Clay stabilizer as well as preparation method and application thereof

Abstract

The invention discloses a clay stabilizer as well as a preparation method and application thereof, and the clay stabilizer is prepared by taking trimesoyl chloride, 1, 2, 3-glycerol and polyether amine as raw materials through esterification, amidation and ester aminolysis reaction. A plurality of amido groups are introduced into the clay stabilizer, amine positive ions can be formed in an aqueous solution, so that the adsorption point location of the clay stabilizer is greatly improved, and meanwhile, the clay stabilizer is high in charge density, can neutralize negative charges on the surface of clay and can be adsorbed with a stratum through static electricity when being used, so that the clay stabilizer has excellent anti-swelling performance and washing resistance; when the addition amount is only 0.1%, the anti-swelling rate can reach 87% or above, and the washing resistance can reach 98% or above; meanwhile, a plurality of rigid groups are contained in the molecular structure, so that the temperature resistance can be effectively improved, and the anti-swelling rate can still reach 86% or above after the anti-swelling agent resists aging at the high temperature of 350 DEG C during use.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of oil exploitation, and particularly relates to a clay stabilizer and a preparation method and application thereof. BACKGROUND

[0002] Clay minerals exist widely in oil layers, and 97% of oil layers in the world contain clay minerals to different degrees. The clay will swell and disperse into fine particles with a diameter less than 10 microns when meeting water or water-based substances in the processes of water injection, acidification and fracturing, thereby blocking the throat of the pore structure of the formation and reducing the permeability of the formation, and causing formation damage. Therefore, for the reservoirs with high clay content and strong water sensitivity, clay stabilizers are generally used to avoid the phenomenon that the clay swelling affects the permeability of the formation when measures such as drilling, cementing, water injection, fracturing, acidification, well repair and well killing are taken.

[0003] The commonly used clay stabilizers at present mainly include inorganic salts, cationic polymers and quaternary ammonium salts. As the earliest used clay anti-swelling agent, the inorganic salt mainly utilizes the ions such as K + embed the clay crystal structure to neutralize the electronegativity of the clay, but the inorganic salt clay anti-swelling agent has weak combination with the formation and poor anti-clay migration capacity. The cationic polymer molecule contains multiple positive charges, can occur multi-point adsorption on the surface of the clay mineral, has good anti-swelling effect and good erosion resistance, but has large molecular weight, is easy to block the pore throat of the formation and damage the permeability of the formation, and is not suitable for use in the dense formation; on the other hand, the cationic polymer has poor temperature resistance and is easy to decompose at high temperature, so that the anti-swelling effect disappears. The quaternary ammonium salt has small molecular weight and will not block the formation, but can only occur single-point adsorption on the surface of the clay, so the anti-swelling effect is not ideal. SUMMARY

[0004] In order to solve the technical problem that the clay stabilizer in the prior art cannot have multi-point adsorption and high temperature resistance, the application provides a clay stabilizer and a preparation method and application thereof, wherein the clay stabilizer contains multiple amine groups in the molecular structure, has multiple adsorption points and good anti-swelling effect, and contains a rigid group in the molecular structure, so that the high temperature resistance of the clay stabilizer can be effectively improved, and the clay stabilizer can have multi-point adsorption and excellent high temperature resistance.

[0005] To achieve the above purpose, the application provides a clay stabilizer having the structure shown in the following formula (1).

[0006]

[0007] wherein n is any value from 1 to 7, R1 and R2 are the same or different and each is independently H or CH3.

[0008] Further, the synthesis reaction process of the clay stabilizer is as follows:

[0009]

[0010] wherein R-OH is a low-carbon alcohol, and the low-carbon alcohol is at least one of methanol and ethanol.

[0011] Another aspect of the present application provides a preparation method of a clay stabilizer, comprising the following steps:

[0012] (1) esterification reaction:

[0013] Under N2 protection, a non-polar solvent and trimesoyl chloride are added into a flask, then a mixed solution of low-carbon alcohol and acid-binding agent is added dropwise into the flask under stirring, and a reflux esterification reaction is performed to obtain an esterification reactant;

[0014] (2) amidation reaction:

[0015] The flask containing the esterification reactant obtained in step 1 is subjected to ice bath or water bath, and a mixed solution of 1,2,3-propanetriamine, acid-binding agent and non-polar solvent is added dropwise into the flask under stirring to perform amidation reaction; after the reaction is completed, extraction and drying are performed to obtain an intermediate product;

[0016] (3) ester aminolysis reaction:

[0017] The intermediate product obtained in step (2) is mixed with a low-carbon alcohol, a mixed solution of polyether amine and acid-binding agent is added dropwise into the mixture of the intermediate product and low-carbon alcohol under stirring, and a reflux ester aminolysis reaction is performed; after the reaction is completed, the solvent is evaporated, and the clay stabilizer is obtained after drying.

[0018] Further, the non-polar solvent is at least one of chloroform, dichloromethane, benzene and toluene.

[0019] Further, the low-carbon alcohol is at least one of methanol and ethanol.

[0020] Further, the acid-binding agent is at least one of diisopropylethylamine and triethylamine.

[0021] Further, in the esterification reaction of step (1), the molar ratio of trimesoyl chloride, low-carbon alcohol and acid-binding agent is: n 均苯三甲酰氯 :n 低碳醇 :n 缚酸剂 = 1: (2-3): (2.5-3.5); and the reaction time of the reflux esterification reaction is 2-4 h.

[0022] Further, in the amidation reaction of step (2), the molar ratio of 1,2,3-propanetriamine, trimesoyl chloride and acid-binding agent is:1,2,3-丙三胺 :n 均苯三甲酰氯 :n 缚酸剂 = 1:(3~4):(3.5~4.5); The reaction temperature of the amidation reaction is 20~40℃, and the reaction time is 1~2h.

[0023] Furthermore, in the ester-amine hydrolysis reaction of step (3), the molar ratio of the intermediate product, the polyetheramine, and the acid-binding agent is: n 中间产物 :n 聚醚胺 :n 缚酸剂 =1:(6~7):(6.5~7.5); the reaction time of the reflux ester aminolysis reaction is 3~5h.

[0024] Another aspect of the present invention provides an application of a clay stabilizer, which is used in oilfield oil production technology.

[0025] The beneficial effects of this invention are:

[0026] 1. The clay stabilizer of the present invention introduces multiple amine groups into its molecular structure, which can form amine cations in aqueous solution, thereby greatly increasing the adsorption sites of the clay stabilizer. At the same time, it has a high charge density, which can neutralize the negative charge on the clay surface and adsorb to the formation through electrostatics during use, thus giving it excellent anti-swelling performance and water washability. When its addition amount is only 0.1%, it can achieve an anti-swelling rate of more than 87% and a water washability of more than 98%.

[0027] 2. The clay stabilizer molecule of the present invention contains multiple rigid groups in its structure, which can effectively improve its temperature resistance and can withstand high temperatures up to 350°C during use.

[0028] 3. The reaction conditions for preparing the clay stabilizer according to this invention are mild, the operation is simple, the post-processing is convenient, and it is easy to apply to industrial production. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of the embodiments will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. In the description of this application, the experimental methods, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, are all commercially available.

[0030] The following disclosure provides many different embodiments or examples for implementing the application. In the interest of simplifying the disclosure, the following description of the various examples is set forth in the context of certain examples. Of course, they are merely examples and are not intended to be limiting of the application. One of ordinary skill in the art, reviewing the following description, will be able to employ the application in other ways and / or with other materials.

[0031] Example 1

[0032] (1) Esterification reaction

[0033] Under the protection of N2, 100 mL of chloroform and 11.95 g of trimesoyl chloride were added to a 250 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 2.88 g of methanol and 11.36 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux esterification reaction was carried out for 3 h to obtain an esterification product.

[0034] (2) Amide reaction

[0035] The three-necked flask containing the esterification product in step 1 was transferred to an ice bath, and a mixed solution of 1.34 g of 1,2,3-propanetriamine, 5.30 g of triethylamine and 50 mL of chloroform was slowly added dropwise to the three-necked flask under stirring, and the temperature was raised to 40°C after the dropwise addition was completed, and reaction was carried out for 1 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was evaporated, and after drying, an intermediate product was obtained.

[0036] (3) Ester aminolysis reaction

[0037] The intermediate product obtained in step 2 and 120 mL of methanol were added to a 500 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 13.32 g of polyether amine and 9.85 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux ester aminolysis reaction was carried out for 5 h; after the reaction was completed, the solvent was evaporated, and drying was carried out to obtain clay stabilizer S1.

[0038] In the step (3), the polyether amine has the following structural formula:

[0039]

[0040] Example 2:

[0041] (1) Esterification reaction

[0042] Under the protection of N2, 100 mL of chloroform and 11.95 g of trimesoyl chloride were added to a 250 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 2.88 g of methanol and 11.36 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux esterification reaction was carried out for 3 h to obtain an esterification product.

[0043] (2) Amidation reaction

[0044] The three-neck flask containing the esterification reactant in step 1 was transferred to an ice bath, and a mixed solution of 1.00 g of 1,2,3-propanetriamine, 5.11 g of triethylamine and 50 mL of chloroform was slowly added dropwise to the three-neck flask under stirring, and after the dropwise addition was completed, the temperature was raised to 35°C and reacted for 1.5 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was evaporated, and after drying, the intermediate product was obtained.

[0045] (3) Ester aminolysis reaction

[0046] The intermediate product obtained in step 2 and 120 mL of methanol were added to a 500 mL three-neck flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 20.87 g of polyether amine and 10.60 g of triethylamine was added dropwise to the three-neck flask under stirring, and the ester aminolysis reaction was carried out under reflux for 3 h; after the reaction was completed, the solvent was evaporated, and after drying, the clay stabilizer S2 was obtained.

[0047] wherein the polyether amine used in step (3) has a structural formula

[0048]

[0049] Example 3:

[0050] (1) Esterification reaction

[0051] Under N2protection, 100 mL of chloroform and 11.95 g of trimesoyl chloride were added to a 250 mL three-neck flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 4.32 g of methanol and 15.91 g of triethylamine was added dropwise to the three-neck flask under stirring, and the esterification reaction was carried out under reflux for 3.5 h to obtain the esterification reactant.

[0052] (2) Amidation reaction

[0053] The three-neck flask containing the esterification reactant in step 1 was transferred to an ice bath, and a mixed solution of 1.00 g of 1,2,3-propanetriamine, 5.11 g of triethylamine and 50 mL of chloroform was slowly added dropwise to the three-neck flask under stirring, and after the dropwise addition was completed, the temperature was raised to 35°C and reacted for 1.5 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was evaporated, and after drying, the intermediate product was obtained.

[0054] (3) Ester aminolysis reaction

[0055] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 24.05 g of polyether amine and 11.40 g of triethylamine was added dropwise into the three-necked flask under stirring, and reflux ester amine decomposition reaction was carried out for 3.5 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S3 was obtained after drying.

[0056] The polyether amine used in step (3) has the structural formula

[0057]

[0058] Example 4:

[0059] (1) Esterification reaction

[0060] Under N2 protection, 100 mL of dichloromethane and 11.95 g of phthaloyl chloride were added into a 250 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 4.14 g of ethanol and 12.73 g of triethylamine was added dropwise into the three-necked flask under stirring, and reflux esterification reaction was carried out for 2 h to obtain an esterification product.

[0061] (2) Amide reaction

[0062] The three-necked flask containing the esterification product in step 1 was transferred into an ice bath, and a mixed solution of 1.07 g of 1,2,3-propanetriamine, 5.23 g of triethylamine and 50 mL of dichloromethane was slowly added into the three-necked flask under stirring, and after the addition was completed, the temperature was increased to 25°C and reacted for 1.5 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was removed by evaporation, and the intermediate product was obtained after drying.

[0063] (3) Ester amine decomposition reaction

[0064] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 24.05 g of polyether amine and 11.40 g of triethylamine was added dropwise into the three-necked flask under stirring, and reflux ester amine decomposition reaction was carried out for 3.5 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S3 was obtained after drying.

[0065] The polyether amine used in step (3) has the structural formula

[0066]

[0067] Example 5:

[0068] (1) Esterification reaction

[0069] Under the protection of N2, 100 mL of dichloromethane and 11.95 g of trimesic acid chloride were added into a 250 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 5.16 g of ethanol and 14.51 g of diisopropylethylamine was added dropwise into the three-necked flask under stirring, and reflux esterification was carried out for 3 h to obtain an esterification product.

[0070] (2) Amide reaction

[0071] The three-necked flask containing the esterification product in step 1 was transferred into an ice bath, and a mixed solution of 1.07 g of 1,2,3-propanetriamine, 6.68 g of diisopropylethylamine and 50 mL of dichloromethane was slowly added dropwise into the three-necked flask under stirring, and the temperature was raised to 30 °C after the addition was completed, and reaction was carried out for 2 h; after the reaction was completed, water was used for extraction, and the organic phase was collected, then dried by molecular sieves, and the solvent was removed by evaporation, and the intermediate product was obtained after drying.

[0072] (3) Ester aminolysis reaction

[0073] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 216.40 g of polyether amine and 13.20 g of diisopropylethylamine was added dropwise into the three-necked flask under stirring, and reflux ester aminolysis reaction was carried out for 4 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S5 was obtained after drying.

[0074] In the step (3), the polyether amine has the following structural formula

[0075]

[0076] Example 6:

[0077] (1) Esterification reaction

[0078] Under the protection of N2, 100 mL of dichloromethane and 11.95 g of trimesic acid chloride were added into a 250 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 5.16 g of ethanol and 14.51 g of diisopropylethylamine was added dropwise into the three-necked flask under stirring, and reflux esterification was carried out for 3 h to obtain an esterification product.

[0079] (2) Amide reaction

[0080] The three-neck flask containing the esterification reactant in step 1 was transferred to an ice bath, and a mixture of 1.00 g of 1,2,3-propanetriamine, 6.53 g of diisopropylethylamine, and 50 mL of toluene was slowly added dropwise to the three-neck flask under stirring, and after the addition was completed, the temperature was raised to 40°C and reacted for 1 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was evaporated, and after drying, the intermediate product was obtained.

[0081] (3) Ester aminolysis reaction

[0082] The intermediate product in step 2 and 120 mL of methanol were added to a 500 mL three-neck flask equipped with magnetic stirring, a thermometer, and a reflux condenser, and a mixture of 38.50 g of polyether amine and 12.60 g of diisopropylethylamine was added dropwise to the three-neck flask under stirring, and reflux ester aminolysis reaction was carried out for 3.5 h; after the reaction was completed, the solvent was evaporated, and after drying, the clay stabilizer S6 was obtained.

[0083] wherein the polyether amine used in step (3) has the structural formula

[0084]

[0085] Example 7:

[0086] (1) Esterification reaction

[0087] Under N2 protection, 100 mL of toluene and 11.95 g of trimesoyl chloride were added to a 250 mL three-neck flask equipped with magnetic stirring, a thermometer, and a reflux condenser, and a mixture of 3.31 g of methanol and 20.32 g of diisopropylethylamine was added dropwise to the three-neck flask under stirring, and reflux esterification reaction was carried out for 4 h to obtain the esterification reactant.

[0088] (2) Amide reaction

[0089] The three-neck flask containing the esterification reactant in step 1 was transferred to an ice bath, and a mixture of 1.00 g of 1,2,3-propanetriamine, 6.53 g of diisopropylethylamine, and 50 mL of toluene was slowly added dropwise to the three-neck flask under stirring, and after the addition was completed, the temperature was raised to 40°C and reacted for 1 h; after the reaction was completed, water was used for extraction and the organic phase was collected, then dried by molecular sieves, and the solvent was evaporated, and after drying, the intermediate product was obtained.

[0090] (3) Ester aminolysis reaction

[0091] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 21.30 g of polyether amine and 13.00 g of diisopropyl ethylamine was added dropwise into the three-necked flask under stirring, and reflux ester amine decomposition reaction was carried out for 5 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S7 was obtained after drying.

[0092] The structure of the polyether amine used in step (3) is as follows:

[0093]

[0094] Example 8:

[0095] (1) Esterification reaction

[0096] Under N2 protection, 100 mL of benzene and 11.95 g of trimesoyl chloride were added into a 250 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 4.03 g of methanol and 16.25 g of diisopropyl ethylamine was added dropwise into the three-necked flask under stirring, and reflux esterification reaction was carried out for 3.5 h to obtain an esterification product.

[0097] (2) Amide reaction

[0098] The three-necked flask containing the esterification product in step 1 was transferred into an ice bath, and a mixed solution of 1.17 g of 1,2,3-propanetriamine, 6.68 g of diisopropyl ethylamine and 50 mL of benzene was slowly added into the three-necked flask under stirring, and the reaction was carried out, after the addition was completed, the temperature was increased to 20℃, and the reaction was carried out for 2 h; after the reaction was completed, water was used for extraction, and the organic phase was collected, then dried by molecular sieves, and the solvent was removed by evaporation, and the intermediate product was obtained after drying.

[0099] (3) Ester amine decomposition reaction

[0100] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, thermometer and reflux condenser, and a mixed solution of 21.30 g of polyether amine and 13.00 g of diisopropyl ethylamine was added dropwise into the three-necked flask under stirring, and reflux ester amine decomposition reaction was carried out for 5 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S7 was obtained after drying.

[0101] The structure of the polyether amine used in step (3) is as follows:

[0102]

[0103] Example 9:

[0104] (1) Esterification reaction

[0105] Under the protection of N2, 100 mL of benzene and 11.95 g of trimesoyl chloride were added to a 250 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 3.74 g of methanol and 14.53 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux esterification was carried out for 3 h to obtain an esterification product.

[0106] (2) Amide reaction

[0107] The three-necked flask containing the esterification product in step 1 was transferred to an ice bath, and a mixed solution of 1.27 g of 1,2,3-propanetriamine, 5.11 g of triethylamine and 50 mL of benzene was slowly added dropwise to the three-necked flask under stirring, and the temperature was raised to 35 °C after the dropwise addition was completed, and reaction was carried out for 2 h; after the reaction was completed, water was used for extraction, and the organic phase was collected, then dried by molecular sieves, and the solvent was removed by evaporation, and the intermediate product was obtained after drying.

[0108] (3) Ester aminolysis reaction

[0109] The intermediate product in step 2 and 120 mL of methanol were added to a 500 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 20.87 g of polyether amine and 10.60 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux ester aminolysis reaction was carried out for 5 h; after the reaction was completed, the solvent was removed by evaporation, and drying was carried out to obtain the clay stabilizer S9.

[0110] In the step (3), the polyether amine has the following structural formula

[0111]

[0112] Example 10:

[0113] (1) Esterification reaction

[0114] Under the protection of N2, 100 mL of benzene and 11.95 g of trimesoyl chloride were added to a 250 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 3.74 g of methanol and 14.53 g of triethylamine was added dropwise to the three-necked flask under stirring, and reflux esterification was carried out for 3 h to obtain an esterification product.

[0115] (2) Amide reaction

[0116] The three-necked flask containing the esterification product in step 1 was transferred to an ice bath, and a mixed solution of 1.27 g of 1,2,3-propanetriamine, 5.11 g of triethylamine and 50 mL of benzene was slowly added dropwise to the three-necked flask under stirring, and the temperature was raised to 35 °C after the dropwise addition was completed, and reaction was carried out for 2 h; after the reaction was completed, water was used for extraction, and the organic phase was collected, then dried by molecular sieves, and the solvent was removed by evaporation, and the intermediate product was obtained after drying.

[0117] (3) Ester aminolysis reaction

[0118] The intermediate product in step 2 and 120 mL of methanol were added into a 500 mL three-necked flask equipped with magnetic stirring, a thermometer and a reflux condenser, and a mixed solution of 24.05 g of polyether amine and 14.50 g of diisopropyl ethylamine was added dropwise into the three-necked flask under stirring, and the ester aminolysis reaction was carried out under reflux for 4 h; after the reaction was completed, the solvent was removed by evaporation, and the clay stabilizer S10 was obtained after drying.

[0119] In the step (3), the polyether amine has the following structural formula:

[0120]

[0121] Comparative Example 1

[0122] The clay stabilizer of commercially available model HJZ-100.

[0123] Performance detection test

[0124] 1. Detection of anti-swelling rate and water washing resistance

[0125] According to the “SY / T5971-2016 Performance Evaluation Method of Clay Stabilizer for Water Injection”, the anti-swelling rate and water washing resistance of the clay stabilizers S1-S10 obtained in Examples 1-10 and the commercially available clay stabilizer of Comparative Example 1 were detected, wherein the mass concentration of the clay stabilizer was 0.1%, and the water washing times were three times.

[0126] 2. Detection of high temperature aging resistance

[0127] After the clay stabilizers S1-S10 obtained in Examples 1-10 and the commercially available clay stabilizer of Comparative Example 1 were aged at 350°C, the anti-swelling rate test was carried out, and the specific steps were as follows:

[0128] 3.00 g of sodium bentonite was added into 60 mL of a clay stabilizer solution with a mass concentration of 0.1%, and after being fully mixed and shaken, it was loaded into an aging kettle; then it was put into a high temperature aging furnace and aged at 350±2°C for 24 h; after cooling to room temperature, the clay stabilizer solution in the aging kettle was completely transferred into a 100 mL beaker, fully shaken, and 10 mL was quickly taken out into a centrifuge tube, loaded into a centrifuge with automatic balancing function, and centrifuged at 1500 r / min for 15 min, and the swelling volume V1 of the bentonite was read out. The high temperature anti-swelling rate calculation formula is shown in the following formula.

[0129]

[0130] In the formula: F— high temperature anti-swelling rate, %;

[0131] V0 - volume of sodium bentonite in kerosene, mL;

[0132] V1 - volume of sodium bentonite in clay anti-swelling agent, mL;

[0133] V2 - volume of sodium bentonite in clean water, mL;

[0134] The results of the detection of the anti-swelling property at room temperature, the washing resistance and the temperature resistance (anti-swelling rate after aging at 350℃ / high-temperature anti-swelling rate) of the clay stabilizers S1-S10 obtained in the above Examples 1-10 and the commercially available clay stabilizer of Comparative Example 1 are shown in Table 1.

[0135] Table 1: Results of the performance detection of the clay stabilizers obtained in each of the Examples and the Comparative Example

[0136] Sample Room temperature anti-swelling ratio, % Washing resistance, % Anti-swelling ratio after 350°C aging, % S1 88.31 99.59 86.35 S2 87.58 98.76 86.15 S3 89.80 100.00 88.95 S4 90.25 100.00 89.15 S5 91.75 99.84 89.81 S6 87.95 98.39 86.21 S7 92.01 100.00 90.05 S8 87.59 99.27 86.51 S9 90.26 99.91 88.62 S10 88.84 100.00 86.54 Commercial sample 52.35 75.12 49.39

[0137] As can be seen from the detection results of Examples 1-10 in the above table, the clay stabilizers prepared by the method of the present application have excellent anti-swelling rate, washing resistance and high-temperature resistance. Among them, the anti-swelling rate of the clay stabilizers prepared by the method of the present application at room temperature is all above 87%, and the highest can reach 91.75%; the washing resistance is all above 98%, and the highest can reach 100%; the anti-swelling rate after aging at 350℃ is all above 86%, and the highest can reach 90.05%. While the anti-swelling rate of the commercially available clay stabilizer at room temperature is only 52.35%, the washing resistance is only 75.12%, and the anti-swelling rate after aging at 350℃ is only 49.39%. Compared with the commercially available clay stabilizer, the anti-swelling rate of the clay stabilizer prepared by the method of the present application at room temperature is increased by more than 67.29% (calculated according to the percentage increase), the washing resistance is increased by more than 30.98%, and the anti-swelling rate after aging at 350℃ is increased by 74.42%.

[0138] In the above examples, the description of each example has its own focus, and the parts not described in detail in a certain example can be referred to the relevant description of other examples.

[0139] The above has introduced in detail the preparation method of the clay stabilizer provided by the embodiments of the present application, and in this paper, specific examples are applied to describe the principles and implementation manners of the present application, and the above example description is only used to help understand the technical solutions and core ideas of the present application; those skilled in the art should understand that: they can still modify the technical solutions recorded in the above examples, or make equivalent replacement to part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A clay stabilizer characterized by: Having a structure as shown in the following formula (1); Wherein, n is any value in 1-7, R1, R2 are the same or different, and each is independently H or CH3.

2. A clay stabilizer according to claim 1, characterized in that: The synthesis reaction process of the clay stabilizer is as follows: Wherein, R-OH is a low carbon alcohol, and the low carbon alcohol is at least one of methanol and ethanol.

3. A method for producing a clay stabilizer, characterized by, Comprising the following steps: (1) esterification reaction: Under the protection of N2, the non-polar solvent and trimesoyl chloride are added into a flask, then a mixed solution of low carbon alcohol and acid binding agent is added dropwise into the flask under stirring, and reflux esterification reaction is carried out to obtain an esterification reactant; (2) amidation reaction: The flask containing the esterification reactant obtained in step 1 is subjected to ice bath or water bath, a mixed solution of 1,2,3-propanetriamine, acid binding agent and non-polar solvent is added dropwise into the flask under stirring, and amidation reaction is carried out; after the reaction is completed, extraction and drying are carried out to obtain an intermediate product; (3) ester aminolysis reaction: The intermediate product obtained in step (2) is mixed with a low carbon alcohol, a mixed solution of polyether amine and acid binding agent is added dropwise into the mixture of the intermediate product and the low carbon alcohol under stirring, and reflux ester aminolysis reaction is carried out; after the reaction is completed, the solvent is evaporated, and after drying, the clay stabilizer is obtained.

4. A method of preparing a clay stabilizer according to claim 3, characterized in that: The non-polar solvent is at least one of chloroform, dichloromethane, benzene and toluene.

5. The method of claim 3, wherein the clay stabilizer is prepared by the steps of: a) mixing the clay with the cationic surfactant; b) adding the mixture to the aqueous solution; and c) mixing the solution until the clay is dispersed in the solution. The low carbon alcohol is at least one of methanol and ethanol.

6. The method of claim 3, wherein the clay stabilizer is prepared by the steps of: The acid binding agent is at least one of diisopropylethylamine and triethylamine.

7. The method for preparing a clay stabilizer according to claim 3, characterized in that: The molar ratio of the trimesoyl chloride, the low carbon alcohol and the acid binding agent in the esterification reaction of step (1) is: n 均苯三甲酰氯 : n 低碳醇 : n 缚酸剂 = 1 : (2-3) : (2.5-3.5); the reaction time is 2-4 h.

8. The method for preparing a clay stabilizer according to claim 3, characterized in that: The molar ratio of the 1,2,3-propanetriamine, the trimesoyl chloride and the acid binding agent in the amidation reaction of step (2) is: n 1,2,3-丙三胺 : n 均苯三甲酰氯 : n 缚酸剂 = 1 : (3-4) : (3.5-4.5); the reaction temperature of the amidation reaction is 20-40℃, and the reaction time is 1-2h.

9. The method for preparing a clay stabilizer according to claim 3, characterized in that: The molar ratio of the intermediate product, the polyether amine and the acid binding agent in the ester aminolysis reaction of step (3) is: n 中间产物 : n 聚醚胺 : n 缚酸剂 = 1 : (6-7) : (6.5-7.5); and the reaction time of the reflux ester aminolysis reaction is 3-5 h.

10. Use of a clay stabilizer, characterized in that: The clay stabilizer of claims 1-2 or the clay stabilizer obtained by the preparation method of any one of claims 3-9 is applied to oilfield production technology.

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