Oil-based drilling fluid emulsifier and preparation method thereof

Abstract

The invention relates to the technical field of oil-based drilling fluid emulsifiers, and discloses an oil-based drilling fluid emulsifier and a preparation method thereof. The invention obtains an oil-based drilling fluid emulsifier by adding a sulfonated amide surfactant, a triazine-modified bisphenol A epoxy resin, lignin, and anhydrous sorbitan oleate into a reactor and stirring. The amide group and the long carbon chain in the sulfonated amide surfactant can be arranged in a directional manner and adsorbed on the oil-water interface to form a high-strength interface film, so that the emulsifier has temperature resistance and emulsification; the sulfonic acid group improves the strength of the emulsifier interface film, thereby enhancing the high temperature resistance and stability of the emulsifier. The epoxy resin helps to form smaller and more stable emulsion droplets, thereby improving the stability of the emulsifier; the chlorine atoms in cyanuric chloride can react with the hydroxyl group and the amine group in the emulsifier molecules to form a stable chemical bond, so that the emulsifier molecules are arranged more closely at the oil-water interface, thereby improving the stability of the emulsifier.

Description

Technical Field

[0001] The present invention relates to the technical field of oil-based drilling fluid emulsifiers, in particular to an oil-based drilling fluid emulsifier and a preparation method thereof. Background Art

[0002] Oil-based drilling fluid is a kind of oil-based drilling fluid, which is widely used in drilling projects. It has the characteristics of high temperature resistance, resistance to salt and calcium corrosion, and good lubricity. Among them, emulsifier, as the core treatment agent of oil-in-water drilling fluid, is the key to ensuring the performance of oil-based drilling fluid. Oil-based drilling fluid is easily affected by the formation temperature. The molecular structure of the emulsifier is easily destroyed at high temperature and loses its emulsification ability, resulting in poor temperature resistance of the oil-based drilling fluid and being unable to meet the drilling requirements of complex formations. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN104531107A discloses an emulsifier for oil-based drilling fluid and its preparation method, which only meets the requirements of high efficiency, environmental protection, and high emulsification rate of oil-based drilling fluid emulsifier, and its high temperature resistance and stability need to be improved. Summary of the Invention

[0003] (1) Technical problems solved

[0004] In view of the deficiencies of the prior art, the present invention provides an oil-based drilling fluid emulsifier and a preparation method thereof, which has good high temperature resistance and stability.

[0005] (2) Technical solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: an oil-based drilling fluid emulsifier, comprising the following components by weight: 18-22 parts by weight of a sulfonated amide surfactant, 12-14 parts by weight of a triazine-modified bisphenol A epoxy resin, 6-9 parts by weight of lignin, and 4-6 parts by weight of anhydrous sorbitan oleate.

[0007] Preferably, the preparation method of the sulfonated amide surfactant is:

[0008] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, nitrogen was introduced for protection, and the reaction was carried out at 70-80°C for 5-7 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0009] (2) Add intermediate 1 to the reactor, heat to 110-135°C, maintain the temperature for 25-30 minutes, add N,N-diethylethylenediamine and sodium hydroxide catalyst, mix evenly at a speed of 150-200 r / min, introduce nitrogen protection, react at 150-175°C for 5-8 hours, and after the reaction is completed, cool, wash and dry to obtain intermediate 2;

[0010] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 8-12°C, raise the temperature to 20-25°C after the addition is complete, continue stirring, raise the temperature to 38-42°C, discharge hydrogen chloride, and after the reaction is complete, distill under reduced pressure to obtain a sulfonated amide surfactant.

[0011] Preferably, the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride and dibenzoyl peroxide in (1) is 1:1.25-1.45:0.02-0.06.

[0012] Preferably, the mass ratio of the intermediate 1, N,N-diethylethylenediamine, and sodium hydroxide in (2) is 1:2.8-3.2:0.01-0.02.

[0013] Preferably, the mass ratio of the intermediate 2 to chlorosulfonic acid in (3) is 1:0.72-0.8.

[0014] Preferably, the preparation method of the triazine-modified bisphenol A epoxy resin is:

[0015] S1. Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, stir and mix, and react at 45-60°C for 18-20 hours. After the reaction, filter, wash, and dry to obtain intermediate 3;

[0016] S2. Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, react at 28-35°C for 6-7.5 hours, wash and dry to obtain a triazine-modified bisphenol A epoxy resin.

[0017] Preferably, the mass ratio of bisphenol A epoxy resin to sodium hydride in S1 is 1:0.75-0.8.

[0018] Preferably, the mass ratio of the intermediate 3 to cyanuric chloride in S2 is 1:1.3-1.5.

[0019] Preferably, the preparation method of the oil-based drilling fluid emulsifier is: adding a sulfonated amide surfactant, a triazine-modified bisphenol A epoxy resin, lignin, and anhydrous sorbitan oleate to a reactor, and stirring at a speed of 1200-1500 rpm for 2.5-3 hours to obtain the oil-based drilling fluid emulsifier.

[0020] (3) Beneficial technical effects

[0021] The invention prepares an oil-based drilling fluid emulsifier by adding a sulfonated amide surfactant, a triazine-modified bisphenol A epoxy resin, lignin and sorbitan oleate into a reactor and stirring the mixture.

[0022] Tall oil acid reacts with 2,3-dimethylmaleic anhydride to produce a tall oil acid-anhydride adduct. This tall oil acid-anhydride adduct then undergoes an amidation reaction with N,N-diethylethylenediamine to introduce an amide group, yielding intermediate 2. Intermediate 2 is then sulfonated with chlorosulfonic acid to introduce a sulfonic acid group, yielding a sulfonated amide surfactant. The hydroxyl groups in bisphenol A epoxy resin react with sodium hydride to remove hydrogen ions from the hydroxyl groups, generating the corresponding anions, yielding intermediate 3. Intermediate 3 undergoes a nucleophilic substitution reaction with cyanuric chloride to yield a triazine-modified bisphenol A epoxy resin.

[0023] The hydrophilic amide groups and lipophilic long carbon chains in sulfonated amide surfactants can be arranged and adsorbed in a directional manner at the oil-water interface, thereby reducing interfacial tension and forming a high-strength interfacial film, giving the emulsifier excellent temperature resistance and emulsification properties. The strong hydration effect of the sulfonic acid groups increases the strength of the emulsifier's interfacial film, thereby enhancing the emulsifier's high temperature resistance and stability. Epoxy resins can significantly reduce tension at the oil-water interface, helping to form smaller, more stable emulsion droplets and improving the stability of the emulsifier. The chlorine atoms in cyanuric chloride react with the hydroxyl and amine groups in the emulsifier molecules to form stable chemical bonds, which allows the emulsifier molecules to be more tightly arranged at the oil-water interface and improves the emulsifier's stability. DETAILED DESCRIPTION Example 1

[0024] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, wherein the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide was 1:1.25:0.02, and nitrogen was introduced for protection. The reaction was carried out at 70°C for 5 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0025] (2) Add intermediate 1 into the reactor, heat to 110°C, maintain the temperature for 25 minutes, add N,N-diethylethylenediamine and sodium hydroxide catalyst, wherein the mass ratio of intermediate 1, N,N-diethylethylenediamine and sodium hydroxide is 1:2.8:0.01, mix evenly at a speed of 150 r / min, introduce nitrogen protection, react at 150°C for 5 hours, cool after the reaction, wash and dry to obtain intermediate 2;

[0026] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 8°C, wherein the mass ratio of intermediate 2 to chlorosulfonic acid is 1:0.72, and after the addition is complete, heat to 20°C, continue stirring, and heat to 38°C, discharge hydrogen chloride, and after the reaction is complete, perform vacuum distillation to obtain a sulfonated amide surfactant;

[0027] (4) Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, wherein the mass ratio of bisphenol A epoxy resin to sodium hydride is 1:0.75, stir and mix, and react at 45°C for 18 hours. After the reaction is completed, filter, wash and dry to obtain intermediate 3;

[0028] (5) Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, wherein the mass ratio of intermediate 3 to cyanuric chloride is 1:1.3, react at 28°C for 6 hours, wash and dry to obtain triazine-modified bisphenol A epoxy resin;

[0029] (6) Sulfonated amide surfactant, triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate were added to the reactor and stirred at 1200 rpm for 2.5 h to obtain an oil-based drilling fluid emulsifier. Example 2

[0030] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, wherein the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide was 1:1.45:0.06, and nitrogen was introduced for protection. The reaction was carried out at 80°C for 7 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0031] (2) Add intermediate 1 into the reactor, heat to 135°C, maintain the temperature for 30 minutes, add N,N-diethylethylenediamine and sodium hydroxide catalyst, wherein the mass ratio of intermediate 1, N,N-diethylethylenediamine and sodium hydroxide is 1:3.2:0.02, mix evenly at a speed of 200 r / min, introduce nitrogen protection, react at 175°C for 8 hours, cool after the reaction, wash and dry to obtain intermediate 2;

[0032] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 12°C, wherein the mass ratio of intermediate 2 to chlorosulfonic acid is 1:0.8, and after the addition is complete, heat to 25°C, continue stirring, and heat to 42°C to discharge hydrogen chloride. After the reaction is complete, distill under reduced pressure to obtain a sulfonated amide surfactant;

[0033] (4) Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, wherein the mass ratio of bisphenol A epoxy resin to sodium hydride is 1:0.8, stir and mix, react at 60°C for 20 hours, and after the reaction is completed, filter, wash and dry to obtain intermediate 3;

[0034] (5) Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, wherein the mass ratio of intermediate 3 to cyanuric chloride is 1:1.5, react at 35°C for 7.5h, wash and dry to obtain triazine-modified bisphenol A epoxy resin;

[0035] (6) Sulfonated amide surfactant, triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate were added to the reactor and stirred at 1500 rpm for 3 h to obtain an oil-based drilling fluid emulsifier. Example 3

[0036] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, wherein the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide was 1:1.35:0.04, and nitrogen was introduced for protection. The reaction was carried out at 75°C for 6 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0037] (2) Add intermediate 1 into the reactor, heat to 122 ° C, maintain the temperature for 27 minutes, add N, N-diethylethylenediamine and sodium hydroxide catalyst, wherein the mass ratio of intermediate 1, N, N-diethylethylenediamine and sodium hydroxide is 1:3:0.015, mix evenly at a speed of 175 r / min, introduce nitrogen protection, react at 162 ° C for 6.5 hours, and after the reaction is completed, cool, wash and dry to obtain intermediate 2;

[0038] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 10°C, wherein the mass ratio of intermediate 2 to chlorosulfonic acid is 1:0.76, and after the addition is complete, heat to 22°C, continue stirring, and heat to 40°C to discharge hydrogen chloride. After the reaction is complete, distill under reduced pressure to obtain a sulfonated amide surfactant;

[0039] (4) Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, wherein the mass ratio of bisphenol A epoxy resin to sodium hydride is 1:0.77, stir and mix, and react at 52°C for 19 hours. After the reaction is completed, filter, wash and dry to obtain intermediate 3;

[0040] (5) Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, wherein the mass ratio of intermediate 3 to cyanuric chloride is 1:1.4, react at 32°C for 6.7h, wash and dry to obtain triazine-modified bisphenol A epoxy resin;

[0041] (6) Sulfonated amide surfactant, triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate were added to the reactor and stirred at 1350 rpm for 2.7 h to obtain an oil-based drilling fluid emulsifier. Example 4

[0042] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, wherein the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide was 1:1.25:0.02, and nitrogen was introduced for protection. The reaction was carried out at 70°C for 5 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0043] (2) Add intermediate 1 into the reactor, heat to 110°C, maintain the temperature for 25 minutes, add N,N-diethylethylenediamine and sodium hydroxide catalyst, wherein the mass ratio of intermediate 1, N,N-diethylethylenediamine and sodium hydroxide is 1:2.8:0.01, mix evenly at a speed of 150 r / min, introduce nitrogen protection, react at 150°C for 5 hours, cool after the reaction, wash and dry to obtain intermediate 2;

[0044] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 12°C, wherein the mass ratio of intermediate 2 to chlorosulfonic acid is 1:0.8, and after the addition is complete, heat to 25°C, continue stirring, and heat to 42°C to discharge hydrogen chloride. After the reaction is complete, distill under reduced pressure to obtain a sulfonated amide surfactant;

[0045] (4) Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, wherein the mass ratio of bisphenol A epoxy resin to sodium hydride is 1:0.8, stir and mix, react at 60°C for 20 hours, and after the reaction is completed, filter, wash and dry to obtain intermediate 3;

[0046] (5) Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, wherein the mass ratio of intermediate 3 to cyanuric chloride is 1:1.4, react at 32°C for 6.7h, wash and dry to obtain triazine-modified bisphenol A epoxy resin;

[0047] (6) Sulfonated amide surfactant, triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate were added to the reactor and stirred at 1350 rpm for 2.7 h to obtain an oil-based drilling fluid emulsifier. Example 5

[0048] (1) Tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide catalyst were added to toluene solvent, wherein the mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride, and dibenzoyl peroxide was 1:1.35:0.04, and nitrogen was introduced for protection. The reaction was carried out at 75°C for 6 hours. After the reaction was completed, the mixture was washed and distilled under reduced pressure to obtain intermediate 1;

[0049] (2) Add intermediate 1 into the reactor, heat to 122 ° C, maintain the temperature for 27 minutes, add N, N-diethylethylenediamine and sodium hydroxide catalyst, wherein the mass ratio of intermediate 1, N, N-diethylethylenediamine and sodium hydroxide is 1:3:0.015, mix evenly at a speed of 175 r / min, introduce nitrogen protection, react at 162 ° C for 6.5 hours, and after the reaction is completed, cool, wash and dry to obtain intermediate 2;

[0050] (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly add chlorosulfonic acid dropwise at 8°C, wherein the mass ratio of intermediate 2 to chlorosulfonic acid is 1:0.72, and after the addition is complete, heat to 20°C, continue stirring, and heat to 38°C, discharge hydrogen chloride, and after the reaction is complete, perform vacuum distillation to obtain a sulfonated amide surfactant;

[0051] (4) Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, wherein the mass ratio of bisphenol A epoxy resin to sodium hydride is 1:0.75, stir and mix, and react at 45°C for 18 hours. After the reaction is completed, filter, wash and dry to obtain intermediate 3;

[0052] (5) Add intermediate 3 to acetonitrile solvent, stir and dissolve, then add cyanuric chloride, wherein the mass ratio of intermediate 3 to cyanuric chloride is 1:1.5, react at 35°C for 7.5h, wash and dry to obtain triazine-modified bisphenol A epoxy resin;

[0053] (6) Sulfonated amide surfactant, triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate were added to the reactor and stirred at 1500 rpm for 3 h to obtain an oil-based drilling fluid emulsifier.

[0054] Comparative Example 1

[0055] Compared with Example 5, this comparative example differs in that no sulfonated amide surfactant is added.

[0056] Comparative Example 2

[0057] Compared with Example 5, this comparative example differs in that no triazine-modified bisphenol A epoxy resin is added.

[0058] The oil-based drilling fluid emulsifier was prepared into an emulsion, and the emulsion was placed in a 180°C oven for 12 hours to test the demulsification voltage before and after high temperature.

[0059] Table 1: Demulsification voltage test.

[0060]

[0061] As can be seen from Table 1, Examples 1-5 of the present invention have better high temperature resistance than Comparative Examples 1-2.

[0062] Dissolve 20g of sodium bentonite for drilling fluid testing in 500mL of distilled water, stir for 2h, and seal and cure for 10h. Measure 150mL of base slurry and add an oil-based drilling fluid emulsifier using an electric stirrer at 1400rpm. Add 200mL of diesel fuel and stir for 50min. Transfer the emulsion to a 500mL graduated cylinder and let it stand for 18h before observation.

[0063] Table 2: Emulsion stability test.

[0064] project Solution appearance Example 1 No oil precipitation Example 2 No oil precipitation Example 3 No oil precipitation Example 4 No oil precipitation Example 5 No oil precipitation Comparative Example 1 A small amount of oil precipitation Comparative Example 2 A small amount of oil precipitation

[0065] As can be seen from Table 2, Examples 1-5 of the present invention have better stability than Comparative Examples 1-2.

[0066] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An oil-based drilling fluid emulsifier, characterized in that: The invention comprises the following components by weight: 18-22 parts by weight of a sulfonated amide surfactant, 12-14 parts by weight of a triazine-modified bisphenol A epoxy resin, 6-9 parts by weight of lignin, and 4-6 parts by weight of sorbitan oleate; The preparation method of the triazine-modified bisphenol A type epoxy resin is as follows: S1. Add bisphenol A epoxy resin and sodium hydride to N,N-dimethylformamide solvent, stir and mix, react at 45-60°C for 18-20h, filter, wash and dry after the reaction to obtain intermediate 3; S2. Add intermediate 3 to acetonitrile solvent, stir to dissolve, then add cyanuric chloride thereto, react at 28-35° C. for 6-7.5 h, wash and dry to obtain a triazine-modified bisphenol A epoxy resin; The mass ratio of bisphenol A epoxy resin to sodium hydride in S1 is 1:0.75-0.8; The mass ratio of intermediate 3 to cyanuric chloride in S2 is 1:1.3-1.5; The preparation method of the sulfonated amide surfactant is as follows: (1) tall oil acid, 2,3-dimethylmaleic anhydride and dibenzoyl peroxide catalyst were added to toluene solvent, nitrogen was introduced for protection, and the reaction was carried out at 70-80°C for 5-7 hours. After the reaction was completed, the intermediate 1 was washed and distilled under reduced pressure to obtain the intermediate 1; (2) Add intermediate 1 into the reactor, heat to 110-135°C, maintain the temperature for 25-30 min, add N,N-diethylethylenediamine and sodium hydroxide catalyst, mix evenly at a speed of 150-200 r / min, introduce nitrogen protection, react at 150-175°C for 5-8 h, and after the reaction is completed, cool, wash and dry to obtain intermediate 2; (3) Add intermediate 2 to N,N-dimethylformamide solvent, stir and mix evenly, slowly drop chlorosulfonic acid at 8-12°C, raise the temperature to 20-25°C after the addition is complete, continue stirring, raise the temperature to 38-42°C, discharge hydrogen chloride, and after the reaction is complete, perform vacuum distillation to obtain a sulfonated amide surfactant; The mass ratio of tall oil acid, 2,3-dimethylmaleic anhydride and dibenzoyl peroxide in (1) is 1:1.25-1.45:0.02-0.06; The mass ratio of the intermediate 1, N,N-diethylethylenediamine, and sodium hydroxide in (2) is 1:2.8-3.2:0.01-0.02; The mass ratio of the intermediate 2 to chlorosulfonic acid in (3) is 1:0.72-0.

8.

2. The oil-based drilling fluid emulsifier according to claim 1, characterized in that: The preparation method of the oil-based drilling fluid emulsifier is as follows: adding a sulfonated amide surfactant, a triazine-modified bisphenol A epoxy resin, lignin, and sorbitan oleate into a reactor, and stirring at a rotation speed of 1200-1500 rpm for 2.5-3 hours to obtain the oil-based drilling fluid emulsifier.

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