CN112341567B - Thickener for supercritical carbon dioxide flooding and preparation method and application thereof - Google Patents
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Abstract
The invention provides a thickener for supercritical carbon dioxide flooding and a preparation method and application thereof. The thickening agent is prepared by polymerizing fluorine-containing acrylate, tertiary amine group-containing acrylate and styrene serving as monomers through a free radical body. The thickener for supercritical carbon dioxide flooding has low cloud point pressure and excellent tackifying performance, and can be used for a supercritical carbon dioxide flooding process for further improving the recovery ratio after oil field polymer flooding.
Description
Technical Field
The invention relates to a thickening agent, in particular to a thickening agent for supercritical carbon dioxide, and belongs to the technical field of oil exploitation.
Background
In recent years, most of domestic main land sandstone oil fields are developed for decades and enter an ultra-high water-cut period, and have large potential for excavation, but the existing oil displacement system cannot efficiently use a low-permeability area and a large amount of residual oil on the upper part of an oil layer and is mainly influenced by factors such as reservoir heterogeneity, gravity differentiation caused by oil-water density difference and the like.
Supercritical carbon dioxide (scCO)2) The oil displacement system has lower density than crude oil, can generate a floating effect in a stratum, and has the potential of using residual oil in a low-permeability area at the upper part of a reservoir and an upper area of an used oil layer. scCO2The carbon dioxide is injected into an oil reservoir to reach a supercritical state under the conditions of formation pressure and temperature, can form strong interaction with light alkane, and is easy to generate lower miscible pressure with crude oil to realize miscible flooding. Although scCO2The oil extraction technology has rapidly developed in the last thirty years, but a plurality of technical problems are gradually exposed in the use process, and the specific influence factors are as follows: (1) premature gas breakthrough and small swept volume; (2) the minimum miscible pressure is higher; (3) corrosion problems; (4) air source problem.
Supercritical carbon dioxide thickeners can solve the first two problems. Huang et al synthesized a series of fluorinated acrylate and styrene random copolymers polyFAST by free radical copolymerization, and found that the polymers have excellent solubility and viscosity-increasing properties through intermolecular association. At 25 deg.CAnd polyFAST in scCO at 34.48MPa2The dissolved amount in the solution is up to 5 wt%, and the relative viscosity is pure CO2400 times higher than the original value. Such as Zhuhua Huang, Chunmei Shi, Jianhang Xu, Sevgi Kilic, Robert M.Enick, and Eric J.Beckman.Enhance of viscidity of carbo dioxide using styrene/fluoroacrylate copolymers, macromolecules.2000,33(15):5437-2Has good solubility, and has the advantages of no toxicity, low cost, easy acquisition and the like. To lower the cloud point pressure of PDMS, small organic molecules can be added to aid dissolution. CN201610182956 proposes a scCO2Thickener, in scCO2The catalyst is prepared by taking micromolecules (toluene and ethylene glycol dimethyl ether) as a cosolvent, PDMS as a dispersant, 2-ethylhexyl acrylate and styrene as monomers, sodium dodecyl benzene sulfonate as an auxiliary dispersant and azodiisobutyronitrile as an initiator by adopting an in-situ polymerization method. The thickener system is prepared under the conditions of 35 ℃, 10MPa and 3 wt% of dosage in scCO2The medium viscosity can reach 4.72 mPas, and the tackifying multiple can reach 160 times. Although the method can reduce the using amount and the using cost of the silicon-containing polymer, a large amount of small molecular organic cosolvent is used, which has some potential hazards to environmental pollution and process operation, thereby limiting the application of the thickening agent in supercritical carbon dioxide flooding. CN201310175367 proposes a method of screening by scCO2The carbon dioxide fracturing fluid consists of a thickening agent and a multi-effect additive. At 40 ℃ and higher cloud point pressure, 0.1 wt% of thickening agent polycarbonate-chlorostyrene copolymer (molecular weight is 10-50 ten thousand) and 0.01 wt% of sodium perfluoroalkyl benzene sulfonate additive mixed system2The viscosity of (3) was 22.3 mPas. But the cloud point pressure of the thickener is too high (higher than the formation pressure) or the using concentration of the thickener is too high, so that the oil displacement effect of the supercritical carbon dioxide is seriously influenced.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an amphiphilic copolymer thickener for supercritical carbon dioxide flooding, which has good tackifying performance and low solubility of cloud point pressure and can maintain long-term and efficient flooding performance for low-permeability and upper-middle reservoirs of oil layers.
In order to achieve the purpose, the invention firstly provides a thickening agent for supercritical carbon dioxide flooding, which is prepared by taking fluorine-containing acrylate, tertiary amine group-containing acrylate and styrene as polymerization monomers and carrying out free radical bulk polymerization.
The thickener for supercritical carbon dioxide flooding disclosed by the invention is an amphiphilic copolymer thickener, can realize the supercritical state of carbon dioxide under lower formation pressure, forms stronger interaction with light alkane, and realizes miscible flooding under lower miscible pressure.
In one embodiment of the present invention, the content of the fluorine-containing acrylate monomer is 55 to 60% of the total molar amount of the polymerized monomers; preferably 58%. Wherein the fluorine-containing acrylate monomer is any one of trifluoroethyl (meth) acrylate, hexafluorobutyl (meth) acrylate and dodecafluoroheptyl (meth) acrylate; dodecafluoroheptyl (meth) acrylate is preferred.
In one embodiment of the invention, the tertiary amino acrylate-containing monomer is present in an amount of 10% to 15% of the total molar amount of polymerized monomers. Wherein the acrylate monomer containing tertiary amine group is 2- (dimethylamino) ethyl methacrylate.
In one embodiment of the invention, the styrene monomer is present in an amount of 27% to 32% of the total molar amount of polymerized monomers.
In one embodiment of the present invention, the azo compound is used as the initiator in the free radical mass polymerization, and the amount of the initiator added is 2.0X 10 times the total molar content of the monomers to be polymerized-5-4.8×10-3(ii) a Wherein the azo compound is azobisisobutyronitrile or azobisisoheptonitrile; preferably azobisisoheptonitrile.
The saturated dissolution amount of the thickener for supercritical carbon dioxide flooding is 1.2%, and the thickener is uniformly dissolved in a supercritical carbon dioxide solution at 45 ℃, so that the minimum cloud point pressure of the supercritical carbon dioxide solution can reach 12MPa, and the viscosity of the supercritical carbon dioxide solution can be increased to 2.0 mPa.
The thickener for supercritical carbon dioxide flooding can be used in a supercritical carbon dioxide flooding process.
The invention also provides a preparation method of the thickener for supercritical carbon dioxide flooding, which comprises the step of carrying out polymerization reaction by uniformly mixing the polymerized monomer and the initiator by ultrasound; wherein the polymerization temperature is 50-55 ℃, and the polymerization time is 12-24 h.
The preparation method of the thickener for supercritical carbon dioxide flooding disclosed by the invention is carried out according to the following reaction formula:
the invention also provides a supercritical carbon dioxide oil-displacing agent, wherein the supercritical carbon dioxide oil-displacing agent comprises the thickener for supercritical carbon dioxide oil displacement. The cloud point pressure of the supercritical carbon dioxide oil displacement agent is 12MPa, and the viscosity is 2.0 mPas.
Supercritical CO of the invention2The thickening agent for oil displacement is prepared by optimizing the composition and adopting a bulk polymerization method to prepare the amphiphilic copolymer, the preparation method is simple, the raw material source is rich, and convenience is provided for industrial production.
Supercritical CO of the invention2The cloud point pressure of the thickener for oil displacement is lower. Based on the principle of polymer dissolving thermodynamics, the tertiary amine chain segment and CO are used2The Lewis acid-base interaction of (A) promoting in scCO2So that the amphiphilic copolymer is dissolved in supercritical CO2Has excellent dissolving performance and lower turbid point pressure. The lower cloud point pressure of the thickening agent is beneficial to reaching a supercritical state with carbon dioxide under the conditions of reservoir formation pressure and temperature, and strong mutual dissolution with light alkane is promoted, so that the oil displacement efficiency is improved.
Supercritical CO of the invention2Oil displacement thickener in scCO2The medium thickening performance is excellent. The amphiphilic copolymer is prepared by copolymerization of hydrophilic and hydrophobic carbon dioxide monomers, and hydrophobic CO is utilized2Intermolecular association enhancing polymer in scCO2The medium aggregate size increases the viscosity of the amphiphilic copolymer in supercritical carbon dioxide, as shown in figure 1. The excellent tackifying performance of the thickener is beneficial to improving the fluidity ratio of a displacement phase and increasing the swept volume, thereby improving the oil displacement efficiency.
Drawings
FIG. 1 shows the thickener in scCO2Schematic representation of intermolecular association.
FIG. 2 is a graph of viscosity versus pressure for the solution of dissolved supercritical carbon dioxide of example 2.
FIG. 3 is a graph of viscosity versus pressure for a solution of supercritical carbon dioxide in example 3.
FIG. 4 is an infrared spectrum of the product of example 3.
FIG. 5 is a photograph of the product of example 31H-NMR spectrum.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Comparative example 1
The comparative example provides a thickener obtained by polymerizing the following polymerization monomers under the action of an initiator:
polymerizing monomers: the dodecafluoroheptyl methacrylate and the styrene respectively account for 73 mol percent and 27 mol percent in the polymerized monomers.
Initiator: azobisisobutyronitrile, in an amount of 0.48% of the total molar content of the polymerized monomers.
The polymerization temperature was 60 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 12MPa and the solution viscosity to be 0.12 mPa.s.
Comparative example 2
The comparative example provides a thickener obtained by polymerizing the following polymerization monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 68 percent, 5 percent and 27 percent respectively.
Initiator: the dosage of the azodiisoheptanonitrile is 0.48 percent of the total molar content of the monomers.
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 17MPa and the solution viscosity to be 0.42 mPa.s.
Comparative example 3
The comparative example provides a thickener obtained by polymerizing the following polymerization monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 63 percent, 10 percent and 27 percent respectively.
Initiator: the dosage of the azodiisoheptanonitrile is 0.48 percent of the total molar content of the monomers.
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 15MPa and the solution viscosity to be 0.63 mPa.s.
Example 1
This example provides a thickener obtained by polymerizing the following monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 58 percent, 15 percent and 27 percent respectively by mol.
Initiator: azobisisoheptonitrile in an amount of 4.8X 10 based on the total molar amount of the monomers-3。
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 14MPa and the solution viscosity to be 0.74 mPas.
Example 2
This example provides a thickener, substantially the same as example 1, except that: the initiator azobisisoheptonitrile is used in an amount of 4.36X 10 based on the total molar content of the monomers-5。
The experimental results are as follows: after uniform dissolution in supercritical carbon dioxide at 45 ℃, the cloud point pressure was measured to be 13MPa, and the solution viscosity was measured to be 1.3MPa · s, as shown in fig. 2.
Example 3
This example provides a thickener obtained by polymerizing the following monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 58 percent, 15 percent and 27 percent respectively by mol. The initiator is azobisisoheptonitrile, and the dosage is 2.37 multiplied by 10 of the total molar content of the monomers-5。
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
The experimental results are as follows: after uniform dissolution in supercritical carbon dioxide at 45 ℃, the cloud point pressure was measured to be 12MPa and the solution viscosity was measured to be about 2.0MPa · s, as shown in fig. 3.
The sample of example 3 was dried and then pressed with KBr and measured by Nicolet Nexus 470 FT-IR infrared spectrometer (Nicolet Co., USA). FIG. 4 is an infrared spectrum of example 3. As can be seen from FIG. 5, 3010cm-1The C-H bond stretching vibration peak of benzene ring is 1560cm-1、1542cm-1、1510cm-1、1458cm-1Is the stretching vibration peak of unsaturated carbon-carbon double bond on benzene ring. 2960cm-1And 2923cm-1Is the C-H bond stretching vibration peak of methyl and methylene, 2850cm-1Is the C-N bond stretching vibration peak. 1774cm-1And 1147cm-1And C ═ O and C-O bond stretching vibration peaks. 1868cm-1Is the stretching vibration peak of carbonyl group connected with fluorocarbon chain. 1072cm-1And 669cm-1Is the stretching vibration peak and bend of C-F bondA peak of flexural vibration. From the results of infrared analysis, it was found that styrene, 2- (dimethylamino) ethyl methacrylate and dodecafluoroheptyl methacrylate monomers had been successfully polymerized.
The polymer of example 3 was used as a deuterated chloroform solvent1The results of H-NMR measurement are shown in FIG. 5. 0.92-1.19ppm is methyl (-CH) attached to the backbone3) Chemical shift of upper hydrogen atom (1), 1.37-1.81ppm is methylene (-CH) in main chain2-) and the chemical shift of the hydrogen atom (2) on the methine group (-CH-), 1.98ppm being the end group of the fluorocarbon chain (-CF)2H) Chemical shift of hydrogen atom (4), 2.37ppm is a methyl group (-CH) bonded to a nitrogen atom3) Chemical shift of the upper hydrogen atom (3), 2.54ppm is methylene (-CH) attached to a tertiary amine2-) chemical shift of the hydrogen atom (5) on the ester, 4.13 to 4.34ppm being the methylene group (-CH) attached to the ester group2-) chemical shift of the hydrogen atom (6) on the ester (-CO-O-H), 4.51ppm is the methylene (-CH) group attached to the ester group and the fluorocarbon chain2-) chemical shift of hydrogen atom (7) on the benzene ring, 6.46-7.29ppm are chemical shifts of hydrogen atom (8) on the benzene ring. By1H-NMR test results show that styrene, 2- (dimethylamino) ethyl methacrylate and dodecafluoroheptyl methacrylate monomers have been successfully polymerized.
Example 4
This example provides a thickener obtained by polymerizing the following monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 58 percent, 15 percent and 27 percent respectively by mol.
The initiator is azobisisoheptonitrile, and the dosage is 2.0X 10 of the total molar content of the monomers-5。
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
The experimental results are as follows: after uniform dissolution in supercritical carbon dioxide at 45 ℃, the cloud point pressure was measured to be 12MPa and the solution viscosity was measured to be 1.5MPa · s.
Comparative example 4
The comparative example provides a thickener obtained by polymerizing the following polymerization monomers under the action of an initiator:
polymerizing monomers: the dodecafluoroheptyl methacrylate, the 2- (dimethylamino) ethyl methacrylate and the styrene respectively account for 60 percent, 15 percent and 25 percent of the molar percentage in the polymerized monomers,
initiator: azobisisoheptonitrile in an amount of 2.37X 10 based on the total molar content of the monomers-5。
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 11MPa and the solution viscosity to be 0.59 mPa.s.
Comparative example 5
The comparative example provides a thickener obtained by polymerizing the following polymerization monomers under the action of an initiator:
polymerizing monomers: the content of the methacrylic acid dodecafluoroheptyl ester, the 2- (dimethylamino) ethyl methacrylate and the styrene in the polymerized monomers is 53 percent, 15 percent and 32 percent respectively.
Initiator: azobisisoheptonitrile in an amount of 2.37X 10 based on the total molar content of the monomers-5。
The polymerization temperature was 55 ℃ and the reaction time was 24 hours.
Placing the product in a high-temperature high-pressure viscometer, and after the product is uniformly dissolved in supercritical carbon dioxide at the temperature of 45 ℃, measuring the cloud point pressure to be 20MPa and the solution viscosity to be 2.6 mPa.s.
Claims (6)
1. A thickener for supercritical carbon dioxide flooding is prepared by taking fluorine-containing acrylate, tertiary amine acrylate and styrene as polymerization monomers and performing bulk polymerization on free radicals;
the fluorine-containing acrylate monomer is dodecafluoroheptyl (meth) acrylate, and the content of the fluorine-containing acrylate monomer is 55-60% of the total molar amount of the polymerized monomers;
the tertiary amine group-containing acrylate monomer is 2- (dimethylamino) ethyl methacrylate, and the content of the tertiary amine group-containing acrylate monomer is 10-15% of the total mole amount of the polymerized monomers;
the content of the styrene monomer is 27 to 32 percent of the total mol amount of the polymerized monomer;
in free matrix polymerization, azo compounds are used as initiator, and the addition amount of the initiator is 2.0 x 10 of the total molar content of the polymerization monomers-5-4.8×10-3(ii) a The azo compound is azobisisoheptonitrile.
2. The thickener of claim 1, wherein the fluoroacrylate monomer is present in an amount of 58% of the total molar amount of polymerized monomers.
3. Use of the thickener for supercritical carbon dioxide flooding according to claim 1 or 2 in a supercritical carbon dioxide flooding process.
4. The method for preparing the thickener for supercritical carbon dioxide flooding according to claim 1 or 2, wherein the polymerization temperature in the preparation method is 50-55 ℃, and the polymerization time is 12-24 h.
5. A supercritical carbon dioxide oil-displacing agent, which comprises the thickener for supercritical carbon dioxide flooding according to claim 1 or 2.
6. The supercritical carbon dioxide oil-displacing agent according to claim 5, wherein dodecafluoroheptyl (meth) acrylate accounting for 58 mol% of the total amount of the polymerized monomers, 2- (dimethylamino) ethyl methacrylate accounting for 15 mol% of the total amount of the polymerized monomers, and styrene accounting for 27 mol% of the total amount of the polymerized monomers are used as reaction monomers, and the total amount of the polymerized monomers is 2.37 x 10-5The azodiisoheptanonitrile is used as an initiator, and the thickener for supercritical carbon dioxide oil displacement prepared by free radical bulk polymerization enables the cloud point pressure of the supercritical carbon dioxide oil displacement agent to be 12MPa and the viscosity to be 2.0mPa & s.
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