A high-efficiency and environmentally friendly petroleum passivator and its preparation method and application

Abstract

This invention proposes a highly efficient and environmentally friendly petroleum passivating agent, its preparation method, and its application, belonging to the field of passivating agent technology. Bismuth nitrate is reacted with tetrakis(4-carboxyphenyl)porphyrin and benzoic acid to prepare carboxyphenylporphyrin bismuth-MOF material; antimony nitrate is reacted with tetrakis(4-pyridyl)porphyrin and benzoic acid to prepare pyridylporphyrin antimony-MOF material; lanthanum isopropoxide and cerium isopropoxide sol-gel are reacted to prepare lanthanum-cerium sol; calcium nitrate and magnesium chloride are mixed with organic acids, organic amines, and hydrogen peroxide to prepare calcium / magnesium organic compounds, which are then added to an acetonitrile / ethanol mixed solvent and stirred until homogeneous to obtain the highly efficient and environmentally friendly petroleum passivating agent. The highly efficient and environmentally friendly petroleum passivating agent prepared by this invention is green, safe, non-toxic, and highly efficient. It has a good capture and passivation effect on metal ions such as nickel and vanadium in the heavy oil catalytic cracking process, improving the activity of the catalyst and extending its service life, thus having broad application prospects.

Description

Technical Field

[0001] This invention relates to the field of passivating agent technology, specifically to a highly efficient and environmentally friendly petroleum passivating agent, its preparation method, and its application. Background Technology

[0002] In the heavy oil catalytic cracking process, heavy metals (such as Ni, Fe, V, Cu, etc.) in the feedstock continuously deposit on the catalyst surface, causing catalyst contamination. As the amount of deposited metals increases, it adversely affects the catalyst's activity and selectivity, leading to a decrease in gasoline and diesel yields and an increase in hydrogen and coke yields. Adding metal passivators to the catalytic cracking feedstock is the most economical and effective way to inhibit heavy metal contamination of the catalytic cracking catalyst. Early passivators used inorganic antimony salts, but now organic antimony compounds are more commonly used, both achieving significant passivation effects. Currently, the metal passivators used in China can be broadly divided into two categories: one is antimony compounds dissolved in organic solvents; the other is aqueous solutions of antimony compounds.

[0003] Oil-soluble antimony compounds were more commonly used in the early stages. For example, the antimony dihydroxydithiophosphate reported in Chinese invention patent CN1014776B and US invention patent US4694324A requires dissolution in an organic solvent before use and has a strong pungent odor. Water-soluble antimony passivating agents are currently the main type used, offering advantages such as convenient delivery, good stability, no pungent odor, and low toxicity. Chinese invention patent application CN1245198A reports a method for preparing an Sb-containing passivating agent, but its function is relatively singular. Chinese invention patent applications CN104028312A and CN104162455A report an Sb-based passivating agent containing rare earth elements, capable of bimetallic passivation, but the preparation process is complex. Currently, the preparation process of bimetallic passivating agents generally involves preparing two single-metal passivating agents separately and then compounding them with a solvent. This requires adjusting the metal content in the two passivating agents, making the process cumbersome, and the resulting passivating agents have high toxicity and poor stability. Summary of the Invention

[0004] The purpose of this invention is to propose a highly efficient and environmentally friendly petroleum passivating agent, its preparation method, and its application. It is green, safe, non-toxic, and highly efficient, and has a good capture and passivation effect on metal ions such as nickel and vanadium in the heavy oil catalytic cracking reaction process, thereby improving the activity of the catalyst and extending its service life, thus having broad application prospects.

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

[0006] This invention provides a method for preparing a highly efficient and environmentally friendly petroleum passivating agent. Bismuth nitrate is reacted with tetrakis(4-carboxyphenyl)porphyrin and benzoic acid to obtain carboxyphenylporphyrin bismuth-MOF material; antimony nitrate is reacted with tetrakis(4-pyridyl)porphyrin and benzoic acid to obtain pyridylporphyrin antimony-MOF material; lanthanum isopropoxide and cerium isopropoxide sol-gel are reacted to obtain lanthanum-cerium sol; calcium nitrate and magnesium chloride are mixed with organic acids, organic amines, and hydrogen peroxide to obtain calcium / magnesium organic compounds; these compounds are then mixed with carboxyphenylporphyrin bismuth-MOF material, pyridylporphyrin antimony-MOF material, and lanthanum-cerium sol in an acetonitrile / ethanol mixed solvent and stirred until homogeneous to obtain the highly efficient and environmentally friendly petroleum passivating agent.

[0007] As a further improvement to the present invention, the following steps are included:

[0008] S1. Bismuth nitrate was mixed evenly, and then mixed with tetrakis(4-carboxyphenyl)porphyrin and benzoic acid. The mixture was added to a mixture of N,N-dimethylformamide and acetic acid, stirred and dissolved at room temperature, subjected to hydrothermal reaction, centrifuged, washed, and dried to obtain carboxyphenylporphyrin bismuth-MOF material.

[0009] S2. Antimony nitrate was mixed evenly, and then mixed with tetrakis(4-pyridyl)porphyrin and benzoic acid and added to a mixture of N,N-dimethylformamide and acetic acid. The mixture was stirred and dissolved at room temperature, subjected to hydrothermal reaction, centrifuged, washed, and dried to obtain pyridylporphyrin antimony-MOF material.

[0010] S3. Dissolve lanthanum isopropoxide and cerium isopropoxide in ethanol, add ammonia to adjust the pH of the solution, add oleic acid, and hydrolyze to form lanthanum-cerium sol;

[0011] S4. Add calcium nitrate, magnesium chloride, organic acid, and organic amine to water, stir and mix evenly, add hydrogen peroxide dropwise, heat and stir to react, filter, wash, and dry to obtain calcium / magnesium organic compound;

[0012] S5. Carboxyphenyl porphyrin bismuth-MOF material, pyridyl porphyrin antimony-MOF material, lanthanum-cerium sol and calcium / magnesium organic matter are mixed and added to acetonitrile / ethanol mixed solvent, and stirred and mixed evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0013] As a further improvement of the present invention, the mass ratio of bismuth nitrate, tetrakis(4-carboxyphenyl)porphyrin, and benzoic acid in step S1 is 1-1.5:4-4.5:100-150, the hydrothermal reaction temperature is 135-145℃, and the time is 70-75h.

[0014] As a further improvement of the present invention, the mass ratio of antimony nitrate, tetrakis(4-pyridyl)porphyrin and benzoic acid in step S2 is 1.2-1.7:4.2-4.6:120-150, the hydrothermal reaction temperature is 135-145℃, and the time is 70-75h.

[0015] As a further improvement of the present invention, the mass ratio of lanthanum isopropoxide, cerium isopropoxide, and oleic acid in step S3 is 10-15:8-12:1-2, the pH of the solution is adjusted to 9-10, and the hydrolysis reaction time is 30-50 min. The addition of oleic acid effectively controls the hydrolysis reaction rate, resulting in more uniformly sized colloidal particles, thus balancing the surface tension of the particles and creating a more regular, grid-like microstructure. As an additive, the oxygen on the carboxyl group of oleic acid can coordinate with metal ions—acting as a chelating agent—opening some of the weaker bonds between the particles and weakening the bond-to-bond force to a certain extent, greatly slowing down gelation and forming a loosely structured gel.

[0016] As a further improvement of the present invention, the mass ratio of calcium nitrate, magnesium chloride, organic acid, organic amine, and hydrogen peroxide in step S4 is 2-3:1-3:5-7:3-4:6-9, the heating and stirring reaction temperature is 90-100℃, and the time is 1-3 hours; the organic acid is selected from at least one of malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, oxalic acid, or acetic acid; the organic amine is selected from at least one of diethanolamine, ethanolamine, triethanolamine, tert-butylamine, hexamethylenetetramine, or trimethylenediammonium.

[0017] As a further improvement of the present invention, the mass ratio of the carboxyphenylporphyrin bismuth-MOF material, pyridylporphyrin antimony-MOF material, lanthanum-cerium sol and calcium / magnesium organic matter in step S5 is 3-5:2-4:7-10:2-3, and the volume ratio of acetonitrile to ethanol in the acetonitrile / ethanol mixed solvent is 5-7:10-20.

[0018] This invention further protects a highly efficient and environmentally friendly petroleum passivating agent prepared by the above-described preparation method.

[0019] This invention further protects the application of the above-mentioned high-efficiency and environmentally friendly petroleum passivating agent in the passivation of metals in heavy oil catalytic cracking reaction.

[0020] The present invention has the following beneficial effects:

[0021] This invention utilizes different porphyrin ligands to prepare carboxyphenylporphyrin bismuth-MOF materials and pyridylporphyrin antimony-MOF materials, respectively. The nitrogen and carboxyl oxygen atoms in tetra(4-carboxyphenyl)porphyrin act as coordinating atoms, providing multiple coordination sites for bismuth ions and enabling the formation of stable coordinate bonds, thus constructing a structurally stable MOF material. The four pyridyl groups in tetra(4-pyridyl)porphyrin act as strong π-electron donors, while the four nitrogen atoms in the porphyrin macrocycle can participate in coordination through lone pair electrons (or act as hydrogen bond acceptors), forming a composite framework of "metal antimony-pyridyl" backbone and "porphyrin macrocycle support". Therefore, the carboxyphenylporphyrin bismuth-MOF materials and pyridylporphyrin antimony-MOF materials exhibit good thermal stability and good solubility in organic solvents, maintaining structural and performance stability under certain high-temperature conditions. Furthermore, they possess a large specific surface area, enabling rapid passivation of metals.

[0022] Among them, pyridyl porphyrin antimony-MOF material has a good passivation effect on nickel, while overcoming the disadvantages of traditional nickel-based passivators, such as strong irritating odor, high toxicity, and inconvenience for workers to operate, making it more low-toxic and environmentally friendly. Carboxyphenyl porphyrin bismuth-MOF material partially replaces antimony, with lower cost and greater environmental friendliness. In synergy with antimony MOF material, it greatly improves the passivation effect on nickel, and can react with nickel to form recalcitrant substances, effectively inhibiting the dehydrogenation activity of low-valent nickel on the catalyst, achieving the purpose of efficient nickel passivation. The porphyrin structure can also utilize its macrocyclic coordination ability to efficiently capture metal ions such as Ni and V, inhibiting their poisoning of the catalyst.

[0023] This invention utilizes isopropoxide salts of rare earth elements to prepare a sol via a sol-gel reaction. This sol exhibits good solubility in organic solvents and water, as well as good stability, overcoming the drawbacks of traditional rare earth salts such as easy decomposition, instability, and hygroscopicity. As passivating components, rare earth elements can react with vanadium under regeneration conditions to form stable compounds, preventing the formation of vanadic acid through reaction with water vapor. This inhibits the dealumination of the zeolite framework caused by vanadic acid attacking the zeolite, thus suppressing the decrease in zeolite crystallinity and specific surface area. The formation of stable compounds also prevents the enrichment of molten vanadium on the catalyst surface, thus preventing pore blockage and a decrease in specific surface area, thereby improving the accessibility of the catalyst.

[0024] The calcium and magnesium salts of this invention, being alkaline earth metals, form calcium hydroxide and magnesium hydroxide under alkaline conditions, providing close-proximity active sites for the catalyst. Simultaneously, alkaline earth metals and their compounds can react with heavy metals such as nickel and vanadium in heavy oil to form stable, high-melting-point compounds, such as alkaline earth metal vanadates. These compounds inhibit the deposition of heavy metals on the catalyst surface and their migration into the molecular sieve, reducing their damage to the catalyst's active sites. This mitigates the poisoning effect of heavy metals on the catalyst and maintains its activity and selectivity.

[0025] The high-efficiency and environmentally friendly petroleum passivating agent prepared by this invention is green, safe, non-toxic, and highly efficient. It has a good capture and passivation effect on metal ions such as nickel and vanadium in the heavy oil catalytic cracking reaction process, improves the activity of the catalyst, and extends its service life, thus having broad application prospects. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention. Example 1

[0027] This embodiment provides a method for preparing a highly efficient and environmentally friendly petroleum passivating agent, including the following steps:

[0028] S1. Mix 100 mg of bismuth nitrate evenly, and mix it with 400 mg of tetrakis(4-carboxyphenyl)porphyrin and 10 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1), stir to dissolve at room temperature, and hydrothermally react at 135 °C for 70 h. Centrifuge, wash, and dry to obtain carboxyphenylporphyrin bismuth-MOF material.

[0029] S2. Mix 120 mg of antimony nitrate evenly, and then mix it with 420 mg of tetrakis(4-pyridyl)porphyrin and 12 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1), stir to dissolve at room temperature, and then perform hydrothermal reaction at 135 °C for 70 h. After centrifugation, washing and drying, pyridylporphyrin antimony-MOF material is obtained.

[0030] S3. Dissolve 1g of lanthanum isopropoxide and 0.8g of cerium isopropoxide in 200mL of ethanol, add ammonia to adjust the pH of the solution to 9, add 0.1g of oleic acid, and hydrolyze for 30min to form lanthanum-cerium sol.

[0031] S4. Add 2g calcium nitrate, 1g magnesium chloride, 5g tartaric acid, and 3g diethanolamine to 250mL of water, stir and mix well, add 6g hydrogen peroxide dropwise, heat to 90℃, stir and react for 1h, filter, wash, and dry to obtain calcium / magnesium organic compound.

[0032] S5. Mix 0.3g of carboxyphenylporphyrin bismuth-MOF material, 0.2g of pyridylporphyrin antimony-MOF material, 0.7g of lanthanum-cerium sol and 0.2g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 5:10), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent. Example 2

[0033] This embodiment provides a method for preparing a highly efficient and environmentally friendly petroleum passivating agent, including the following steps:

[0034] S1. Mix 150 mg of bismuth nitrate evenly, and mix it with 450 mg of tetrakis(4-carboxyphenyl)porphyrin and 15 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1), stir to dissolve at room temperature, and hydrothermally react at 145 °C for 75 h. Centrifuge, wash, and dry to obtain carboxyphenylporphyrin bismuth-MOF material.

[0035] S2. Mix 170 mg of antimony nitrate evenly, and then mix it with 460 mg of tetrakis(4-pyridyl)porphyrin and 15 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1), stir to dissolve at room temperature, and then perform hydrothermal reaction at 145 °C for 75 h. After centrifugation, washing and drying, pyridylporphyrin antimony-MOF material is obtained.

[0036] S3. Dissolve 1.5g of lanthanum isopropoxide and 1.2g of cerium isopropoxide in 200mL of ethanol, add ammonia to adjust the pH of the solution to 10, add 0.2g of oleic acid, and hydrolyze for 50min to form lanthanum-cerium sol.

[0037] S4. Add 3g calcium nitrate, 3g magnesium chloride, 7g benzoic acid, and 4g triethanolamine to 250mL of water, stir and mix well, add 9g hydrogen peroxide dropwise, heat to 100℃, stir and react for 3h, filter, wash, and dry to obtain calcium / magnesium organic compound.

[0038] S5. Mix 0.5g of carboxyphenylporphyrin bismuth-MOF material, 0.4g of pyridylporphyrin antimony-MOF material, 1g of lanthanum-cerium sol and 0.3g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 7:20), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent. Example 3

[0039] This embodiment provides a method for preparing a highly efficient and environmentally friendly petroleum passivating agent, including the following steps:

[0040] S1. Mix 15 mg of bismuth nitrate evenly, and mix it with 42 mg of tetrakis(4-carboxyphenyl)porphyrin and 12 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1). Stir and dissolve at room temperature, and hydrothermally react at 140 °C for 73 h. Centrifuge, wash, and dry to obtain carboxyphenylporphyrin bismuth-MOF material.

[0041] S2. Mix 150 mg of antimony nitrate evenly, and mix it with 450 mg of tetrakis(4-pyridyl)porphyrin and 13 g of benzoic acid. Add the mixture to 100 mL of N,N-dimethylformamide and acetic acid mixture (volume ratio 10:1), stir to dissolve at room temperature, and hydrothermally react at 140 °C for 72 h. Centrifuge, wash, and dry to obtain pyridylporphyrin antimony-MOF material.

[0042] S3. Dissolve 1.2g of lanthanum isopropoxide and 1g of cerium isopropoxide in 200mL of ethanol, add ammonia to adjust the pH of the solution to 9.5, add 0.15g of oleic acid, and hydrolyze for 40min to form lanthanum-cerium sol.

[0043] S4. Add 2.5g calcium nitrate, 2g magnesium chloride, 6g citric acid, and 3.5g ethanolamine to 250mL of water, stir and mix well, add 7.5g hydrogen peroxide dropwise, heat to 95℃, stir and react for 2h, filter, wash, and dry to obtain calcium / magnesium organic compound;

[0044] S5. Mix 0.4g of carboxyphenylporphyrin bismuth-MOF material, 0.4g of pyridylporphyrin antimony-MOF material, 0.85g of lanthanum-cerium sol and 0.25g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0045] Comparative Example 1

[0046] The difference from Example 3 is that lanthanum isopropoxide was not added in step S3.

[0047] Specifically as follows:

[0048] S3. Dissolve 2.2g of cerium isopropoxide in 200mL of ethanol, add ammonia to adjust the pH of the solution to 9.5, add 0.15g of oleic acid, and hydrolyze for 40min to form cerium sol.

[0049] Comparative Example 2

[0050] The difference from Example 3 is that cerium isopropoxide was not added in step S3.

[0051] Specifically as follows:

[0052] S3. Dissolve 2.2g of lanthanum isopropoxide in 200mL of ethanol, add ammonia to adjust the pH of the solution to 9.5, add 0.15g of oleic acid, and hydrolyze for 40min to form lanthanum sol.

[0053] Comparative Example 3

[0054] The difference from Example 3 is that carboxyphenylporphyrin bismuth-MOF material was not added in step S5.

[0055] Specifically as follows:

[0056] S5. Mix 0.8g of pyridylporphyrin antimony-MOF material, 0.85g of lanthanum-cerium sol and 0.25g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0057] Comparative Example 4

[0058] The difference from Example 3 is that pyridyl porphyrin antimony-MOF material was not added in step S5.

[0059] Specifically as follows:

[0060] S5. Mix 0.8g of carboxyphenylporphyrin bismuth-MOF material, 0.85g of lanthanum-cerium sol and 0.25g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0061] Comparative Example 5

[0062] The difference from Example 3 is that carboxyphenyl porphyrin bismuth-MOF material and pyridyl porphyrin antimony-MOF material were not added in step S5.

[0063] Specifically as follows:

[0064] S5. Mix 0.85g of lanthanum-cerium sol and 0.25g of calcium / magnesium organic matter and add them to 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15). Stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0065] Comparative Example 6

[0066] The difference from Example 3 is that lanthanum-cerium sol was not added in step S5.

[0067] Specifically as follows:

[0068] S5. Mix 0.4g of carboxyphenylporphyrin bismuth-MOF material, 0.4g of pyridylporphyrin antimony-MOF material and 0.25g of calcium / magnesium organic matter into 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0069] Comparative Example 7

[0070] The difference from Example 3 is that no calcium / magnesium organic matter was added in step S5.

[0071] Specifically as follows:

[0072] S5. Mix 0.4g of carboxyphenylporphyrin bismuth-MOF material, 0.4g of pyridylporphyrin antimony-MOF material, and 0.85g of lanthanum-cerium sol in 50mL of acetonitrile / ethanol mixed solvent (the volume ratio of acetonitrile to ethanol is 6:15), stir and mix evenly to obtain a high-efficiency and environmentally friendly petroleum passivating agent.

[0073] Test Example 1 Performance Evaluation

[0074] Feedstock used in the experiment: fresh feedstock from a catalytic cracking unit of a refinery. The physical property data are shown in Table 1.

[0075] Table 1

[0076]

[0077] Before the feed oil enters the reactor, add the high-efficiency and environmentally friendly petroleum passivating agent prepared in Examples 1-3 or Comparative Examples 1-7 (no addition in the blank group) to make its final content 10 μg / g.

[0078] Experimental conditions: catalyst amount 50 mL; feedstock oil 100 mL; reaction temperature 510 ± 2℃; volume hourly space velocity 1.8-2 h⁻¹ -1 Since the initial boiling point of the feedstock oil for catalytic cracking is 323℃, the yield of liquid products at temperatures below 320℃ is used as the light oil yield to characterize the cracking activity.

[0079] The results are shown in Table 2.

[0080] Table 2

[0081]

[0082] As shown in the table above, after adding the high-efficiency and environmentally friendly petroleum passivating agent prepared in Examples 1-3 of this invention to the feedstock oil, the light oil yield increases, the coke yield decreases, the H2 in the gas decreases, and the H2 / CH4 ratio decreases, indicating a significant passivation effect.

[0083] The above description is only a preferred embodiment of the present invention and is 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 environmentally friendly petroleum passivating agent, characterized in that, Includes the following steps: S1. Bismuth nitrate was mixed evenly, and then mixed with tetrakis(4-carboxyphenyl)porphyrin and benzoic acid. The mixture was added to a mixture of N,N-dimethylformamide and acetic acid, stirred and dissolved at room temperature, subjected to hydrothermal reaction, centrifuged, washed, and dried to obtain carboxyphenylporphyrin bismuth-MOF material. S2. Antimony nitrate was mixed evenly, and then mixed with tetrakis(4-pyridyl)porphyrin and benzoic acid and added to a mixture of N,N-dimethylformamide and acetic acid. The mixture was stirred and dissolved at room temperature, subjected to hydrothermal reaction, centrifuged, washed, and dried to obtain pyridylporphyrin antimony-MOF material. S3. Dissolve lanthanum isopropoxide and cerium isopropoxide in ethanol, add ammonia to adjust the pH of the solution, add oleic acid, and hydrolyze to form lanthanum-cerium sol; S4. Add calcium nitrate, magnesium chloride, organic acid, and organic amine to water, stir and mix evenly, add hydrogen peroxide dropwise, heat and stir to react, filter, wash, and dry to obtain calcium / magnesium organic compound; S5. Carboxyphenyl porphyrin bismuth-MOF material, pyridyl porphyrin antimony-MOF material, lanthanum-cerium sol and calcium / magnesium organic matter are mixed and added to acetonitrile / ethanol mixed solvent, and stirred and mixed evenly to obtain an environmentally friendly petroleum passivating agent.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of bismuth nitrate, tetrakis(4-carboxyphenyl)porphyrin, and benzoic acid is 1-1.5:4-4.5:100-150, and the hydrothermal reaction temperature is 135-145℃, with a time of 70-75h.

3. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of antimony nitrate, tetrakis(4-pyridyl)porphyrin, and benzoic acid is 1.2-1.7:4.2-4.6:120-150, and the hydrothermal reaction temperature is 135-145℃, with a time of 70-75h.

4. The preparation method according to claim 1, characterized in that, In step S3, the mass ratio of lanthanum isopropoxide, cerium isopropoxide, and oleic acid is 10-15:8-12:1-2, the pH of the solution is adjusted to 9-10, and the hydrolysis reaction takes 30-50 minutes.

5. The preparation method according to claim 1, characterized in that, In step S4, the mass ratio of calcium nitrate, magnesium chloride, organic acid, organic amine, and hydrogen peroxide is 2-3:1-3:5-7:3-4:6-9. The heating and stirring reaction is carried out at a temperature of 90-100℃ for 1-3 hours. The organic acid is selected from at least one of malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, oxalic acid, or acetic acid. The organic amine is selected from at least one of diethanolamine, ethanolamine, triethanolamine, tert-butylamine, hexamethylenetetramine, or trimethylenediammonium.

6. The preparation method according to claim 1, characterized in that In step S5, the mass ratio of the carboxyphenylporphyrin bismuth-MOF material, pyridylporphyrin antimony-MOF material, lanthanum-cerium sol, and calcium / magnesium organic matter is 3-5:2-4:7-10:2-3, and the volume ratio of acetonitrile to ethanol in the acetonitrile / ethanol mixed solvent is 5-7:10-20.

7. An environmentally friendly petroleum passivating agent prepared by the preparation method according to any one of claims 1-6.

8. The application of the environmentally friendly petroleum passivating agent as described in claim 7 in the passivation of metals in heavy oil catalytic cracking reaction.

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