Antimony multi-metal passivator and preparation method thereof

Abstract

The invention discloses an antimony-based multi-metal passivator and a preparation method thereof, and relates to the field of petrochemical engineering, and the antimony-based multi-metal passivator comprises the following components by mass: 10-15% of an organic antimony compound; 20%-30% of an inorganic compound; 20%-25% of a dispersant; 25%-35% of a polar solvent; 0.1%-0.2% of hydrogen peroxide; 3%-8% of a solubilizer; 1%-2% of a pH regulator; and 0.1%-0.2% of an antirust agent. The catalyst is prepared by reasonably compounding multiple components, has the characteristics of simple process, short reaction time, low cost, high stability and no toxicity, and can significantly improve the selectivity and prolong the service life of the catalyst, reduce the production cost and reduce the pollution to the environment.

Description

Technical Field

[0001] The present invention relates to the field of petrochemical industry, and in particular to an antimony-based multi-metal passivator for treating crude oil containing multiple harmful metals (such as nickel, vanadium, etc.) and a preparation method thereof. Background Art

[0002] In the oil refining process, metal impurities (such as nickel, vanadium, etc.) in crude oil have a significant impact on the performance and service life of the catalyst. Nickel can catalyze the dehydrogenation reaction of hydrocarbons, increase carbon accumulation on the catalyst surface, and lead to carbon deposition pollution; vanadium can not only promote the formation of coke, but also destroy the lattice structure of the catalyst molecular sieve, causing the catalyst to deactivate. At present, the passivators commonly used in the market are mainly antimony-based passivators, but the existing antimony-based passivators have problems such as turbid appearance, poor stability, high production cost, and low production safety. Summary of the invention

[0003] The purpose of the present invention is to overcome the shortcomings of the above-mentioned technology and provide an antimony-based multi-metal passivator and a preparation method thereof which has simple process, short reaction time, low cost, high stability and non-toxicity. The present invention can significantly improve the selectivity and service life of the catalyst, reduce production costs, and reduce pollution to the environment.

[0004] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention is:

[0005] An antimony-based multi-metal passivator, characterized in that it is composed of the following components in percentage by mass:

[0006] Organic antimony compounds 10%-15%;

[0007] Inorganic antimony compounds 20%-30%;

[0008] Dispersant 20%-25%;

[0009] Polar solvent 25%-35%;

[0010] Hydrogen peroxide 0.1%-0.2%;

[0011] Solubilizer 3%-8%;

[0012] PH regulator 1%-2%;

[0013] Rust inhibitor 0.1%-0.2%.

[0014] A further improvement of the present invention is that the organic antimony compound is one or a combination of antimony thiolate, trisoxalyl antimony, triphenyl antimony, and diisopropyl dithiophosphate antimony.

[0015] A further improvement of the present invention is that the inorganic antimony compound is one of antimony trioxide and antimony pentoxide.

[0016] A further improvement of the present invention is that the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is (3.5-4.5):(4-5). The dispersant is used to improve the stability and transparency of the passivator and prevent precipitation or stratification during the preparation and use process. The citric acid in the formula has a strong chelating ability and can form a complex with the metal surface to form a protective film to prevent the metal from contacting with external oxides and causing rust. At the same time, ethanolamine itself has corrosion inhibition performance, and the product after the reaction of the two can also play an anti-rust role to a certain extent, and has a good effect in metal protection.

[0017] A further improvement of the present invention is that the polar solvent is one of petroleum acid, fatty acid, toluene, ethylbenzene and propylbenzene.

[0018] A further improvement of the present invention is that the solubilizer is one of dimethylformamide, dimethylacetamide, diethylformamide, and benzamide. The above materials have good solubility and stability and are used to increase the solubility between materials and improve the dispersibility and stability of the passivator.

[0019] A further improvement of the present invention is that the pH regulator is one of sodium hydroxide, sodium bicarbonate, hydrochloric acid and hydrofluoric acid, which is used to adjust the pH value of the passivator so that it remains stable within a specific pH range and ensures that the pH value is controlled within the range of 2-6.

[0020] A further improvement of the present invention is that the rust remover is one of phosphate ester, triethanolamine borate, and potassium salt of fatty alcohol ether phosphate, which is used to prevent the metal parts in the crude oil catalyst system from rusting and having a negative impact on the catalyst performance. Combined with the inhibitory effect of the passivator itself on metal ions, it can protect the catalyst in many aspects.

[0021] A method for preparing an antimony-based multi-metal passivator, characterized in that it comprises the following specific steps:

[0022] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 30-40 min, filter to remove impurities, and obtain a mixed solution A;

[0023] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 30-40 min, filtering to remove impurities, and obtaining a mixed solution B;

[0024] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 1-2 hours to obtain a solution with a pH value of 2-6. This solution is the desired antimony-based multi-metal passivator.

[0025] A further improvement of the present invention is that the dispersant in step S1 is prepared by mixing citric acid and ethanolamine in water, the molar ratio of citric acid to ethanolamine is (3.5-4.5):(4-5), and the pH value of the prepared dispersant is 4-6.

[0026] The beneficial effects of the present invention are:

[0027] The present invention adopts a dual-system formula of an organic antimony compound and an inorganic antimony compound. The organic antimony compound system has good solubility and stability, and the inorganic antimony compound formula has higher stability and dispersibility. By combining the characteristics of the two, the two are efficiently combined by using a solubilizer and a pH regulator, so that the prepared multi-metal passivator has good solubility, stability and dispersibility. The antimony active component in the material formula is relatively high, and it has a good inhibitory effect on metal ions. In combination with a rust inhibitor, it can protect the catalyst in many aspects. DETAILED DESCRIPTION

[0028] The technical solution of the present invention is further described in detail below through specific embodiments:

[0029] Example 1

[0030] The invention discloses an antimony-based multi-metal passivator, which is composed of the following components in percentage by mass: 10% of an organic antimony compound; 30% of an inorganic antimony compound; 20% of a dispersant; 35% of a polar solvent; 0.2% of hydrogen peroxide; 3.7% of a solubilizer; 1% of a pH regulator; and 0.1% of a rust preventive.

[0031] In this embodiment, the organic antimony compound is antimony thiol.

[0032] In this embodiment, the inorganic antimony compound is antimony trioxide.

[0033] In this embodiment, the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is 3.5:5.

[0034] In this embodiment, the polar solvent is petroleum acid.

[0035] In this embodiment, the solubilizing agent is dimethylformamide.

[0036] In this embodiment, the pH adjuster is sodium hydroxide.

[0037] In this embodiment, the rust remover is phosphate ester.

[0038] The preparation method of the antimony-based multi-metal passivator comprises the following specific steps:

[0039] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 30 min, filter to remove impurities, and obtain a mixed solution A;

[0040] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 30 min, filtering to remove impurities, and obtaining a mixed solution B;

[0041] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 2 hours to obtain an antimony-based multi-metal passivator.

[0042] Example 2

[0043] An antimony-based multi-metal passivator is composed of the following components in percentage by mass: 15% of an organic antimony compound; 20% of an inorganic antimony compound; 25% of a dispersant; 29.8% of a polar solvent; 0.1% of hydrogen peroxide; 8% of a solubilizer; 2% of a pH regulator; and 0.1% of a rust inhibitor.

[0044] In this embodiment, the organic antimony compound is a mixture of trisoxalyl antimony and triphenyl antimony.

[0045] In this embodiment, the inorganic antimony compound is antimony pentoxide.

[0046] In this embodiment, the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is 4.5:4.

[0047] In this embodiment, the polar solvent is fatty acid.

[0048] In this embodiment, the solubilizing agent is dimethylacetamide.

[0049] In this embodiment, the pH adjuster is sodium bicarbonate.

[0050] In this embodiment, the rust remover is triethanolamine borate.

[0051] The preparation method of the antimony-based multi-metal passivator comprises the following specific steps:

[0052] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 40 min, filter to remove impurities, and obtain a mixed solution A;

[0053] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 30 min, filtering to remove impurities, and obtaining a mixed solution B;

[0054] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 1 hour to obtain an antimony-based multi-metal passivator.

[0055] Example 3

[0056] An antimony-based multi-metal passivator is composed of the following components in percentage by mass: 14% of an organic antimony compound; 28% of an inorganic antimony compound; 24% of a dispersant; 29.2% of a polar solvent; 0.15% of hydrogen peroxide; 3% of a solubilizer; 1.5% of a pH regulator; and 0.15% of a rust inhibitor.

[0057] In this embodiment, the organic antimony compound is diisopropyl antimony dithiophosphate.

[0058] In this embodiment, the inorganic antimony compound is antimony trioxide.

[0059] In this embodiment, the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is 4:4.5.

[0060] In this embodiment, the polar solvent is toluene.

[0061] In this embodiment, the solubilizing agent is diethyl formate.

[0062] In this embodiment, the pH adjuster is hydrochloric acid.

[0063] In this embodiment, the rust remover is potassium salt of fatty alcohol ether phosphate.

[0064] The preparation method of the antimony-based multi-metal passivator comprises the following specific steps:

[0065] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 35 min, filter to remove impurities, and obtain a mixed solution A;

[0066] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 35 min, filtering to remove impurities, and obtaining a mixed solution B;

[0067] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 1.5 hours to obtain an antimony-based multi-metal passivator.

[0068] Example 4

[0069] An antimony-based multi-metal passivator is composed of the following components in percentage by mass: 15% of an organic antimony compound; 25% of an inorganic antimony compound; 25% of a dispersant; 25% of a polar solvent; 0.12% of hydrogen peroxide; 8% of a solubilizer; 1.7% of a pH regulator; and 0.18% of a rust inhibitor.

[0070] In this embodiment, the organic antimony compound is antimony thiol.

[0071] In this embodiment, the inorganic antimony compound is antimony trioxide.

[0072] In this embodiment, the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is 3.5:5.

[0073] In this embodiment, the polar solvent is propylbenzene.

[0074] In this embodiment, the solubilizing agent is benzamide.

[0075] In this embodiment, the pH adjuster is hydrofluoric acid.

[0076] In this embodiment, the rust remover is phosphate ester.

[0077] The preparation method of the antimony-based multi-metal passivator comprises the following specific steps:

[0078] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 40 min, filter to remove impurities, and obtain a mixed solution A;

[0079] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 30 min, filtering to remove impurities, and obtaining a mixed solution B;

[0080] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 2 hours to obtain an antimony-based multi-metal passivator.

[0081] Example 5

[0082] The invention discloses an antimony-based multi-metal passivator, which is composed of the following components in percentage by mass: 11% of an organic antimony compound, 28% of an inorganic antimony compound, 22% of a dispersant, 30% of a polar solvent, 0.2% of hydrogen peroxide, 6.7% of a solubilizer, 2% of a pH regulator, and 0.1% of a rust inhibitor.

[0083] In this embodiment, the organic antimony compound is diisopropyl antimony dithiophosphate.

[0084] In this embodiment, the inorganic antimony compound is antimony pentoxide.

[0085] In this embodiment, the dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is 4.5:4.

[0086] In this embodiment, the polar solvent is ethylbenzene.

[0087] In this embodiment, the solubilizing agent is dimethylacetamide.

[0088] In this embodiment, the pH adjuster is sodium hydroxide.

[0089] In this embodiment, the rust remover is phosphate ester.

[0090] The preparation method of the antimony-based multi-metal passivator comprises the following specific steps:

[0091] S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 32 minutes, filter to remove impurities, and obtain a mixed solution A;

[0092] S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 33 min, filtering to remove impurities, and obtaining a mixed solution B;

[0093] S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 1.6 hours to obtain an antimony-based multi-metal passivator.

[0094] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present invention. Ordinary technicians in the field can change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An antimony-based multi-metal passivator, characterized in that: It is composed of the following components in percentage by mass: Organic antimony compounds 10%-15%; Inorganic antimony compounds 20%-30%; Dispersant 20%-25%; Polar solvent 25%-35%; Hydrogen peroxide 0.1%-0.2%; Solubilizer 3%-8%; PH regulator 1%-2%; Rust inhibitor 0.1%-0.2%.

2. The antimony-based multi-metal passivator according to claim 1, characterized in that: The organic antimony compound is one or a combination of antimony thiolate, trisoxalyl antimony, triphenyl antimony, and diisopropyl dithiophosphate antimony.

3. The antimony-based multi-metal passivator according to claim 1, characterized in that: The inorganic antimony compound is one of antimony trioxide and antimony pentoxide.

4. The antimony-based multi-metal passivator according to claim 1, characterized in that: The dispersant is a mixture of citric acid and ethanolamine, wherein the molar ratio of citric acid to ethanolamine is (3.5-4.5):(4-5).

5. The antimony-based multi-metal passivator according to claim 1, characterized in that: The polar solvent is one of petroleum acid, fatty acid, toluene, ethylbenzene and propylbenzene.

6. The antimony-based multi-metal passivator according to claim 1, characterized in that: The solubilizing agent is one of dimethylformamide, dimethylacetamide, diethylformamide and benzamide.

7. The antimony-based multi-metal passivator according to claim 1, characterized in that: The pH adjuster is one of sodium hydroxide, sodium bicarbonate, hydrochloric acid and hydrofluoric acid.

8. The antimony-based multi-metal passivator according to claim 1, characterized in that: The rust remover is one of phosphate ester, triethanolamine borate, and potassium salt of fatty alcohol ether phosphate.

9. A method for preparing the antimony-based multi-metal passivator according to claim 1, characterized in that: The specific steps include: S1. Mix the inorganic antimony compound, dispersant and hydrogen peroxide according to the proportion, stir evenly at 80-90° C. for 30-40 min, filter to remove impurities, and obtain a mixed solution A; S2, mixing the organic antimony compound and the polar solvent according to the ratio, stirring evenly at 80-90° C. for 30-40 min, filtering to remove impurities, and obtaining a mixed solution B; S3. Mix the mixed solution A, the mixed solution B, the solubilizer, the pH regulator and the rust inhibitor, and stir evenly at room temperature for 1-2 hours to obtain a solution with a pH value of 2-6. This solution is the desired antimony-based multi-metal passivator.

10. The method for preparing an antimony-based multi-metal passivator according to claim 9, characterized in that: The dispersant in step S1 is prepared by mixing citric acid and ethanolamine in water, the molar ratio of citric acid to ethanolamine is (3.5-4.5):(4-5), and the pH value of the prepared dispersant is 4-6.