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CN-122010840-A - Salt-resistant functional monomer suitable for high-salt oilfield environment and preparation method thereof

CN122010840ACN 122010840 ACN122010840 ACN 122010840ACN-122010840-A

Abstract

The salt-resistant functional monomer suitable for the high-salt oilfield environment comprises, by weight, 210-260 parts of acrylamide, 15-30 parts of AMPS, 6-15 parts of AEO-9, 20-50 parts of functional monomer S, 10-20 parts of urea, 0.2-0.3 part of 1# initiator, 0.05-0.15 part of 2# initiator, 0.05-0.15 part of 3# initiator, 0.1-0.3 part of 4# initiator and 1000 parts of water. The polymer synthesized by using the functional monomer has the characteristics of high salt tolerance, high tackifying property, high viscosity stability and capability of preparing produced sewage from an oil field, and can keep good solubility and viscosity under the sewage condition, thereby improving the petroleum recovery ratio.

Inventors

  • LI SHIQI
  • CHEN LILI
  • HONG WEI
  • ZHANG TINGTING
  • SUN ANSHUN

Assignees

  • 黑龙江吉地油田服务股份有限公司

Dates

Publication Date
20260512
Application Date
20260109

Claims (8)

  1. 1. The salt-resistant functional monomer is characterized in that the molecular structure is shown in the following figure, and is hereinafter referred to as functional monomer S, and the functional monomer S is as follows: 。
  2. 2. The method for preparing the salt-resistant functional monomer S applicable to the high-salt oilfield environment according to claim 1, wherein the method for preparing the functional monomer S comprises the following steps: step one, adding a solvent p-tert-butyl bromobenzene into a reaction kettle, wherein the molecular formula is as follows: Continuously adding cyclohexylboric acid into a reaction kettle, continuously introducing nitrogen, then adding a palladium catalyst Pd (dppf) Cl 2 , adding a water-soluble potassium carbonate solution, and then adding a solvent 1, 4-dioxane, heating the reaction kettle to 80-90 ℃, stirring and refluxing for reaction for about 12 hours, wherein the reaction formula is as follows: After the reaction is finished, cooling the reaction solution to room temperature, adding water and ethyl acetate in a ratio of about 1:1, starting to extract for 2-3 times, merging all organic phases, washing the organic phases once by using a saturated sodium chloride solution, drying the organic phases by using anhydrous sodium sulfate, filtering, steaming to remove a solvent in a rotary way, and purifying by using a mixed solvent of petroleum ether and ethyl acetate as an eluent through a silica gel column chromatography to obtain an intermediate 1; step two, adding the intermediate 1 obtained in the step one and solvent methylene dichloride into a reaction kettle, and slowly dropwise adding nitric acid and sulfuric acid mixed acid at the temperature of 0-5 ℃ for reaction, wherein the reaction formula is as follows: ; After the reaction, pouring the reaction mixture into ice water for quenching, extracting with dichloromethane, and purifying the extracted solution by using a mixed solution of ethanol and water through a recrystallization method to obtain an intermediate 2; Step three, the intermediate 2 obtained in the step two is placed into a reaction kettle, solvent ethanol is added, catalyst Pd/C is added, H 2 is introduced at room temperature under 2 atmospheres for reaction, and the reaction formula is: Filtering to remove the solid catalyst after the reaction is finished, and recrystallizing and purifying to obtain an intermediate 3; step four, adding the intermediate 3 obtained in the step three into a round-bottom flask, placing the round-bottom flask into an ice-water bath, adding a solvent DCM, adding a little sodium hydroxide solution, slowly dripping acryloyl chloride, and keeping the temperature at 0-5 ℃, wherein the reaction formula is as follows: After the reaction is finished, the temperature is raised to room temperature, stirring is continued for 2 hours, a small amount of sodium hydroxide solution is added to react out residual acryloyl chloride, a separating funnel is used for filtering, saturated sodium chloride is used for washing an organic phase, anhydrous sodium sulfate is added for filtering, then low-temperature rotary evaporation is carried out, and an intermediate 4 is obtained after recrystallization and purification; step five, after the intermediate 4 obtained in the step four is dissolved in anhydrous toluene, adding the anhydrous toluene into a round bottom flask, slowly dripping phosphorus trichloride into a reaction liquid, and heating to 110 ℃ for reaction for 8 hours, wherein the reaction formula is as follows: After the reaction, the reaction solution is slowly cooled to 0 ℃, the reaction solution is slowly poured into saturated sodium bicarbonate solution under vigorous stirring, the water phase is extracted by ethyl acetate for 3 times, the organic phase is combined and washed by saturated sodium chloride, the organic phase is dried by anhydrous sodium sulfate, filtered and distilled to crude products, and then the crude products are purified by silica gel column chromatography (petroleum ether/ethyl acetate mixture is used as eluent) to obtain an intermediate 5; Step six, dissolving the intermediate 5 obtained in the step five in dichloromethane, cooling to 0 ℃ in an ice water bath, slowly dripping the acetyl nitrate solution cooled to 0 ℃ into a reaction liquid through a dripping funnel under intense stirring, keeping the temperature at 0 ℃ in the dripping process, and continuing to stir at 0 ℃ for 3 hours after the dripping is finished, wherein the reaction formula is as follows: After the reaction is finished, pouring the reaction solution into ice water, extracting the water phase with dichloromethane three times, combining the organic phases, washing the organic phases with ice water, saturated sodium bicarbonate solution and saturated sodium chloride, drying the organic phases with anhydrous magnesium sulfate, and filtering and steaming the organic phases to obtain an intermediate 6; Step seven, the intermediate 6 obtained in the step six is heated and refluxed in an ethanol/hydrochloric acid solution by using excessive stannous chloride in a flask to react, wherein the reaction formula is as follows: after the reaction is finished, filtering to remove the solid catalyst, and recrystallizing and purifying to obtain an intermediate 7; And step eight, dissolving the intermediate 7 obtained in the step seven in dilute hydrochloric acid (HCl), and cooling to 0-5 ℃ in an ice bath. Slowly dropwise adding an aqueous solution of NaNO 2 under intense stirring, and after the reaction is completed, adding the obtained diazonium salt solution into a sodium sulfite solution under cooling and then properly heating to complete the reaction, wherein the reaction formula is as follows: drying and purifying the obtained product to obtain an intermediate 8; step nine, after the intermediate 8 obtained in the step eight is dissolved in dichloromethane, pouring the dichloromethane into a round bottom flask, adding a little triethylamine, slowly dropwise adding acryloyl chloride at 0 ℃, reacting for 1-2 hours after dropwise adding, gradually heating to room temperature, and continuously stirring for 12 hours, wherein the reaction formula is as follows: After the reaction was completed, the reaction solution was poured into a saturated ammonium chloride solution, extracted 3 times with DCM, and the organic phases were combined, washed with a saturated sodium bicarbonate solution and a sodium chloride solution, then dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain functional monomer S.
  3. 3. The application of the salt-resistant functional monomer suitable for the high-salt oilfield environment according to claim 1, wherein the functional monomer S is used for synthesizing a salt-resistant polymer suitable for the high-salt oilfield environment, and the salt-resistant polymer suitable for the high-salt oilfield environment comprises, by weight, 210-260 parts of acrylamide, 15-30 parts of AMPS, 6-15 parts of AEO-9, 20-50 parts of the functional monomer S, 10-20 parts of urea, 0.2-0.3 part of 1# initiator, 0.05-0.15 part of 2# initiator, 0.05-0.15 part of 3# initiator, 0.1-0.3 part of 4# initiator and water for up to 1000 parts.
  4. 4. The use of a salt-tolerant functional monomer suitable for use in a high salt oilfield environment of claim 3, wherein: the initiator # 1 is one or more of azodiisobutyronitrile, azodiisoheptonitrile or azodiisobutylamidine hydrochloride.
  5. 5. The method of claim 3, wherein the initiator # 2 is one or more of sodium formate, sodium acetate or isopropanol.
  6. 6. The method of claim 3, wherein the 3# initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
  7. 7. The method of claim 3, wherein the initiator # 4 is one or more of sodium bisulphite, sodium thiosulfate and triethanolamine.
  8. 8. The use of the salt-resistant functional monomer for high-salt oilfield environments according to any one of claims 3 to 7, wherein the preparation method of the salt-resistant polymer comprises the following steps: (1) Mixing the functional monomer S and AEO-9 for later use; (2) Dissolving AMPS with ice water and then neutralizing with sodium carbonate; (3) Adding urea and water into acrylamide and the monomer prepared in the steps (1) and (2), uniformly stirring and mixing, and then adjusting the pH value to 7.0-7.5 by using 30% sodium hydroxide solution; (4) Transferring the solution prepared in the step (3) to an adiabatic reaction kettle after the temperature of the solution is regulated to 4-6 ℃, and then introducing nitrogen for 30min to remove oxygen, adding a 1# initiator 2# initiator into the reaction kettle after deoxidization, adding a 3# initiator after 5min, adding a 4# initiator after 5min, stopping introducing nitrogen after the temperature of the system in the kettle begins to rise, and continuing to age for 4h after the temperature is not raised any more after the reaction is completed, thus obtaining polymer colloid; (5) Crushing the polymer colloid obtained in the step (4), adding solid sodium hydroxide, fully mixing, hydrolyzing for 6 hours at the temperature of 75 ℃, drying for 12 hours at the temperature of 60 ℃, crushing and screening to obtain particles with the particle size of 400-800 mu m, wherein the particles are the finished product of the salt-resistant polymer suitable for the environment of a high-salt oil field.

Description

Salt-resistant functional monomer suitable for high-salt oilfield environment and preparation method thereof Technical Field The invention belongs to the technical field of petroleum exploitation, and particularly relates to a salt-resistant functional monomer suitable for a high-salt oilfield environment and a preparation method thereof. Background With the continuous growth of global energy demands and the increasing exhaustion of easily-extracted petroleum resources, efficient development of complex oil reservoirs has become an urgent task for the petroleum industry. The high-salinity oil reservoir is rich in reserves, but the exploitation difficulty is extremely high. Polymer flooding is one of key technologies for improving crude oil recovery efficiency in tertiary oil recovery, and is characterized in that high polymer solution is injected into an oil layer, so that the viscosity of an aqueous phase is increased, the fluidity ratio of water to oil is reduced, the swept volume is enlarged, and more residual oil is displaced. At present, the partially hydrolyzed polyacrylamide is the most widely applied polymer in the polymer flooding technology, and mainly benefits from the advantages of low cost, strong tackifying capability, easy industrial production and the like. However, the application of HPAM in high-salt oil reservoir environment faces serious challenges, and although the salt-resistant functional monomers and polymers used in high-salt oil fields in the prior art have a certain effect, one or more defects of limited salt resistance, high synthesis cost, poor polymerization activity, poor solubility of the final product and the like are commonly existed. Therefore, the field has urgent need of a novel functional monomer which has simple synthetic route, controllable cost and high polymerization activity and can endow the polymer with excellent salt resistance and calcium resistance, and the product has huge market space. Disclosure of Invention In order to solve the problems, the invention provides a salt-resistant functional monomer suitable for a high-salt oilfield environment and a preparation method thereof, and a polymer synthesized by using the functional monomer has the characteristics of high salt resistance, high tackifying property, high viscosity stability and capability of being prepared by using oilfield produced sewage, can keep good solubility under the sewage condition, and improves petroleum recovery ratio. The invention adopts the technical scheme that a salt-resistant functional monomer suitable for the high-salt oilfield environment is synthesized, and the functional monomer is used for synthesizing a salt-resistant polymer suitable for the high-salt oilfield environment; The salt-resistant polymer comprises, by weight, 210-260 parts of acrylamide, 15-30 parts of AMPS, 6-15 parts of AEO-9, 20-50 parts of functional monomers S, 10-20 parts of urea, 0.2-0.3 part of 1# initiator, 0.05-0.15 part of 2# initiator, 0.05-0.15 part of 3# initiator, 0.1-0.3 part of 4# initiator and 1000 parts of water. Further, the 1# initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile or azodiisobutylamidine hydrochloride. Further, the 2# initiator is one or more of sodium formate, sodium acetate or isopropanol. Further, the 3# initiator is one or more of ammonium persulfate, potassium persulfate or sodium persulfate. Further, the 4# initiator is one or more of sodium bisulphite, sodium thiosulfate or triethanolamine. Further, the functional monomer S is: further, the preparation method of the functional monomer S comprises the following steps: step one, adding a solvent p-tert-butyl bromobenzene into a reaction kettle, wherein the molecular formula is as follows: Continuously adding cyclohexylboric acid into a reaction kettle, continuously introducing nitrogen, then adding a palladium catalyst Pd (dppf) Cl 2, adding a water-soluble potassium carbonate solution, and then adding a solvent 1, 4-dioxane, heating the reaction kettle to 80-90 ℃, stirring and refluxing for reaction for about 12 hours, wherein the reaction formula is as follows: After the reaction is finished, cooling the reaction solution to room temperature, adding water and ethyl acetate in a ratio of about 1:1, starting to extract for 2-3 times, merging all organic phases, washing the organic phases once by using a saturated sodium chloride solution, drying the organic phases by using anhydrous sodium sulfate, filtering, steaming to remove a solvent in a rotary way, and purifying by using a mixed solvent of petroleum ether and ethyl acetate as an eluent through a silica gel column chromatography to obtain an intermediate 1; step two, adding the intermediate 1 obtained in the step one and solvent methylene dichloride into a reaction kettle, and slowly dropwise adding nitric acid and sulfuric acid mixed acid at the temperature of 0-5 ℃ for reaction, wherein the reaction formula is as follows: ; After the reaction, pour