A clay stabilizer, its preparation method and application

Abstract

The present invention provides a clay stabilizer, a clay stabilizer, which comprises the following raw materials: a bistrimethyl hydroxypropyl quaternary ammonium salt, a carboxylic acid monomer and a solvent; wherein the molar ratio of the bistrimethyl hydroxypropyl quaternary ammonium salt to the carboxylic acid monomer is 1:(1-3), and the mass ratio of the sum of the mass of the bistrimethyl hydroxypropyl quaternary ammonium salt, the carboxylic acid monomer and the catalyst to the solvent is 1:(3-8). At the same time, the present invention also provides a preparation method and application of the clay stabilizer.

Description

Technical Field

[0001] The invention relates to an oil extraction auxiliary agent, in particular to a clay stabilizer and a preparation method and application thereof. Background Art

[0002] Clay expansion mainly includes surface hydration expansion and osmotic hydration expansion. The increase in clay volume caused by osmotic hydration expansion is much greater than that of surface hydration expansion. Both will cause the permeability of the reservoir to decrease. In order to prevent clay expansion, people have studied many clay stabilizers, for example: Chinese patent CN114805682A discloses an amphoteric clay stabilizer, which includes 1 part of a main agent, 0.2-0.4 parts of potassium chloride, 0.1-0.2 parts of ammonium sulfate, 0.2-0.4 parts of dodecyltrimethylammonium chloride and 200 parts of water; wherein the main agent is obtained by emulsion polymerization of dimethyl dodecyl allyl ammonium chloride, sodium styrene sulfonate and diallylamine under the action of an initiator, and the molecular weight is 100000-2000000. However, the high polymer obtained by emulsion polymerization has poor stability and may cause blockage and damage to the oil seepage layer.

[0003] In order to solve the above problems, people have been seeking an ideal technical solution. Summary of the invention

[0004] The purpose of the present invention is to provide a clay stabilizer and a preparation method and application thereof in view of the deficiencies in the prior art.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A clay stabilizer comprises the following raw materials: a bistrimethyl hydroxypropyl quaternary ammonium salt, a carboxylic acid monomer and a solvent; wherein the molar ratio of the bistrimethyl hydroxypropyl quaternary ammonium salt to the carboxylic acid monomer is 1:(1-3), and the mass ratio of the sum of the mass of the bistrimethyl hydroxypropyl quaternary ammonium salt, the carboxylic acid monomer and the catalyst to the solvent is 1:(3-8);

[0007] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is shown in Formula Ⅰ:

[0008]

[0009] The structural formula of the carboxylic acid monomer is R-COOH, wherein R- is a straight-chain alkyl group, a branched alkyl group, an aromatic group, a halogenated alkyl group or a halogenated aromatic group.

[0010] Preferably, R- is a straight-chain alkyl group, and the carboxylic acid monomer is palmitic acid, caprylic acid, undecanoic acid, propionic acid, or glycolic acid; R- is an aromatic group, and the structural formula of the carboxylic acid monomer is:

[0011]

[0012] R- is a halogenated aromatic group, and the structural formula of the carboxylic acid monomer is:

[0013]

[0014] The solvents are trifluoroacetic acid, chloroform, phenol, tetrachloroethane, o-chlorophenol, benzene, chlorobenzene, chloroform, ethyl acetate, ethanol, acetone, and ether.

[0015] A method for preparing a clay stabilizer comprises the following steps:

[0016] Place ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent in a reaction container, fully stir at 120-140° C., react for 20-30 hours, discharge water generated by esterification reaction in time, purify after the reaction is completed, and obtain a clay stabilizer.

[0017] A method for applying a clay stabilizer, characterized in that the amount of the clay stabilizer used is 1-3 g / dL.

[0018] The present invention has outstanding substantial features and significant progress compared with the prior art. Specifically, the present invention provides a clay stabilizer, which has excellent anti-swelling effect and excellent durability. At the same time, the present invention also provides a method for preparing the clay stabilizer, using ditrimethylhydroxypropyl quaternary ammonium salt and carboxylic acid monomer as raw materials for esterification reaction to prepare the clay stabilizer. The method is simple, easy to operate, and suitable for industrial production. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is further described in detail below through specific implementation methods.

[0020] Example

[0021] A clay stabilizer comprises the following raw materials: a bistrimethyl hydroxypropyl quaternary ammonium salt, a carboxylic acid monomer and a solvent; wherein the molar ratio of the bistrimethyl hydroxypropyl quaternary ammonium salt to the carboxylic acid monomer is 1:(1-3), and the mass ratio of the sum of the mass of the bistrimethyl hydroxypropyl quaternary ammonium salt, the carboxylic acid monomer and the catalyst to the solvent is 1:(3-8);

[0022] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is shown in Formula Ⅰ:

[0023]

[0024] The structural formula of the carboxylic acid monomer is R-COOH, wherein R- is a straight-chain alkyl group, a branched alkyl group, an aromatic group, a halogenated alkyl group or a halogenated aromatic group.

[0025] Preferably, R- is a straight-chain alkyl group, and the carboxylic acid monomer is palmitic acid, caprylic acid, undecanoic acid, propionic acid, or glycolic acid; R- is an aromatic group, and the structural formula of the carboxylic acid monomer is:

[0026]

[0027] R- is a halogenated aromatic group, and the structural formula of the carboxylic acid monomer is:

[0028]

[0029] The solvents are trifluoroacetic acid, chloroform, phenol, tetrachloroethane, o-chlorophenol, benzene, chlorobenzene, chloroform, ethyl acetate, ethanol, acetone, and ether.

[0030] A method for preparing a clay stabilizer comprises the following steps:

[0031] Place ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent in a reaction container, fully stir at 120-140° C., react for 20-30 hours, discharge water generated by esterification reaction in time, purify after the reaction is completed, and obtain a clay stabilizer.

[0032] Example 1

[0033] A clay stabilizer comprises the following raw materials: bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent, wherein the molar ratio of bistrimethyl hydroxypropyl quaternary ammonium salt to carboxylic acid monomer is 1:2, and the mass ratio of the sum of the mass of bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and catalyst to the solvent is 1:5. The solvent is chlorobenzene.

[0034] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is:

[0035] Wherein, R is CH3.

[0036] The structural formula of the carboxylic acid monomer is:

[0037]

[0038] A method for preparing a clay stabilizer comprises the following steps:

[0039] The ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent were placed in a reaction vessel, fully stirred at 130°C, reacted for 24 hours, and the water generated by the esterification reaction was discharged in time. After the reaction was completed, the clay stabilizer was purified to obtain the clay stabilizer. The yield of the clay stabilizer was 78%.

[0040] Example 2

[0041] A clay stabilizer comprises the following raw materials: bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent, wherein the molar ratio of bistrimethyl hydroxypropyl quaternary ammonium salt to carboxylic acid monomer is 1:2, and the mass ratio of the sum of the mass of bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and catalyst to the solvent is 1:5. The solvent is chlorobenzene.

[0042] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is:

[0043] Wherein, R is CH3.

[0044] The structural formula of the carboxylic acid monomer is:

[0045]

[0046] A method for preparing a clay stabilizer comprises the following steps:

[0047] The ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent were placed in a reaction vessel, fully stirred at 120°C, reacted for 24 hours, and the water generated by the esterification reaction was discharged in time. After the reaction was completed, the mixture was purified to obtain a clay stabilizer. The yield of the clay stabilizer was 72%.

[0048] Example 3

[0049] A clay stabilizer comprises the following raw materials: bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent, wherein the molar ratio of bistrimethyl hydroxypropyl quaternary ammonium salt to carboxylic acid monomer is 1:2.5, and the mass ratio of the sum of the mass of bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and catalyst to the solvent is 1:6. The solvent is chlorobenzene.

[0050] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is:

[0051] Wherein, R is CH3.

[0052] The structural formula of the carboxylic acid monomer is:

[0053]

[0054] A method for preparing a clay stabilizer comprises the following steps:

[0055] The ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent were placed in a reaction vessel, fully stirred at 130°C, reacted for 24 hours, and the water generated by the esterification reaction was discharged in time. After the reaction was completed, the clay stabilizer was purified to obtain the clay stabilizer. The yield of the clay stabilizer was 67%.

[0056] Example 4

[0057] A clay stabilizer comprises the following raw materials: bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent, wherein the molar ratio of bistrimethyl hydroxypropyl quaternary ammonium salt to carboxylic acid monomer is 1:3, and the mass ratio of the sum of the mass of bistrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and catalyst to the solvent is 1:4. The solvent is chlorobenzene.

[0058] The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is:

[0059] Wherein, R is CH3.

[0060] The structural formula of the carboxylic acid monomer is:

[0061]

[0062] A method for preparing a clay stabilizer comprises the following steps:

[0063] The ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent were placed in a reaction vessel, fully stirred at 120°C, reacted for 30 hours, the water generated by the esterification reaction was discharged in time, and after the reaction was completed, the clay stabilizer was purified to obtain the clay stabilizer. The yield of the clay stabilizer was 71%.

[0064] Example 5

[0065] The clay stabilizer obtained in Examples 1-4 and water were uniformly mixed to prepare a clay stabilizer solution, wherein the concentration of the clay stabilizer in the clay stabilizer solution was 2.5 g / dL; the solution was fully reacted with calcium montmorillonite. The crystal plane spacing d0 of the calcium montmorillonite was measured by an X-ray diffractometer to determine the anti-swelling effect of the clay stabilizer.

[0066] The average d0 value of dry calcium montmorillonite is 1.55279nm, and the average d0 value of fully hydrated calcium montmorillonite is 1.95963nm. Calcium montmorillonite is soaked in clay stabilizer solution, fully mixed, and wet sample is prepared. The average d0 value of wet calcium montmorillonite is 1.45369nm determined by X-ray diffractometer. After wet calcium montmorillonite is soaked in clean water for 24 hours, wet sample is prepared, and the average d0 value of wet calcium montmorillonite is 1.46223nm determined by X-ray diffractometer. After wet calcium montmorillonite is placed in ethylene glycol vapor, wet sample is prepared, and the average d0 value of wet calcium montmorillonite is 1.45364nm determined by X-ray diffractometer. After wet calcium montmorillonite is soaked in 100℃ clean water for 24 hours, wet sample is prepared, and the average d0 value of wet calcium montmorillonite is 1.50214nm determined by X-ray diffractometer.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or some technical features can be replaced by equivalents without departing from the spirit of the technical solution of the present invention, which should be included in the scope of the technical solution for protection of the present invention.

Claims

1. A compound used as a clay stabilizer, the preparation of the compound comprising the following raw materials: ditrimethyl hydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent; wherein, The molar ratio of bistrimethylhydroxypropyl quaternary ammonium salt to carboxylic acid monomer is 1:(1-3), and the mass ratio of the sum of the mass of bistrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and catalyst to the solvent is 1:(3-8); the solvent is trifluoroacetic acid, chloroform, phenol, tetrachloroethane, o-chlorophenol, benzene, chlorobenzene, chloroform, ethyl acetate, ethanol, acetone and ether; The structural formula of bistrimethylhydroxypropyl quaternary ammonium salt is shown in Formula Ⅰ: Formula I; ; The structural formula of the carboxylic acid monomer is Formula II, Formula III or Formula IV; Formula II Formula III Formula IV ; The preparation method of the compound comprises the following steps: Place ditrimethylhydroxypropyl quaternary ammonium salt, carboxylic acid monomer and solvent in a reaction container, fully stir at 120-140°C, react for 20-30 hours, discharge water generated by esterification reaction in time, purify after the reaction is completed, and obtain a clay stabilizer.

2. The use according to claim 1, characterized in that: The compound is used as a clay stabilizer at a level of 1-3 g / dL.

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