A pressure-reducing and injection-increasing surfactant and its preparation method

Abstract

The invention relates to the technical field of oilfield chemistry, and discloses a pressure-reducing and injection-increasing surfactant and a preparation method thereof. The invention provides a pressure-reducing and injection-increasing surfactant by adding quaternized carbon nanotubes, adamantane-modified nano silicon dioxide, sodium dodecyl diphenyl ether disulfonate, methyl amyl alcohol, trimethylsilyl glucoside and water into a reaction kettle and stirring the mixture. The pressure-reducing and injection-increasing surfactant can reduce the tension of the oil-water interface and inhibit clay expansion, thereby improving the permeability of injected water and playing the role of pressure-reducing and injection-increasing. The intermediate 2 contains a large number of hydroxyl groups, which increase the grafting sites and substitution degree of the carbon nanotubes. The carbon nanotubes can prevent clay expansion and form a nano film on the surface of the rock. The nano film can change the wettability of the rock, thereby reducing the flow resistance of water in the rock pores and achieving the effect of reducing the injection pressure. The nano silicon dioxide itself can also reduce the pressure and injection-increasing.

Description

Technical Field

[0001] The invention relates to the technical field of oilfield chemistry, in particular to a pressure-reducing and injection-increasing surfactant and a preparation method thereof. Background Art

[0002] Due to the characteristics of low permeability oil reservoirs such as high mud content, fine pores, and significant capillary force, in order to ensure that water is injected into the injection wells and maintain a certain injection volume, the injection pump pressure is continuously increased. Therefore, the main contradiction in development is high injection pressure, small single well injection volume, small water drive swept volume, and reduced oil recovery efficiency. In China, it is generally adopted to add pressure-reducing and injection-increasing surfactants during the water injection process to improve the water drive effect. For example, patent CN112552893A discloses a molecular membrane pressure-reducing and injection-increasing surfactant and a preparation method thereof. The molecular membrane pressure-reducing and injection-increasing surfactant prepared by the preparation method of the molecular membrane pressure-reducing and injection-increasing surfactant provided in the application can effectively reduce the oil-water interfacial tension, change the wettability, and has good compatibility with the injected water and the oil layer. However, its component type is relatively single and the pressure-reducing and injection-increasing rate is not high. Therefore, how to avoid this phenomenon is the key to solving the problem. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies of the prior art, the present invention provides a pressure-reducing and injection-increasing surfactant and a preparation method thereof, which reduces the injection pressure and the oil-water interfacial tension and improves the water phase permeability.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a pressure-reducing and injection-increasing surfactant, comprising the following components by weight: 4-5 parts by weight of quaternized carbon nanotubes, 4-6 parts by weight of adamantane-modified nano-silica, 2-3 parts by weight of sodium dodecyl diphenyl ether disulfonate, 1-3 parts by weight of methyl amyl alcohol, 1-2 parts by weight of trimethylsilyl glucoside, and 3-4 parts by weight of water.

[0007] Preferably, the preparation method of the quaternized carbon nanotubes is:

[0008] (1) Add 5-aminoisophthalic acid and acryloyl chloride to dimethyl sulfoxide solvent, stir to dissolve, continue to add sodium hydroxide, and then react at 15-20°C for 16-20 hours. After the reaction, add a 10-14% hydrochloric acid solution to adjust the pH of the solution to 2-2.5. After the reaction, distill under reduced pressure, wash with acetone, filter and dry to obtain olefinated dicarboxylic acid;

[0009] (2) Add olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid into a reactor, introduce nitrogen protection, react at 135-150°C for 3-6 hours, continue heating at 195-200°C, remove hydroxyethylethylenediamine, filter, wash and dry to obtain intermediate 1;

[0010] (3) Add 5-12 parts by weight of intermediate 1 and 7-9 parts by weight of 2-bromoethanol to N,N-dimethylformamide solvent, stir evenly, and reflux at 75-90° C., then continue to add 8-10 parts by weight of propylene alcohol and 6-9 parts by weight of ammonium persulfate, react at 90-110° C. for 7-12 hours, and then rotary evaporate and recrystallize from ethanol to obtain intermediate 2;

[0011] (4) Add 8-15 parts by weight of hydroxylated carbon nanotubes to N,N-dimethylformamide solvent, disperse by ultrasonication, and continue to add 6-8 parts by weight of hexamethylene diisocyanate and 9-15 parts by weight of intermediate 2, heat the reaction for 7-12 hours, centrifuge after reaction, wash with ethanol, and dry to obtain quaternized carbon nanotubes.

[0012] Preferably, the mass ratio of 5-aminoisophthalic acid, acryloyl chloride and sodium hydroxide in (1) is 2.2-3:1:1.1-1.2.

[0013] Preferably, the mass ratio of olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid in (2) is 1:1.3-1.5:0.01-0.03.

[0014] Preferably, the reaction time in (3) is 32-35 hours.

[0015] Preferably, the reaction temperature in (4) is 80-95°C.

[0016] Preferably, the preparation method of the adamantane-modified nano-silica is:

[0017] S1. 6-10 parts by weight of nano-silica are ultrasonically dispersed into a mixed solution of 15-30 parts by weight of anhydrous ethanol and 8-10 parts by weight of deionized water, mixed evenly, and then 5-9 parts by weight of γ-aminopropyltriethoxysilane are added, reacted at 70-85 ° C for 20-25h, centrifuged after the reaction, washed and dried to obtain amino-modified nano-silica;

[0018] S2. Add 3-6 parts by weight of amino-modified nano-silica, 2-4 parts by weight of alkyl diacyl chloride and 5-8 parts by weight of 3-hydroxy-1-adamantane methanol to N,N-dimethylformamide solvent, react at 50-75°C for 10-14h, and then distill under reduced pressure, filter and dry to obtain adamantane-modified nano-silica.

[0019] Preferably, the preparation method of the pressure-reducing and injection-increasing surfactant is: adding quaternized carbon nanotubes, adamantane-modified nano-silica, sodium dodecyl diphenyl ether disulfonate, methyl amyl alcohol, trimethylsilyl glucoside, and water into a reaction kettle, stirring at 25-30° C. for 20-30 minutes to obtain the pressure-reducing and injection-increasing surfactant.

[0020] 3. Beneficial technical effects

[0021] The invention adds quaternized carbon nanotubes, adamantane-modified nano silicon dioxide, sodium dodecyl diphenyl ether disulfonate, methyl amyl alcohol, trimethylsilyl glucoside and water into a reaction kettle, and stirs the mixture to obtain a pressure-reducing and injection-increasing surfactant.

[0022] The quaternary ammonium salt group and adamantane structure in the pressure-reducing and injection-increasing surfactant can reduce the tension of the oil-water interface, inhibit clay expansion, and improve the penetration capacity of the injected water, thereby playing a role in pressure reduction and injection-increasing; intermediate 2 contains a large number of hydroxyl groups, which increase the grafting sites of carbon nanotubes and their degree of substitution. Carbon nanotubes can prevent clay expansion and can form a nanofilm on the rock surface. This film can significantly change the wettability of the rock, thereby reducing the flow resistance of water in the rock pores and achieving the effect of reducing the injection pressure; nano-silica itself can also reduce pressure and increase injection. DETAILED DESCRIPTION

[0023] Preparation of hydroxylated carbon nanotubes: 0.3 g of carbon nanotubes were added into concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 for acidification to obtain hydroxylated carbon nanotubes. Example 1

[0024] (1) Add 5-aminoisophthalic acid and acryloyl chloride to dimethyl sulfoxide solvent, stir to dissolve, continue to add sodium hydroxide, wherein the mass ratio of 5-aminoisophthalic acid, acryloyl chloride and sodium hydroxide is 2.2:1:1.1, and then react at 15°C for 16 hours. After the reaction, add a 10% hydrochloric acid solution by mass to adjust the pH of the solution to 2. After the reaction, distill under reduced pressure, wash with acetone, filter and dry to obtain olefinated dicarboxylic acid;

[0025] (2) Adding olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid into a reactor, wherein the mass ratio of olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid is 1:1.3:0.01, introducing nitrogen protection, reacting at 135°C for 3 hours, and continuing to heat at 195°C to remove hydroxyethylethylenediamine, filtering, washing and drying to obtain intermediate 1;

[0026] (3) Add 5 parts by weight of intermediate 1 and 7 parts by weight of 2-bromoethanol to N,N-dimethylformamide solvent, stir evenly, and reflux at 75°C for 32 hours. Then, add 8 parts by weight of propylene alcohol and 6 parts by weight of ammonium persulfate, and react at 90°C for 7 hours. After the reaction, rotary evaporate and recrystallize from ethanol to obtain intermediate 2.

[0027] (4) adding 8 parts by weight of hydroxylated carbon nanotubes to N,N-dimethylformamide solvent, dispersing by ultrasonication, adding 6 parts by weight of hexamethylene diisocyanate and 9 parts by weight of intermediate 2, heating to 80° C. for 7 h, centrifuging after reaction, washing with ethanol, and drying to obtain quaternized carbon nanotubes;

[0028] (5) ultrasonically dispersing 6 parts by weight of nano-silica into a mixed solution of 15 parts by weight of anhydrous ethanol and 8 parts by weight of deionized water, mixing evenly, adding 5 parts by weight of γ-aminopropyltriethoxysilane, reacting at 70° C. for 20 h, centrifuging after the reaction, washing and drying to obtain amino-modified nano-silica;

[0029] (6) Add 3 parts by weight of amino-modified nano-silica, 2 parts by weight of alkyl diacyl chloride and 5 parts by weight of 3-hydroxy-1-adamantane methanol to N,N-dimethylformamide solvent, react at 50° C. for 10 h, and then perform vacuum distillation, filter and dry to obtain adamantane-modified nano-silica;

[0030] (7) 4 parts by weight of quaternized carbon nanotubes, 4 parts by weight of adamantane-modified nano-silica, 2 parts by weight of sodium dodecyl diphenyl ether disulfonate, 1 part by weight of methyl amyl alcohol, 1 part by weight of trimethylsilyl glucoside, and 3 parts by weight of water were added into a reactor and stirred at 25° C. for 20 min to obtain a pressure-reducing and injection-increasing surfactant. Example 2

[0031] (1) Add 5-aminoisophthalic acid and acryloyl chloride to dimethyl sulfoxide solvent, stir to dissolve, continue to add sodium hydroxide, wherein the mass ratio of 5-aminoisophthalic acid, acryloyl chloride and sodium hydroxide is 3:1:1.2, and then react at 20°C for 20 hours. After the reaction, add a 14% hydrochloric acid solution by mass to adjust the solution pH to 2.5. After the reaction, distill under reduced pressure, wash with acetone, filter and dry to obtain olefinated dicarboxylic acid;

[0032] (2) Adding olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid into a reactor, wherein the mass ratio of olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid is 1:1.5:0.03, introducing nitrogen protection, reacting at 150°C for 6 hours, and continuing to heat at 200°C to remove hydroxyethylethylenediamine, filtering, washing and drying to obtain intermediate 1;

[0033] (3) Add 12 parts by weight of intermediate 1 and 9 parts by weight of 2-bromoethanol to N,N-dimethylformamide solvent, stir evenly, and reflux at 90°C for 35 hours. Then, add 10 parts by weight of propylene alcohol and 9 parts by weight of ammonium persulfate, and react at 110°C for 12 hours. After the reaction, perform rotary evaporation and recrystallize from ethanol to obtain intermediate 2.

[0034] (4) adding 15 parts by weight of hydroxylated carbon nanotubes to N,N-dimethylformamide solvent, dispersing by ultrasonication, adding 8 parts by weight of hexamethylene diisocyanate and 15 parts by weight of intermediate 2, heating to 95° C. for 12 h, centrifuging after reaction, washing with ethanol, and drying to obtain quaternized carbon nanotubes;

[0035] (5) ultrasonically dispersing 10 parts by weight of nano-silica into a mixed solution of 30 parts by weight of anhydrous ethanol and 10 parts by weight of deionized water, and after mixing evenly, adding 9 parts by weight of γ-aminopropyltriethoxysilane, reacting at 85° C. for 25 hours, centrifuging after the reaction, washing and drying to obtain amino-modified nano-silica;

[0036] (6) adding 6 parts by weight of amino-modified nano-silica, 4 parts by weight of alkyl diacyl chloride and 8 parts by weight of 3-hydroxy-1-adamantane methanol to N,N-dimethylformamide solvent, reacting at 75° C. for 14 h, and then distilling under reduced pressure, filtering and drying to obtain adamantane-modified nano-silica;

[0037] (7) Add 5 parts by weight of quaternized carbon nanotubes, 6 parts by weight of adamantane-modified nano-silica, 3 parts by weight of sodium dodecyl diphenyl ether disulfonate, 3 parts by weight of methyl amyl alcohol, 2 parts by weight of trimethylsilyl glucoside, and 4 parts by weight of water into a reactor, and stir at 30° C. for 30 min to obtain a pressure-reducing and injection-increasing surfactant. Example 3

[0038] (1) Add 5-aminoisophthalic acid and acryloyl chloride to dimethyl sulfoxide solvent, stir to dissolve, continue to add sodium hydroxide, wherein the mass ratio of 5-aminoisophthalic acid, acryloyl chloride and sodium hydroxide is 2.6:1:1.15, and then react at 17.5°C for 18 hours. After the reaction, add a 12% hydrochloric acid solution by mass to adjust the solution pH to 2.25. After the reaction, distill under reduced pressure, wash with acetone, filter and dry to obtain olefinated dicarboxylic acid;

[0039] (2) Adding olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid into a reactor, wherein the mass ratio of olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid is 1:1.4:0.02, introducing nitrogen protection, reacting at 142.5°C for 4.5 hours, and continuing to heat at 197.5°C to remove hydroxyethylethylenediamine, filtering, washing and drying to obtain intermediate 1;

[0040] (3) Add 8.5 parts by weight of intermediate 1 and 8 parts by weight of 2-bromoethanol to N,N-dimethylformamide solvent, stir evenly, reflux at 82.5°C for 33.5 hours, then continue to add 9 parts by weight of propylene alcohol and 7.5 parts by weight of ammonium persulfate, react at 100°C for 9.5 hours, and then rotary evaporate and recrystallize from ethanol to obtain intermediate 2;

[0041] (4) adding 11.5 parts by weight of hydroxylated carbon nanotubes to N,N-dimethylformamide solvent, dispersing by ultrasonication, adding 7 parts by weight of hexamethylene diisocyanate and 12 parts by weight of intermediate 2, heating to 87.5°C for 9.5 hours, centrifuging after reaction, washing with ethanol, and drying to obtain quaternized carbon nanotubes;

[0042] (5) ultrasonically dispersing 8 parts by weight of nano-silica into a mixed solution of 22.5 parts by weight of anhydrous ethanol and 9 parts by weight of deionized water, and after mixing evenly, adding 7 parts by weight of γ-aminopropyltriethoxysilane, reacting at 77.5° C. for 22.5 hours, centrifuging after the reaction, washing and drying to obtain amino-modified nano-silica;

[0043] (6) adding 4.5 parts by weight of amino-modified nano-silica, 3 parts by weight of alkyl diacyl chloride and 6.5 parts by weight of 3-hydroxy-1-adamantane methanol to N,N-dimethylformamide solvent, reacting at 62.5° C. for 12 h, and then performing reduced pressure distillation, filtering and drying to obtain adamantane-modified nano-silica;

[0044] (7) 4.5 parts by weight of quaternized carbon nanotubes, 5 parts by weight of adamantane-modified nano-silica, 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate, 2 parts by weight of methyl amyl alcohol, 1.5 parts by weight of trimethylsilyl glucoside, and 3.5 parts by weight of water were added into a reactor and stirred at 27.5° C. for 25 min to obtain a pressure-reducing and injection-increasing surfactant.

[0045] Comparative Example 1

[0046] (1) Add 5 parts by weight of adamantane-modified nano-silica, 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate, 2 parts by weight of methyl amyl alcohol, 1.5 parts by weight of trimethylsilyl glucoside, and 3.5 parts by weight of water into a reactor, and stir at 27.5° C. for 25 minutes to obtain a pressure-reducing and injection-increasing surfactant.

[0047] Comparative Example 2

[0048] (1) 4.5 parts by weight of quaternized carbon nanotubes, 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate, 2 parts by weight of methyl amyl alcohol, 1.5 parts by weight of trimethylsilyl glucoside, and 3.5 parts by weight of water were added to a reactor and stirred at 27.5° C. for 25 minutes to obtain a pressure-reducing and injection-increasing surfactant.

[0049] The depressurization and injection surfactant prepared in Examples 1-3 and Comparative Examples 1-2 of the present invention was used to prepare a 0.08wt% depressurization and injection surfactant solution using oilfield water with a salinity of 55000mg / L. A surface tension meter was used to measure the surface tension of the depressurization and injection surfactant and its ability to reduce the oil-water interfacial tension (the experimental oil used dehydrated crude oil from Shengli Oilfield). The depressurization rate was determined in accordance with Q / SLCG0026-2013 "Technical Requirements for Depressurization and Injection Surfactants", and the test liquid was 0.08wt% of the depressurization and injection surfactant.

[0050] Table 1: Pressure reducing surfactant performance test.

[0051] index Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Surface tension (mN / m) 13 15 14 25 27 Interfacial tension (mN / m) <![CDATA[1.2*10 -4 ]]> <![CDATA[1.5*10 -4 ]]> <![CDATA[1.3*10 -4 ]]> <![CDATA[3.2*10 -3 ]]> <![CDATA[3.5*10 -3 ]]> Core drive pressure drop rate (%) 55 58 56 41 38

[0052] It can be seen from Table 1 that the performance of the pressure-reducing and injection-increasing surfactants prepared in Examples 1-3 is better than that in Comparative Examples 1-2.

[0053] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A pressure-reducing and injection-increasing surfactant, characterized in that: The invention comprises the following components by weight: 4-5 parts by weight of quaternized carbon nanotubes, 4-6 parts by weight of adamantane-modified nano-silica, 2-3 parts by weight of sodium dodecyl diphenyl ether disulfonate, 1-3 parts by weight of methyl amyl alcohol, 1-2 parts by weight of trimethylsilyl glucoside, and 3-4 parts by weight of water; The preparation method of the quaternized carbon nanotubes is: (1) Add 5-aminoisophthalic acid and acryloyl chloride to dimethyl sulfoxide solvent, stir to dissolve, continue to add sodium hydroxide, and then react at 15-20°C for 16-20 hours. After the reaction, add a 10-14% hydrochloric acid solution to adjust the pH of the solution to 2-2.

5. After the reaction, distill under reduced pressure, wash with acetone, filter and dry to obtain olefinated dicarboxylic acid; (2) Add olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid into a reactor, introduce nitrogen protection, react at 135-150°C for 3-6 hours, continue heating at 195-200°C, remove hydroxyethylethylenediamine, filter, wash and dry to obtain intermediate 1; (3) Add 5-12 parts by weight of intermediate 1 and 7-9 parts by weight of 2-bromoethanol to N,N-dimethylformamide solvent, stir evenly, and reflux at 75-90° C., then continue to add 8-10 parts by weight of propylene alcohol and 6-9 parts by weight of ammonium persulfate, react at 90-110° C. for 7-12 hours, and then rotary evaporate and recrystallize from ethanol to obtain intermediate 2; (4) adding 8-15 parts by weight of hydroxylated carbon nanotubes to N,N-dimethylformamide solvent, dispersing by ultrasonication, and continuously adding 6-8 parts by weight of hexamethylene diisocyanate and 9-15 parts by weight of intermediate 2, heating the reaction for 7-12 hours, centrifuging after reaction, washing with ethanol, and drying to obtain quaternary ammonium carbon nanotubes; the hydroxylated carbon nanotubes are prepared by adding 0.3 g of carbon nanotubes to concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 for acidification to obtain hydroxylated carbon nanotubes; The mass ratio of 5-aminoisophthalic acid, acryloyl chloride and sodium hydroxide in (1) is 2.2-3:1:1.1-1.2; The mass ratio of olefinic dicarboxylic acid, hydroxyethylethylenediamine and phosphoric acid in (2) is 1:1.3-1.5:0.01-0.03; The reaction time in (3) is 32-35h; The reaction temperature in (4) is 80-95°C; The preparation method of the adamantane-modified nano-silica is: S1. 6-10 parts by weight of nano-silica are ultrasonically dispersed into a mixed solution of 15-30 parts by weight of anhydrous ethanol and 8-10 parts by weight of deionized water, mixed evenly, and then 5-9 parts by weight of γ-aminopropyltriethoxysilane are added, reacted at 70-85 ° C for 20-25h, centrifuged after the reaction, washed and dried to obtain amino-modified nano-silica; S2. Add 3-6 parts by weight of amino-modified nano-silica, 2-4 parts by weight of alkyl diacyl chloride and 5-8 parts by weight of 3-hydroxy-1-adamantane methanol to N,N-dimethylformamide solvent, react at 50-75°C for 10-14h, and then distill under reduced pressure, filter and dry to obtain adamantane-modified nano-silica.

2. A method for preparing a pressure-reducing and injection-increasing surfactant as claimed in claim 1, characterized in that: The preparation method of the pressure-reducing and injection-increasing surfactant is as follows: quaternized carbon nanotubes, adamantane-modified nano-silica, sodium dodecyl diphenyl ether disulfonate, methyl amyl alcohol, trimethylsilyl glucoside and water are added into a reaction kettle, and stirred at 25-30° C. for 20-30 minutes to obtain the pressure-reducing and injection-increasing surfactant.