A high-yield petroleum sulfonate, its preparation method and application

Abstract

This invention relates to the field of petroleum sulfonate technology, and proposes a high-yield petroleum sulfonate, its preparation method, and its applications. The preparation method of the high-yield petroleum sulfonate includes the following steps: hydrogenating the feedstock oil under the action of a catalyst to obtain a hydrogenated product; sulfonating the hydrogenated product and a sulfonating agent, and neutralizing them to obtain the petroleum sulfonate; the catalyst comprises the following components by weight: 10 parts of flake alumina-supported metal oxide and 1-5 parts of titanium dioxide. This technical solution solves the problem of low petroleum sulfonate yield in related technologies.

Description

Technical Field

[0001] This invention relates to the field of petroleum sulfonate technology, specifically to a high-yield petroleum sulfonate, its preparation method, and its application. Background Technology

[0002] Petroleum sulfonates, as an important class of anionic surfactants, have excellent properties such as reducing oil-water interfacial tension, regulating formation rock wettability, improving crude oil dispersibility, and improving crude oil rheology. They are one of the most widely used and cost-effective oil displacement agents in the field of tertiary oil recovery. They are also widely used in many industrial fields such as metal processing, lubricant additives, and oil drilling mud. The market demand is strong and the application prospects are broad.

[0003] Currently, the preparation of petroleum sulfonates mainly uses petroleum distillate oil, crude oil, or their semi-finished products as raw materials. The process involves sulfonation with a sulfonating agent, followed by neutralization, extraction, separation, and drying to obtain the final product. The sulfonation reaction and subsequent separation and purification processes are crucial in determining the product yield. However, existing preparation processes generally suffer from low petroleum sulfonate yields, which restricts their industrial application. Low yields indirectly increase the generation of waste acid, wastewater, and solid waste during production, raising the cost of waste treatment.

[0004] Therefore, in order to address the problem of low yield in existing petroleum sulfonate preparation processes, it is of great significance to develop preparation technologies that can improve sulfonation efficiency, reduce active ingredient loss, and make full use of raw materials to achieve a significant increase in petroleum sulfonate yield. Summary of the Invention

[0005] This invention proposes a high-yield petroleum sulfonate, its preparation method, and its application, solving the problem of low yield of petroleum sulfonates in related technologies.

[0006] The technical solution of the present invention is as follows: This invention proposes a method for preparing high-yield petroleum sulfonates, comprising the following steps: The feedstock oil is hydrogenated under the action of a catalyst to obtain the hydrogenated product; The hydrogenation product and the sulfonating agent are subjected to a sulfonation reaction and then neutralized to obtain petroleum sulfonate. The catalyst comprises the following components in parts by weight: 10 parts of sheet-like alumina supported on metal oxide and 1-5 parts of titanium dioxide.

[0007] As a further technical solution, in the lamellar alumina supported metal oxide, the D50 particle size of the lamellar alumina is 5~20μm, and the metal oxide includes nickel oxide.

[0008] As a further technical solution, the titanium dioxide is tungsten-doped titanium dioxide.

[0009] In this invention, the yield of petroleum sulfonates is further improved through the synergistic effect of a composite catalyst consisting of lamellar alumina-supported nickel oxide and tungsten-doped titanium dioxide. Tungsten-doped titanium dioxide can regulate surface acidity and electronic structure, while lamellar alumina-supported nickel oxide provides highly active hydrogenation sites. The two work synergistically to enhance catalytic activity and selectivity, promoting the directional hydrogenation of feedstock into suitable sulfonation intermediates, significantly suppressing side reactions, improving hydrogenation conversion and sulfonation efficiency, and thus increasing the yield of petroleum sulfonates.

[0010] As a further technical solution, the metal oxide content of the sheet-like alumina supported on the metal oxide is 8wt%~12wt%; The tungsten-doped titanium dioxide has a tungsten oxide content of 5wt%~8wt%; Preferably, the metal oxide content of the sheet-like alumina supported on the metal oxide is 10 wt%; and the tungsten oxide content of the tungsten-doped titanium dioxide is 6 wt%.

[0011] In this invention, when the content of metal oxide supported on the flake alumina is controlled at 10 wt% and the content of tungsten oxide in the tungsten-doped titanium dioxide is controlled at 6 wt%, the distribution of active sites of the catalyst is optimal, the hydrogenation activity and selectivity are significantly improved, the effect of promoting the directional conversion of feedstock oil into intermediates suitable for sulfonation and suppressing side reactions is optimal, and the yield of petroleum sulfonate reaches the best.

[0012] As a further technical solution, the method for preparing the sheet-like alumina supported on metal oxide includes the following steps: A mixture is obtained by mixing water-soluble metal salts and water; Flake alumina was added to the mixture and mixed, then dried to obtain a preliminary mixture. The initial mixture was calcined to obtain sheet-like alumina-supported metal oxide.

[0013] As a further technical solution, the calcination temperature is 450~650℃ and the time is 4~5h.

[0014] As a further technical solution, the water-soluble metal salt includes nickel nitrate hexahydrate.

[0015] As a further technical solution, the sulfonating agent includes sulfur trioxide; the sulfonation reaction temperature is 50~55℃.

[0016] As a further technical solution, the molar ratio of the hydrogenation product to the sulfonating agent is 6~8:1.

[0017] The present invention also proposes the application of the high-yield petroleum sulfonate obtained by the preparation method described above in oil displacement agents.

[0018] The working principle and beneficial effects of this invention are as follows: In this invention, crude oil is used as the starting material, and hydrogenation is carried out under the synergistic effect of a composite catalyst of plate-like alumina-supported metal oxide and titanium dioxide. This composite catalyst has a large specific surface area, and the metal oxide and titanium dioxide form a synergistic catalytic system, which can effectively regulate the hydrogenation activity and selectivity, promoting the directional conversion of crude oil into intermediates suitable for sulfonation. This improves the activity and conversion rate of subsequent sulfonation reactions. The hydrogenation product is then reacted with a sulfonating agent for sulfonation, and after neutralization, petroleum sulfonate is obtained, significantly increasing the yield of petroleum sulfonate. Detailed Implementation

[0019] 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.

[0020] In the following examples and comparative examples, the feedstock oil was an intermediate-base reduced-second distillate: distillation range 352~447℃, average molecular weight 380, acid value 8 mgKOH / g, gum + asphaltenes 10.5%, aromatics 45.3%, viscosity at 40℃ 84.0 mm. 2 / s.

[0021] Example 1 A method for preparing high-yield petroleum sulfonates includes the following steps: The feedstock oil is hydrogenated under the action of a catalyst to obtain the hydrogenated product; The hydrogenation product and sulfur trioxide (volume concentration 7%, diluted with nitrogen gas) in a molar ratio of 8:1 were subjected to sulfonation at 50°C for 1 hour, and then neutralized with 10% sodium hydroxide solution to pH=8.0 to obtain petroleum sulfonate. The catalyst comprises the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content is 8 wt% based on the mass of alumina) and 1 part of titanium dioxide (average particle size 20 nm). A method for preparing sheet-like alumina supported on metal oxides includes the following steps: Nickel nitrate hexahydrate and water were mixed to obtain a mixture; Add flaky alumina (D50 particle size of 5μm, model FF-PB05) to the mixture, mix, and dry to obtain the initial mixture; The initial mixture was heated to 450℃ at 5℃ / min and calcined for 2 hours, then heated to 650℃ at 5℃ / min and calcined for 2 hours. After cooling in air, sheet-like alumina supported metal oxide was obtained.

[0022] Example 2 A method for preparing high-yield petroleum sulfonates includes the following steps: The feedstock oil is hydrogenated under the action of a catalyst to obtain the hydrogenated product; The hydrogenation product and sulfur trioxide (volume concentration 7%, diluted with nitrogen gas) in a molar ratio of 6:1 were subjected to sulfonation at 55°C for 1 hour, and then neutralized with 10% sodium hydroxide solution to pH=8.0 to obtain petroleum sulfonate. The catalyst comprises the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content is 12wt% based on the mass of alumina) and 5 parts of titanium dioxide (average particle size 20nm). A method for preparing sheet-like alumina supported on metal oxides includes the following steps: Nickel nitrate hexahydrate and water were mixed to obtain a mixture; Add flaky alumina (D50 particle size 20μm, model FF-PB20) to the mixture, mix, and dry to obtain the initial mixture; The initial mixture was heated to 450℃ at 5℃ / min and calcined for 2 hours, then heated to 650℃ at 5℃ / min and calcined for 2 hours. After cooling in air, sheet-like alumina supported metal oxide was obtained.

[0023] Example 3 A method for preparing high-yield petroleum sulfonates includes the following steps: The feedstock oil is hydrogenated under the action of a catalyst to obtain the hydrogenated product; The hydrogenation product and sulfur trioxide (volume concentration 7%, diluted with nitrogen gas) in a molar ratio of 8:1 were subjected to sulfonation at 52°C for 1 hour, and then neutralized with 10% sodium hydroxide solution to pH=8.0 to obtain petroleum sulfonate. The catalyst comprises the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content is 12wt% based on the mass of alumina) and 3 parts of titanium dioxide (average particle size 20nm). A method for preparing sheet-like alumina supported on metal oxides includes the following steps: Nickel nitrate hexahydrate and water were mixed to obtain a mixture; Add flaky alumina (D50 particle size of 15μm, model FF-PB15) to the mixture, mix, and dry to obtain the initial mixture; The initial mixture was heated to 450℃ at 5℃ / min and calcined for 2 hours, then heated to 650℃ at 5℃ / min and calcined for 2 hours. After cooling in air, sheet-like alumina supported metal oxide was obtained.

[0024] Example 4 The difference between this embodiment and Example 3 is that the catalyst includes the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content is 12wt% based on the mass of alumina) and 3 parts of tungsten-doped titanium dioxide (average particle size 20nm, tungsten oxide content is 5wt% based on the mass of titanium dioxide).

[0025] Example 5 The difference between this embodiment and Example 4 is that the catalyst includes the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content of 8 wt% based on the mass of alumina) and 3 parts of tungsten-doped titanium dioxide (average particle size of 20 nm, tungsten oxide content of 8 wt% based on the mass of titanium dioxide).

[0026] Example 6 The difference between this embodiment and Example 3 is that the catalyst includes the following components in parts by weight: 10 parts of nickel oxide supported on alumina (nickel oxide content is 10 wt% based on the mass of alumina) and 3 parts of tungsten-doped titanium dioxide (average particle size 20 nm, tungsten oxide content is 6 wt% based on the mass of titanium dioxide).

[0027] Comparative Example 1 The only difference between this comparative example and Example 3 is that the catalyst includes the following components in parts by weight: 13 parts of nickel oxide supported on alumina flakes (the nickel oxide content is 12 wt% based on the mass of the alumina flakes).

[0028] Comparative Example 2 The only difference between this comparative example and Example 3 is that the catalyst includes the following components in parts by weight: 13 parts of titanium dioxide (average particle size 20 nm).

[0029] Comparative Example 3 The only difference between this comparative example and Example 3 is that the catalyst includes the following components in parts by weight: 10 parts of spherical alumina-supported nickel oxide (based on the mass of flake alumina, the nickel oxide content is 12 wt%, and the particle size of the spherical alumina is 15 μm) and 3 parts of titanium dioxide (average particle size 20 nm).

[0030] The yields of petroleum sulfonates prepared in Examples 1-6 and Comparative Examples 1-3 were recorded and calculated, and the results are shown in Table 1 below.

[0031] Table 1. Yields of petroleum sulfonates in Examples 1-6 and Comparative Examples 1-3

[0032] Compared with Comparative Examples 1-3, the petroleum sulfonate yields obtained in Examples 1-6 were higher, at 96.8% and above, indicating that the hydrogenation treatment under the synergistic effect of the alumina-supported metal oxide and titanium dioxide composite catalyst improved the yield of petroleum sulfonate.

[0033] Compared with Example 3, the petroleum sulfonate yields obtained in Examples 4-6 were even higher, indicating that the synergistic catalytic effect of introducing tungsten-doped titanium dioxide with nickel oxide supported by lamellar alumina was better, further improving the yield of petroleum sulfonate. In particular, the yield of petroleum sulfonate reached its highest level when the content of metal oxide supported by lamellar alumina was controlled at 10 wt% and the tungsten oxide content in tungsten-doped titanium dioxide was 6 wt%.

[0034] 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 high-yield petroleum sulfonate, characterized in that, Includes the following steps: The feedstock oil is hydrogenated under the action of a catalyst to obtain the hydrogenated product; The hydrogenation product and the sulfonating agent are subjected to a sulfonation reaction and then neutralized to obtain petroleum sulfonate. The catalyst comprises the following components in parts by weight: 10 parts of sheet-like alumina supported on metal oxide and 1-5 parts of titanium dioxide.

2. The method for preparing a high-yield petroleum sulfonate according to claim 1, characterized in that, In the lamellar alumina supported on metal oxide, the D50 particle size of the lamellar alumina is 5~20μm, and the metal oxide includes nickel oxide.

3. The method for preparing a high-yield petroleum sulfonate according to claim 2, characterized in that, The titanium dioxide is tungsten-doped titanium dioxide.

4. The method for preparing a high-yield petroleum sulfonate according to claim 3, characterized in that, The content of the metal oxide in the sheet-like alumina supported on the metal oxide is 8wt%~12wt%; The tungsten-doped titanium dioxide has a tungsten oxide content of 5wt%~8wt%; Preferably, the metal oxide content of the sheet-like alumina supported on the metal oxide is 10 wt%; and the tungsten oxide content of the tungsten-doped titanium dioxide is 6 wt%.

5. The method for preparing a high-yield petroleum sulfonate according to claim 1, characterized in that, The method for preparing the sheet-like alumina supported metal oxide includes the following steps: A mixture is obtained by mixing water-soluble metal salts and water; Flake alumina was added to the mixture and mixed, then dried to obtain a preliminary mixture. The initial mixture was calcined to obtain sheet-like alumina-supported metal oxide.

6. The method for preparing a high-yield petroleum sulfonate according to claim 5, characterized in that, The roasting temperature is 450~650℃ and the time is 4~5h.

7. The method for preparing a high-yield petroleum sulfonate according to claim 5, characterized in that, The water-soluble metal salt includes nickel nitrate hexahydrate.

8. The method for preparing a high-yield petroleum sulfonate according to claim 5, characterized in that, The sulfonating agent includes sulfur trioxide; the sulfonation reaction temperature is 50~55℃.

9. The method for preparing a high-yield petroleum sulfonate according to claim 1, characterized in that, The molar ratio of the hydrogenation product to the sulfonating agent is 6~8:

1.

10. The application of high-yield petroleum sulfonates prepared by the preparation method according to any one of claims 1 to 9 in oil displacement agents.

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