CN-121759179-B - Sulfonated asphalt for drilling fluid and preparation method thereof

CN121759179BCN 121759179 BCN121759179 BCN 121759179BCN-121759179-B

Abstract

The invention relates to the technical field of drilling fluid treatment agents, and discloses sulfonated asphalt for drilling fluid and a preparation method thereof, wherein the preparation method of the sulfonated asphalt for drilling fluid comprises the following steps: crushing asphalt, adding the crushed asphalt and quaternized modified SEBS into kerosene, refluxing and dissolving the mixture for 1 to 2 hours at a temperature of between 100 and 110 ℃, cooling the mixture to a temperature of between 50 and 60 ℃, adding fuming sulfuric acid, continuing to react for 2 to 3 hours, then adjusting the pH value of the system to be 8 to 9 by using a sodium hydroxide solution with a mass fraction of 20 percent, distilling and recovering a kerosene solvent, drying the obtained solid in an oven, and crushing the dried solid to obtain the sulfonated asphalt for drilling fluid. The sulfonated asphalt for the drilling fluid has good filtrate loss reducing performance at high temperature and high pressure, and also has good shale inhibition performance and well wall stability.

Inventors

WANG SHUYONG
GAO JINPING
ZANG YUNGANG

Assignees

山东得顺源石油科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260302

Claims (3)

1. The sulfonated asphalt for the drilling fluid is characterized by comprising, by weight, 20-25 parts of asphalt, 2-4 parts of quaternized modified SEBS, 35-40 parts of kerosene and 6-8 parts of fuming sulfuric acid; wherein the quaternized modified SEBS is obtained by reacting chloromethylated SEBS with an intermediate 1; the intermediate 1 is prepared by reacting 3-pyridine isocyanate and 2-aminobenzene-1, 3, 5-tricarboxylic acid; The preparation method of the quaternized modified SEBS comprises the following steps: S1, dissolving SEBS in chloroform, dropwise adding 1, 4-dichloro methoxybutane and anhydrous tin tetrachloride by using a constant pressure dropping funnel after dissolution, reacting for 3-4 hours at 45-55 ℃ after dropwise adding, precipitating the reaction solution in methanol after the reaction is completed, separating flocculent precipitate, dissolving and washing by using tetrahydrofuran, repeating for 3-4 times, and drying to obtain chloromethylated SEBS; S2, adding deionized water and sodium azide into a reactor, uniformly mixing to obtain a sodium azide aqueous solution, dispersing nicotinoyl chloride hydrochloride into acetone, fully stirring at 0-5 ℃ to obtain a mixture, dripping the mixture into the sodium azide aqueous solution, keeping the liquid level below a dropper during dripping, stirring at 0-5 ℃ for 3-4 hours after dripping, removing a lower water layer after the reaction, taking an upper yellow transparent solution, placing the upper yellow transparent solution into toluene at the temperature of 60-65 ℃, stirring for 2-3 hours until nitrogen is not discharged any more, cooling at low temperature, precipitating solids, filtering and freeze-drying to obtain 3-pyridine isocyanate; S3, adding 3-pyridine isocyanate and 2-aminobenzene-1, 3, 5-tricarboxylic acid into N, N-dimethylformamide solvent, uniformly mixing, stirring at room temperature for reaction for 4-6h, slowly dripping the reaction solution into anhydrous diethyl ether under stirring after the reaction is finished, collecting precipitate, filtering, washing and drying to obtain an intermediate 1; S4, adding chloromethylated SEBS into N, N-dimethylformamide solvent under the protection of nitrogen gas, stirring at 60-80 ℃ until the SEBS is completely dissolved, then adding intermediate 1, uniformly mixing, heating to 80-90 ℃, stirring and reacting for 24-48 hours, cooling to room temperature after the reaction is finished, slowly dripping the reaction solution into methanol under stirring, collecting precipitate, filtering, washing and drying to obtain quaternized modified SEBS; the dosage ratio of SEBS, chloroform, 1, 4-dichloro methoxybutane and anhydrous stannic chloride in the S1 is 2-2.2g:60-65mL:7.2-7.4mL:0.8-1mL; The dosage ratio of deionized water, sodium azide, nicotinyl chloride hydrochloride, acetone and toluene in the S2 is 12-15mL:3.9-4.1g:3.56-3.66g:15-18mL:10-12mL; In the S3, the dosage ratio of the N, N-dimethylformamide, the 3-pyridine isocyanate and the 2-aminobenzene-1, 3, 5-tricarboxylic acid is 35-45mL:2.4-2.5g:4.5-4.6g; In the S4, the dosage ratio of the N, N-dimethylformamide to the chloromethylated SEBS to the intermediate 1 is 50-60mL:1.5-1.6g:1.1-1.2g; The preparation method of the sulfonated asphalt for the drilling fluid comprises the steps of crushing asphalt, adding the crushed asphalt and quaternized modified SEBS into kerosene, refluxing and dissolving the asphalt for 1-2 hours at 100-110 ℃, cooling the asphalt to 50-60 ℃, adding fuming sulfuric acid, continuing to react for 2-3 hours, then adjusting the pH value of a system to 8-9 by using a sodium hydroxide solution with the mass fraction of 20%, distilling and recovering a kerosene solvent, drying the obtained solid in an oven, and crushing the dried solid to obtain the sulfonated asphalt for the drilling fluid.
2. A process for preparing sulfonated asphalt for drilling fluid as defined in claim 1, wherein said process comprises pulverizing asphalt, adding into kerosene together with quaternized modified SEBS, refluxing and dissolving at 100-110 ℃ for 1-2h, cooling to 50-60 ℃, adding fuming sulfuric acid, continuing reacting for 2-3h, regulating pH of system to 8-9 with 20% sodium hydroxide solution, distilling to recover kerosene solvent, drying the obtained solid in oven, pulverizing to obtain sulfonated asphalt for drilling fluid.
3. The method for producing a sulfonated asphalt for a drilling fluid according to claim 2, wherein the temperature of drying in said oven is 110 to 120 ℃.

Description

Sulfonated asphalt for drilling fluid and preparation method thereof Technical Field The invention relates to the technical field of drilling fluid treatment agents, in particular to sulfonated asphalt for drilling fluid and a preparation method thereof. Background With the advancement of oil and gas exploration and development to deep, ultra-deep and complex stratum, geological conditions are more severe, higher requirements are put forward on the comprehensive performance of drilling fluid treatment agents, sulfonated asphalt is an anti-collapse plugging treatment agent widely applied in drilling engineering, and has hydrophilic sulfonate groups and lipophilic asphaltene groups in molecular structures, so that the sulfonated asphalt can be adsorbed on the surface of a well wall to form a protective film, block rock pores and microcracks, reduce the invasion of drilling fluid filtrate, and stabilize the well wall, but the traditional sulfonated asphalt has the problems of poor thermal stability and weak shale inhibition capability, so that the sulfonated asphalt is limited to be applied to complex stratum. How to avoid this phenomenon is therefore the key to solving the problem. For example, the Chinese patent publication No. CN105885809B discloses a sulfonated asphalt for drilling fluid, a preparation method and application thereof, and the sulfonated asphalt obtained by the invention has high water solubility, high dispersion in the drilling fluid, low production cost and low high-temperature high-pressure filtration loss, but shale inhibition performance and well wall stability are still to be improved. Disclosure of Invention In order to overcome the defects of the prior art, the invention aims to provide the sulfonated asphalt for the drilling fluid and the preparation method thereof, and the sulfonated asphalt for the drilling fluid has good filtrate loss reducing performance at high temperature and high pressure, and also has good shale inhibition performance and well wall stability. The invention provides the technical scheme that the sulfonated asphalt for the drilling fluid comprises, by weight, 20-25 parts of asphalt, 2-4 parts of quaternized modified SEBS, 35-40 parts of kerosene and 6-8 parts of fuming sulfuric acid. Further, the preparation method of the quaternized modified SEBS comprises the following steps: S1, dissolving SEBS in chloroform, dropwise adding 1, 4-dichloro methoxybutane and anhydrous tin tetrachloride by using a constant pressure dropping funnel after dissolution, reacting for 3-4 hours at 45-55 ℃ after dropwise adding, precipitating the reaction solution in methanol after the reaction is completed, separating flocculent precipitate, dissolving and washing by using tetrahydrofuran, repeating for 3-4 times, and drying to obtain chloromethylated SEBS; S2, adding deionized water and sodium azide into a reactor, uniformly mixing to obtain a sodium azide aqueous solution, dispersing nicotinoyl chloride hydrochloride into acetone, fully stirring at 0-5 ℃ to obtain a mixture, dripping the mixture into the sodium azide aqueous solution, keeping the liquid level below a dropper during dripping, stirring at 0-5 ℃ for 3-4 hours after dripping, removing a lower water layer after the reaction is finished, taking an upper yellow transparent solution, placing the upper yellow transparent solution into toluene at the temperature of 60-65 ℃, stirring for 2-3 hours until nitrogen is not discharged any more, cooling at 0-5 ℃ and then separating out solids, filtering and freeze-drying to obtain 3-pyridine isocyanate; S3, adding 3-pyridine isocyanate and 2-aminobenzene-1, 3, 5-tricarboxylic acid into N, N-dimethylformamide solvent, uniformly mixing, stirring at room temperature for reaction for 4-6h, slowly dripping the reaction solution into anhydrous diethyl ether under stirring after the reaction is finished, collecting precipitate, filtering, washing and drying to obtain an intermediate 1; S4, adding chloromethylated SEBS into N, N-dimethylformamide solvent under the protection of nitrogen gas, stirring at 60-80 ℃ until the SEBS is completely dissolved, then adding intermediate 1, uniformly mixing, heating to 80-90 ℃, stirring and reacting for 24-48h, cooling to room temperature after the reaction is finished, slowly dripping the reaction solution into methanol under stirring, collecting precipitate, filtering, washing and drying to obtain the quaternized modified SEBS. In the above steps, the chlorine on chloromethylated SEBS and nitrogen atom on pyridine ring in intermediate 1 are quaternized to obtain quaternized modified SEBS with side chain containing pyridine quaternary ammonium salt cationic group. Further, the dosage ratio of SEBS, chloroform, 1, 4-dichloro methoxybutane and anhydrous stannic chloride in the S1 is 2-2.2g:60-65mL:7.2-7.4mL:0.8-1mL. Further, the dosage ratio of deionized water, sodium azide, nicotinyl chloride hydrochloride, acetone and toluene in the S2 is 12-15mL, 3.