst evaluation device, mainly evaluating the anti-iron vanadium-capturing effect.

[0083] The evaluation test was conducted on the FFB-II fixed fluidized bed catalytic cracking test unit, which is a small-scale, fully automated fixed fluidized bed catalytic cracking unit designed and manufactured by Beijing Huier Sanji Green Chemical Technology Co., Ltd.

[0084] First, the fresh FCC catalyst was saturated with vanadium oxalate and ferric naphthenate to achieve a target vanadium content of 8000 ppm and a target iron content of 10000 ppm. The impregnated sample was dried at 150°C and then calcined at 600°C to obtain a catalyst sample contaminated with vanadium and iron (contaminated sample). The fresh FCC catalyst was aged at 800°C for 17 h and named a blank sample. The catalytic cracking anti-ferrous nickel vanadium capture aid prepared in Example 1 was mixed with the contaminated agent at mass percentages of 0%, 8%, 15%, and 20%, respectively. Finally, the mixture was aged at 800°C for 17 h to obtain the samples to be evaluated, named contaminated sample, contaminated sample + 8% aid, contaminated sample + 15% aid, and contaminated sample + 20% aid, respectively.

[0085] Evaluation scheme and conditions

[0086] Evaluation scheme: The performance of feedstock oil with different amounts of additives was compared and evaluated under the same reaction conditions.

[0087] Reaction conditions: reaction temperature 510~512℃; catalyst amount 200g; space velocity 18h -1 The agent-to-oil ratio is 5.

[0088] Catalyst: Main agent + catalytic cracking anti-iron-nickel vanadium capture additives with different contents.

[0089] Table 1 FCC Feedstock

[0090]

[0091] (1) Gas product analysis: The purpose of gas product analysis is to obtain detailed gas product composition and to separate the gas into dry gas, liquefied gas and C5. + Three parts, C5 + The fractions were grouped together as gasoline fractions. The gaseous products were analyzed using capillary column gas chromatography and a data processing system.

[0092] (2) Analysis of liquid products: The catalytic cracking product is a wide boiling range fraction containing three fractions: gasoline, light diesel oil and unconverted oil (heavy oil). The liquid products are analyzed by using a simulated distillation method instead of actual boiling point distillation on gas chromatography.

[0093] (3) Coke analysis: The coke on the catalyst was analyzed by an online carbon monoxide and carbon dioxide analyzer and then converted into C content for determination.

[0094] (4) The product distribution results obtained from the fixed fluidized bed evaluation experiment are shown in Tables 2-3.

[0095] Table 2 Product distribution results

[0096]

[0097] Analysis of the results in Table 2 above regarding the effect of vanadium-iron vanadium capture shows that the performance of fresh FCC catalysts significantly decreased after vanadium-iron contamination, essentially confirming that vanadium and iron severely damaged the active components of the catalyst. Adding an anti-vanadium-iron vanadium capture agent for catalytic cracking largely restored the catalyst's performance; however, considering cost, the addition amount of this agent should be between 8 wt% and 15 wt%. Adding this anti-vanadium-iron vanadium capture agent plays a significant role in restoring the activity of the main catalyst.

[0098] The catalytic cracking anti-iron-nickel vanadium capture additives prepared in Examples 1-7 and Comparative Example 1 were mixed with the above-mentioned contaminant samples at an addition amount of 8 wt%. Finally, the samples were aged at 800°C for 17 h to obtain the samples to be evaluated, which were named as contaminant sample, contaminant sample + 8% Example 1, contaminant sample + 8% Example 2, contaminant sample + 8% Example 3, contaminant sample + 8% Example 4, contaminant sample + 8% Example 5, contaminant sample + 8% Example 6, contaminant sample + 8% Example 7, and contaminant sample + 8% Comparative Example 1.

[0099] Table 3 Product distribution results

[0100]

[0101] As shown in Table 3, compared with Comparative Example 1, the product distribution of gasoline, diesel, and liquefied petroleum gas was higher after adding the catalytic cracking anti-ferrous nickel vanadium-capturing agents prepared in Examples 1-7 as catalytic additives. This indicates that the addition of yttrium aluminum garnet to the raw materials of the catalytic cracking anti-ferrous nickel vanadium-capturing agents improved the anti-ferrous vanadium-capturing performance. Compared with Examples 1-4, the product distribution of gasoline, diesel, and liquefied petroleum gas was higher after using the catalytic cracking anti-ferrous nickel vanadium-capturing agents prepared in Examples 5-6 as catalytic additives. This indicates that the mass ratio of alumina to yttrium oxide in the raw materials of the catalytic cracking anti-ferrous nickel vanadium-capturing agents was 2:1-4, which further improved the anti-ferrous vanadium-capturing performance. In Example 7, the raw materials of the anti-catalytic cracking anti-ferrous nickel vanadium-capturing agent were replaced with aluminum phosphate composite yttrium aluminum garnet, and the anti-ferrous vanadium-capturing effect was optimal.

[0102] 2. Evaluation of anti-iron-nickel effect

[0103] In this experiment, the catalytic cracking anti-iron-nickel vanadium-capturing agents prepared in Examples 1-3 and Comparative Example 1 were mixed with iron-nickel contaminants at an addition amount of 8 wt% on a fixed fluidized bed catalytic cracking experimental apparatus. Finally, the samples were aged at 800℃ for 17 h to obtain the samples to be evaluated. The samples were named as contaminant sample + 8% Example 1, contaminant sample + 8% Example 2, contaminant sample + 8% Example 3, and contaminant sample + 8% Comparative Example 1, respectively. In the iron-nickel contaminant, the target amount of iron was 10000 ppm and the target amount of nickel was 8000 ppm. The results are shown in Table 4.

[0104] Table 4 Product distribution results

[0105]

[0106] As shown in Table 4, compared with Comparative Example 1, the catalytic cracking anti-iron-nickel vanadium-capturing agents prepared in Examples 1-3 exhibit higher product distributions in gasoline, diesel, and liquefied petroleum gas after catalysis, indicating that the catalytic cracking anti-iron-nickel vanadium-capturing agents prepared in the embodiments of the present invention also have excellent anti-iron-nickel effects.

[0107] 3. Evaluation of fixed fluidized beds with balancing agents and additives

[0108] In this experiment, a balance agent (obtained from a refinery, which was contaminated with contaminated metals; the XRF test results of the contaminated metal content on the balance agent are shown in Table 5) was mixed with the catalytic cracking anti-iron-nickel vanadium-capturing agent prepared in Examples 1-3 and Comparative Example 1 (the mass of the anti-iron-nickel vanadium-capturing agent was 8% of the mass of the balance agent) in a fixed fluidized bed catalytic cracking experimental apparatus. The mixture was then aged in hot air at 800℃ for 17 hours to evaluate the reaction. The mixtures were named Balance Agent + 8% Example 1, Balance Agent + 8% Example 2, Balance Agent + 8% Example 3, and Balance Agent + 8% Comparative Example 1, respectively. To meet the needs of actual industrial production, the performance of different mixed catalysts was evaluated under FCC reaction conditions, with the catalyst-to-oil ratio set at 6.5 and the oil-gas reaction time at 3 seconds. The results are shown in Tables 6-7.

[0109] Table 5. XRF test results of contaminant metal content in the balancer.

[0110]

[0111] Table 6 Evaluation of microreaction activity

[0112]

[0113] Table 7 Product Distribution

[0114]

[0115] As shown in Table 5, the micro-reaction activity of the catalytic cracking anti-iron-nickel vanadium-capturing agent is improved after being mixed with the balance agent of a certain refinery. Compared with Comparative Example 1, the catalytic cracking anti-iron-nickel vanadium-capturing agent prepared in Example 1 has higher micro-reaction activity.

[0116] As shown in Table 6, compared with Comparative Example 1, the catalytic cracking anti-iron-nickel vanadium-capturing agents prepared in Examples 1-3 showed higher product distributions of gasoline, diesel, and liquefied petroleum gas during the catalytic evaluation process, indicating that the catalytic cracking anti-iron-nickel vanadium-capturing agents prepared in Examples 1-3 of this invention have a better anti-iron-nickel vanadium-capturing effect.

[0117] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an anti-ferro-nickel vanadium-capturing agent for catalytic cracking, characterized in that, Includes the following steps: S1. Mix water, boehmite, and acid to obtain boehmite slurry; S2. Water, metal oxide, and acid are mixed to obtain a metal oxide slurry; the metal oxide includes magnesium oxide and component A; component A includes one of gallium oxide, zirconium oxide, molybdenum oxide, calcium oxide, barium oxide, and zinc oxide; the mass ratio of magnesium oxide to component A is 4~6:1; S3. Mix water and rare earth nitrates to obtain a rare earth solution; the rare earth nitrates include one of cerium nitrate and lanthanum nitrate. S4. Yttrium aluminum garnet, the boehmite slurry, the metal oxide slurry and the rare earth solution are mixed, spray-dried and calcined to obtain the catalytic cracking anti-ferro-nickel vanadium capture agent; The preparation method of the yttrium aluminum garnet includes the following steps: mixing alumina and yttrium oxide, then solid-state sintering and pulverizing to obtain yttrium aluminum garnet; The solid-state sintering temperature is 1500~1600℃, and the time is 3~4h; The mass ratio of alumina to yttrium oxide is 2:1~4.

2. The preparation method of the catalytic cracking anti-ferro-nickel vanadium-capturing agent according to claim 1, characterized in that, In step S1, the mass ratio of water to acid is 20-25:1; the mass ratio of boehmite to acid is 3-5:

1. The pH value of the hydrated alumina slurry is 3.5~4.

0.

3. The preparation method of the catalytic cracking anti-ferronickel vanadium scavenging agent according to claim 1, characterized in that, In step S2, the mass ratio of water to acid is 10~13:1; the mass ratio of metal oxide to acid is 2~3:

1. The pH value of the metal oxide slurry is 11~11.

5.

4. The preparation method of the catalytic cracking anti-ferronickel vanadium scavenging agent according to claim 1, characterized in that, In step S3, the mass ratio of water to rare earth nitrate is 1.2~1.4:1; The acids in steps S1 and S2 each independently include one of nitric acid, formic acid, acetic acid, oxalic acid, and citric acid.

5. The preparation method of the catalytic cracking anti-ferronickel vanadium scavenging agent according to claim 1, characterized in that, The mass ratio of yttrium aluminum garnet to rare earth nitrate is 0.5~1:1; The mass ratio of the pseudoboehmite, metal oxide, and rare earth nitrate is 1.7~1.8:2~3:

1.

6. The preparation method of the catalytic cracking anti-ferronickel vanadium-capturing agent according to claim 1, characterized in that, The yttrium aluminum garnet is an aluminum phosphate composite yttrium aluminum garnet.

7. A catalytic cracking agent for resisting vanadium ore capture by iron and nickel, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 6.

8. The application of a catalytic cracking anti-iron-nickel vanadium-capturing agent prepared by the preparation method according to any one of claims 1 to 6, or the catalytic cracking anti-iron-nickel vanadium-capturing agent according to claim 7, in heavy oil catalytic cracking.

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