Green and efficient petroleum passivator and preparation method thereof

Abstract

The invention provides a green and efficient petroleum passivator and a preparation method thereof, and belongs to the technical field of passivators. Carboxymethyl chitosan, phytic acid and beta-cyclodextrin are coupled to prepare a chitosan-phytic acid-cyclodextrin compound, bismuth, lanthanum, cerium and aluminum are compounded, and the green and efficient petroleum passivator is prepared through tannic acid polymerization modification. The prepared green and efficient petroleum passivator is green, safe, non-toxic and efficient, has good capturing and passivating capacity on ions such as iron, nickel and vanadium, greatly improves the activity of a catalyst, prolongs the service life of the catalyst, and has wide application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of passivators, and in particular to a green and efficient petroleum passivator and a preparation method thereof. Background Art

[0002] With the development of oil fields in western my country and the continuous increase in imported crude oil (such as Middle Eastern oil), the processing proportion of crude oil with high metal content is increasing. The metals in crude oil mainly include nickel, vanadium, sodium, etc. Among them, nickel can catalyze the dehydrogenation reaction of hydrocarbons, increase the carbon accumulation on the catalyst surface, and cause carbon deposition pollution; vanadium can not only promote the formation of coke, but also destroy the lattice structure of the catalyst molecular sieve, deactivate the catalyst, cause the selectivity of the target product to deteriorate, the conversion rate to decrease, and the dry gas and coke yield to increase; iron can not only neutralize the acid center of the fluid catalytic cracking (FCC) catalyst, making the catalyst permanently deactivated, but also form a low melting point eutectic with vanadium, reduce the thermal stability of the catalyst, and also cause CO combustion aid poisoning, so that the amount of combustion aid used increases exponentially.

[0003] One of the most effective and widely used methods to solve this problem is to add metal passivators to deactivate harmful metal elements. Passivators are mainly divided into three types: nickel passivators, vanadium passivators and bifunctional types. Their effective components include bismuth type, non-bismuth type, water-soluble type and oil-soluble type. Currently, bismuth type passivators are more widely used. Summary of the invention

[0004] The purpose of the present invention is to provide a green and efficient petroleum passivator and a preparation method, which is green, safe, non-toxic and efficient, has good capture and passivation capabilities for iron, nickel, vanadium and other ions, greatly improves the activity of the catalyst, and prolongs its service life, thus having broad application prospects.

[0005] The technical solution of the present invention is achieved in this way: The invention provides a method for preparing a green and efficient petroleum passivator. Carboxymethyl chitosan, phytic acid and beta-cyclodextrin are coupled to obtain a chitosan-phytic acid-cyclodextrin complex, and bismuth, lanthanum, cerium and aluminum are compounded and modified by tannic acid polymerization to obtain a green and efficient petroleum passivator.

[0006] As a further improvement of the present invention, the following steps are included: S1. Carboxymethyl chitosan, phytic acid, β-cyclodextrin and potassium dihydrogen phosphate were added to water, heated to reflux with stirring for reaction, and then hydrothermally reacted. The product was added to an alkali solution with stirring, ethanol was added for precipitation, filtered, washed, and dried to obtain a chitosan-phytic acid-cyclodextrin complex; S2. Add bismuth trioxide, antimony trioxide, lanthanum chloride, cerium chloride, aluminum chloride, magnesium chloride, organic acid and organic amine to water, stir and mix, add chitosan-phytic acid-cyclodextrin complex, add hydrogen peroxide dropwise, heat and stir to react, add ethanol to precipitate, filter, wash and dry to obtain a primary passivating agent; S3. Add the primary passivator into Tris-HCl solution, add tannic acid, heat and stir to react, add ethanol to precipitate, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0007] As a further improvement of the present invention, the mass ratio of carboxymethyl chitosan, phytic acid, β-cyclodextrin and potassium dihydrogen phosphate in step S1 is 10:3-5:4-6:1-2.

[0008] As a further improvement of the present invention, the time of the heating reflux stirring reaction in step S1 is 1-2 hours, the temperature of the hydrothermal reaction is 140-150° C., the time is 2-4 hours, and the alkali solution is 0.5-1 mol / L NaOH or KOH solution.

[0009] As a further improvement of the present invention, the mass ratio of bismuth trioxide, antimony trioxide, lanthanum chloride, cerium chloride, aluminum chloride, magnesium chloride, organic acid, organic amine, chitosan-phytic acid-cyclodextrin complex, and hydrogen peroxide in step S2 is 3-5:0.5-1:2-3:1-2:2-4:1-2:7-10:2-5:10-15:2-3.

[0010] As a further improvement of the present invention, the temperature of the heating and stirring reaction in step S2 is 90-100° C. and the time is 2-3 h.

[0011] As a further improvement of the present invention, the organic acid in step S2 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.

[0012] As a further improvement of the present invention, the pH value of the Tris-HCl solution in step S3 is 8.5-9.5; the mass ratio of the primary passivating agent to tannic acid is 10:2-3, the temperature of the heating and stirring reaction is 40-50° C., and the time is 2-4 hours.

[0013] As a further improvement of the present invention, the following steps are included: S1. 10 parts by weight of carboxymethyl chitosan, 3-5 parts by weight of phytic acid, 4-6 parts by weight of β-cyclodextrin and 1-2 parts by weight of potassium dihydrogen phosphate are added to water, heated to reflux with stirring for 1-2 hours, and then hydrothermally reacted at 140-150° C. for 2-4 hours, the product is added to 0.5-1 mol / L NaOH or KOH solution with stirring, ethanol is added for precipitation, filtered, washed, and dried to obtain a chitosan-phytic acid-cyclodextrin complex; S2. 3-5 parts by weight of bismuth trioxide, 0.5-1 parts by weight of antimony trioxide, 2-3 parts by weight of lanthanum chloride, 1-2 parts by weight of cerium chloride, 2-4 parts by weight of aluminum chloride, 1-2 parts by weight of magnesium chloride, 7-10 parts by weight of organic acid, 2-5 parts by weight of organic amine are added to water, stirred and mixed evenly, 10-15 parts by weight of chitosan-phytic acid-cyclodextrin complex is added, 2-3 parts by weight of hydrogen peroxide is added dropwise, heated to 90-100° C., stirred for reaction for 2-3 hours, ethanol is added for precipitation, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10 parts by weight of primary passivator to a Tris-HCl solution with a pH value of 8.5-9.5, add 2-3 parts by weight of tannic acid, heat to 40-50°C, stir and react for 2-4h, add ethanol to precipitate, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0014] The present invention further protects a green and efficient petroleum passivator prepared by the above preparation method.

[0015] The present invention has the following beneficial effects: The cavity of beta-cyclodextrin has a good fixation effect of heavy metals, and the chitosan-phytic acid-cyclodextrin complex formed by coupling phytic acid with carboxymethyl chitosan has a large amount of hydroxyl, amino, phosphoric acid structure and cyclodextrin cavity, and heavy metal nickel, vanadium, and iron are formed with complex bonds, so as to fix heavy metals, avoid their destructive effect on catalysts, and at the same time, rare earth metals and bismuth and aluminum can be fixed, and the rare earth metals can form cerium colloids and lanthanum colloids that are miscible with water as vanadium suppressing active agents and catalysts. The active agent, rich in olefin oxide, is deposited on the catalyst surface, and can be directly added to the reaction system, preferentially generating stable compounds with vanadium, avoiding the destruction of vanadium to the molecular sieve structure, so as to achieve the purpose of suppressing vanadium, slowing down the deactivation of catalysts, reducing the unit consumption of catalysts, and having a synergistic effect. The present invention partially replaces traditional antimony with bismuth trioxide, has low cost, is more environmentally friendly, and greatly improves the passivation effect on nickel in coordination with antimony, can react with nickel to generate difficult-to-reduce substances, effectively suppresses the dehydrogenation activity of low-priced nickel on the catalyst, and achieves the purpose of efficient passivation of nickel. The aluminum of the present invention forms aluminum hydroxide under alkaline conditions, providing close active centers for the catalyst. Further, the surface of the primary passivator of the present invention is modified by tannic acid polymerization, which greatly improves the ability to capture iron, nickel, vanadium and other ions, thereby effectively passivating them, greatly improving the activity of the catalyst and extending its service life.

[0016] The green and efficient petroleum passivator prepared by the invention is green, safe, non-toxic and efficient, has good capture and passivation capabilities for iron, nickel, vanadium and other ions, greatly improves the activity of the catalyst, prolongs its service life, and thus has broad application prospects. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Example 1 This embodiment provides a method for preparing a green and efficient petroleum passivator, comprising the following steps: S1. 10g carboxymethyl chitosan, 3g phytic acid, 4g β-cyclodextrin and 1g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1h, then hydrothermally reacted at 140℃ for 2h, the product was added to 0.5mol / L NaOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. 3g of bismuth trioxide, 0.5g of antimony trioxide, 2g of lanthanum chloride, 1g of cerium chloride, 2g of aluminum chloride, 1g of magnesium chloride, 7g of malic acid, and 2g of diethanolamine were added to 200mL of water, stirred and mixed for 15min, 10g of chitosan-phytic acid-cyclodextrin complex was added, 2g of hydrogen peroxide was added dropwise, heated to 90°C, stirred and reacted for 2h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 8.5, add 2g of tannic acid, heat to 40℃, stir and react for 2h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0019] Example 2 This embodiment provides a method for preparing a green and efficient petroleum passivator, comprising the following steps: S1. 10g carboxymethyl chitosan, 5g phytic acid, 6g β-cyclodextrin and 2g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 2h, then hydrothermally reacted at 150℃ for 4h, the product was added to 1mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 5g of bismuth trioxide, 1g of antimony trioxide, 3g of lanthanum chloride, 2g of cerium chloride, 4g of aluminum chloride, 2g of magnesium chloride, 10g of oxalic acid, and 5g of ethanolamine to 200mL of water, stir and mix for 15min, add 15g of chitosan-phytic acid-cyclodextrin complex, drop 3g of hydrogen peroxide, heat to 100°C, stir and react for 3h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash, and dry to obtain a primary passivator; S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9.5, add 3g of tannic acid, heat to 50℃, stir and react for 3h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0020] Example 3 This embodiment provides a method for preparing a green and efficient petroleum passivator, comprising the following steps: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. 4 g of bismuth trioxide, 0.7 g of antimony trioxide, 2.5 g of lanthanum chloride, 1.5 g of cerium chloride, 3 g of aluminum chloride, 1.5 g of magnesium chloride, 8 g of citric acid, and 4 g of triethanolamine were added to 200 mL of water, stirred and mixed for 15 min, 12 g of chitosan-phytic acid-cyclodextrin complex was added, 2.5 g of hydrogen peroxide was added dropwise, heated to 95 ° C, stirred and reacted for 2.5 h, ethanol was added until the ethanol content of the system was 70 wt%, precipitated for 1 h, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0021] Comparative Example 1 Compared with Example 3, the difference is that lanthanum chloride is not added in step S2.

[0022] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4g of bismuth trioxide, 0.7g of antimony trioxide, 4g of cerium chloride, 3g of aluminum chloride, 1.5g of magnesium chloride, 8g of citric acid and 4g of triethanolamine into 200mL of water, stir and mix for 15min, add 12g of chitosan-phytic acid-cyclodextrin complex, add 2.5g of hydrogen peroxide dropwise, heat to 95°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0023] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0024] Comparative Example 2 Compared with Example 3, the difference is that cerium chloride is not added in step S2.

[0025] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4g of bismuth trioxide, 0.7g of antimony trioxide, 4g of lanthanum chloride, 3g of aluminum chloride, 1.5g of magnesium chloride, 8g of citric acid and 4g of triethanolamine into 200mL of water, stir and mix for 15min, add 12g of chitosan-phytic acid-cyclodextrin complex, add 2.5g of hydrogen peroxide dropwise, heat to 95°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0026] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0027] Comparative Example 3 Compared with Example 3, the difference is that lanthanum chloride and cerium chloride are not added in step S2.

[0028] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4g of bismuth trioxide, 0.7g of antimony trioxide, 3g of aluminum chloride, 1.5g of magnesium chloride, 8g of citric acid and 4g of triethanolamine into 200mL of water, stir and mix for 15min, add 12g of chitosan-phytic acid-cyclodextrin complex, add 2.5g of hydrogen peroxide dropwise, heat to 95°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0029] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0030] Comparative Example 4 Compared with Example 3, the difference is that bismuth trioxide is not added in step S2.

[0031] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4.7g antimony trioxide, 2.5g lanthanum chloride, 1.5g cerium chloride, 3g aluminum chloride, 1.5g magnesium chloride, 8g citric acid and 4g triethanolamine into 200mL water, stir and mix for 15min, add 12g chitosan-phytic acid-cyclodextrin complex, add 2.5g hydrogen peroxide dropwise, heat to 95℃, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0032] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0033] The difference between Comparative Example 5 and Example 3 is that antimony trioxide is not added in step S2.

[0034] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4.7g bismuth trioxide, 2.5g lanthanum chloride, 1.5g cerium chloride, 3g aluminum chloride, 1.5g magnesium chloride, 8g citric acid and 4g triethanolamine into 200mL water, stir and mix for 15min, add 12g chitosan-phytic acid-cyclodextrin complex, add 2.5g hydrogen peroxide dropwise, heat to 95℃, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0035] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0036] Comparative Example 6 Compared with Example 3, the difference is that bismuth trioxide and antimony trioxide are not added in step S2.

[0037] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 2.5g of lanthanum chloride, 1.5g of cerium chloride, 3g of aluminum chloride, 1.5g of magnesium chloride, 8g of citric acid and 4g of triethanolamine into 200mL of water, stir and mix for 15min, add 12g of chitosan-phytic acid-cyclodextrin complex, add 2.5g of hydrogen peroxide dropwise, heat to 95°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator.

[0038] S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0039] Comparative Example 7 Compared with Example 3, the difference is that β-cyclodextrin is not added in step S1.

[0040] The details are as follows: S1. Add 10g carboxymethyl chitosan, 4g phytic acid and 1.5g potassium dihydrogen phosphate into 500mL water, heat to reflux and stir to react for 1.5h, then hydrothermally react at 145℃ for 3h, add the product into 0.75mol / L KOH solution and stir for 1h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain chitosan-phytic acid complex.

[0041] S2. 4 g of bismuth trioxide, 0.7 g of antimony trioxide, 2.5 g of lanthanum chloride, 1.5 g of cerium chloride, 3 g of aluminum chloride, 1.5 g of magnesium chloride, 8 g of citric acid, and 4 g of triethanolamine were added to 200 mL of water, stirred and mixed for 15 min, 12 g of chitosan-phytic acid complex was added, 2.5 g of hydrogen peroxide was added dropwise, heated to 95 ° C, stirred and reacted for 2.5 h, ethanol was added until the ethanol content of the system was 70 wt%, precipitated for 1 h, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0042] Comparative Example 8 Compared with Example 3, the difference is that carboxymethyl chitosan is not added in step S1.

[0043] The details are as follows: S1. Add 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate into 500mL water, heat to reflux and stir to react for 1.5h, then hydrothermally react at 145℃ for 3h, add the product into 0.75mol / L KOH solution and stir for 1h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain phytic acid-cyclodextrin complex.

[0044] S2. 4 g of bismuth trioxide, 0.7 g of antimony trioxide, 2.5 g of lanthanum chloride, 1.5 g of cerium chloride, 3 g of aluminum chloride, 1.5 g of magnesium chloride, 8 g of citric acid, and 4 g of triethanolamine were added to 200 mL of water, stirred and mixed for 15 min, 12 g of phytic acid-cyclodextrin complex was added, 2.5 g of hydrogen peroxide was added dropwise, heated to 95 ° C, stirred and reacted for 2.5 h, ethanol was added until the ethanol content of the system was 70 wt%, precipitated for 1 h, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10g of primary passivator into 200mL of Tris-HCl solution with a pH value of 9, add 2.5g of tannic acid, heat to 45°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a green and efficient petroleum passivator.

[0045] Comparative Example 9 Compared with Example 3, the difference is that step S3 is not performed.

[0046] The details are as follows: S1. 10g carboxymethyl chitosan, 4g phytic acid, 5g β-cyclodextrin and 1.5g potassium dihydrogen phosphate were added to 500mL water, heated to reflux and stirred for 1.5h, then hydrothermally reacted at 145℃ for 3h, the product was added to 0.75mol / L KOH solution and stirred for 1h, ethanol was added until the ethanol content of the system was 70wt%, precipitated for 1h, filtered, washed and dried to obtain chitosan-phytic acid-cyclodextrin complex; S2. Add 4g of bismuth trioxide, 0.7g of antimony trioxide, 2.5g of lanthanum chloride, 1.5g of cerium chloride, 3g of aluminum chloride, 1.5g of magnesium chloride, 8g of citric acid and 4g of triethanolamine into 200mL of water, stir and mix for 15min, add 12g of chitosan-phytic acid-cyclodextrin complex, drop 2.5g of hydrogen peroxide, heat to 95°C, stir and react for 2.5h, add ethanol until the ethanol content of the system is 70wt%, precipitate for 1h, filter, wash and dry to obtain a primary passivator, which is a green and efficient petroleum passivator.

[0047] Test Example 1 The green and efficient petroleum passivators prepared in Examples 1-3 of the present invention and Comparative Examples 1-9 were used to test the crude oil (properties shown in Table 1). The addition amount of the passivators was 5 μg / g. The results are shown in Tables 2 and 3.

[0048] Raw oil properties: Table 1

[0049] Table 2

[0050] Table 3

[0051] It can be seen from the above table that the green and efficient petroleum passivators prepared in Examples 1-3 of the present invention can significantly improve the micro-reaction activity of the catalyst, increase the yield of gasoline and diesel, reduce the coke yield, and improve the overall conversion rate.

[0052] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a green and efficient petroleum passivator, characterized in that: The chitosan-phytic acid-cyclodextrin complex is prepared by coupling carboxymethyl chitosan, phytic acid and β-cyclodextrin, and the complex is compounded with bismuth, lanthanum, cerium and aluminum, and then modified by tannic acid polymerization to obtain a green and efficient petroleum passivator.

2. The preparation method according to claim 1, characterized in that: The following steps are involved: S1. Carboxymethyl chitosan, phytic acid, β-cyclodextrin and potassium dihydrogen phosphate were added to water, heated to reflux with stirring for reaction, and then hydrothermally reacted. The product was added to an alkali solution with stirring, ethanol was added for precipitation, filtered, washed, and dried to obtain a chitosan-phytic acid-cyclodextrin complex; S2. Add bismuth trioxide, antimony trioxide, lanthanum chloride, cerium chloride, aluminum chloride, magnesium chloride, organic acid and organic amine to water, stir and mix, add chitosan-phytic acid-cyclodextrin complex, add hydrogen peroxide dropwise, heat and stir to react, add ethanol to precipitate, filter, wash and dry to obtain a primary passivating agent; S3. Add the primary passivator into Tris-HCl solution, add tannic acid, heat and stir to react, add ethanol to precipitate, filter, wash and dry to obtain a green and efficient petroleum passivator.

3. The preparation method according to claim 2, characterized in that: The mass ratio of carboxymethyl chitosan, phytic acid, β-cyclodextrin and potassium dihydrogen phosphate in step S1 is 10:3-5:4-6:1-2.

4. The preparation method according to claim 2, characterized in that: The time of the heating reflux stirring reaction in step S1 is 1-2 hours, the temperature of the hydrothermal reaction is 140-150° C., the time is 2-4 hours, and the alkali solution is 0.5-1 mol / L NaOH or KOH solution.

5. The preparation method according to claim 2, characterized in that: The mass ratio of bismuth trioxide, antimony trioxide, lanthanum chloride, cerium chloride, aluminum chloride, magnesium chloride, organic acid, organic amine, chitosan-phytic acid-cyclodextrin complex, and hydrogen peroxide in step S2 is 3-5:0.5-1:2-3:1-2:2-4:1-2:7-10:2-5:10-15:2-3.

6. The preparation method according to claim 2, characterized in that: The temperature of the heating and stirring reaction in step S2 is 90-100° C. and the time is 2-3 hours.

7. The preparation method according to claim 2, characterized in that: In step S2, 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.

8. The preparation method according to claim 2, characterized in that: The pH value of the Tris-HCl solution in step S3 is 8.5-9.5; the mass ratio of the primary passivating agent to tannic acid is 10:2-3, the temperature of the heating and stirring reaction is 40-50° C., and the time is 2-4 hours.

9. The preparation method according to claim 2, characterized in that: The following steps are involved: S1. 10 parts by weight of carboxymethyl chitosan, 3-5 parts by weight of phytic acid, 4-6 parts by weight of β-cyclodextrin and 1-2 parts by weight of potassium dihydrogen phosphate are added to water, heated to reflux with stirring for 1-2 hours, and then hydrothermally reacted at 140-150° C. for 2-4 hours, the product is added to 0.5-1 mol / L NaOH or KOH solution with stirring, ethanol is added for precipitation, filtered, washed, and dried to obtain a chitosan-phytic acid-cyclodextrin complex; S2. 3-5 parts by weight of bismuth trioxide, 0.5-1 parts by weight of antimony trioxide, 2-3 parts by weight of lanthanum chloride, 1-2 parts by weight of cerium chloride, 2-4 parts by weight of aluminum chloride, 1-2 parts by weight of magnesium chloride, 7-10 parts by weight of organic acid, 2-5 parts by weight of organic amine are added to water, stirred and mixed evenly, 10-15 parts by weight of chitosan-phytic acid-cyclodextrin complex is added, 2-3 parts by weight of hydrogen peroxide is added dropwise, heated to 90-100° C., stirred for reaction for 2-3 hours, ethanol is added for precipitation, filtered, washed, and dried to obtain a primary passivating agent; S3. Add 10 parts by weight of primary passivator to a Tris-HCl solution with a pH value of 8.5-9.5, add 2-3 parts by weight of tannic acid, heat to 40-50°C, stir and react for 2-4h, add ethanol to precipitate, filter, wash and dry to obtain a green and efficient petroleum passivator.

10. A green and efficient petroleum passivator prepared by the preparation method according to any one of claims 1 to 9.

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