CN115261002B - Superparamagnetism graphene oxide oil displacement agent and preparation method thereof - Google Patents
Superparamagnetism graphene oxide oil displacement agent and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 196
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- 229940075468 lauramidopropyl betaine Drugs 0.000 claims description 17
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- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 4
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- 229920000120 polyethyl acrylate Polymers 0.000 claims description 2
- GEGGDDNVHQPTCS-QXMHVHEDSA-N 2-[3-[[(z)-docos-13-enoyl]amino]propyl-dimethylazaniumyl]acetate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O GEGGDDNVHQPTCS-QXMHVHEDSA-N 0.000 claims 1
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- 239000003381 stabilizer Substances 0.000 description 1
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention discloses a superparamagnetic graphene oxide oil displacement agent and a preparation method thereof. The preparation method comprises the following steps: dispersing graphene oxide in N, N-dimethylformamide, and adding ethylenediamine to react to obtain aminated graphene oxide; combining the aminated graphene oxide, an iron source and NH 3 ·H 2 O‑NH 4 NO 3 Mixing the solutions to react to obtain the magnetic amination graphene oxide; and adding the magnetic amination graphene oxide, a surfactant and a polycarboxylate water reducer into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent. The invention designs a novel surfactant material with a magnetic group structural unit, endows the novel surfactant material with the capability of bidirectional reversible regulation and control according to the change of an external magnetic field, realizes the full-flow intelligent regulation and control of the performance of the oil-displacing surfactant, improves the salt resistance, further greatly improves the oil-water separation efficiency of produced liquid in the oil-displacing process, simplifies the production flow and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to a superparamagnetic graphene oxide oil displacement agent and a preparation method thereof.
Background
A large number of oil fields enter a tertiary oil recovery stage mainly comprising chemical flooding, but are limited by resource grade, oil reservoir conditions, high salt content of oil reservoirs and development modes, and nearly 50% of crude oil still remains underground in a residual oil mode after tertiary oil recovery. In view of the huge reserves of the residual oil resources, if the residual oil can be effectively utilized, the contribution of the residual oil is not inferior to that of a plurality of newly discovered large oil fields, so the development of the residual oil is of great importance. The residual oil distribution is scattered, the reservoir heterogeneity is prominent, the existing exploitation technology is difficult to effectively drive, and the development of a main body succession technology is urgently needed. Only breakthroughs in innovative technology can be made to increase the recovery of the remaining oil. More and more research considers that emulsion flooding or microemulsion flooding is an important mechanism for greatly improving recovery efficiency of chemical flooding.
Surfactants having the functions of reducing surface tension, improving medium wettability, emulsifying, penetrating, improving salt resistance, foaming and the like are required to solubilize hydrophobic organics, stabilize gas-liquid or liquid-liquid interfaces in various oil and gas development processes (such as drilling and completion, fracturing and acidizing, chemical compound flooding, gas well drainage and gas production, thickened oil chemical exploitation, high-efficiency treatment of produced liquid, oil and gas gathering and transportation, and the like). However, after the conventional surfactant acts, the conventional surfactant is often difficult to separate from the solubilizing substances, so that the subsequent treatment cost is high, the produced liquid is difficult to treat, and the produced liquid is directly discharged, so that a large amount of waste is caused, and serious environmental pollution is caused. Research data shows that if the surfactant can be effectively recycled, the running cost can be saved by about 70%.
Magnetically responsive surfactants are a novel class of surfactants that are nanoparticles with superparamagnetism. Superparamagnetism refers to a ferromagnetic substance with a single domain structure when the particle is smaller than the critical dimension, and the particle is paramagnetic when the temperature is lower than the curie temperature and higher than the transition temperature, but the paramagnetic susceptibility of the particle is far higher than that of a common paramagnetic material under the action of an external magnetic field. The magnetization curve of the superparamagnetic body is different from that of the ferromagnetic body, and hysteresis phenomenon is avoided. When the external magnetic field is removed, the remanence quickly disappears. The magnetic particles can be used as emulsion stabilizers to prepare Pickering emulsion (magnetic emulsion), and the magnetic emulsion can be demulsified through magnetic response under the action of an external magnetic field. The interface activity can be regulated and controlled bidirectionally according to the environmental change. The active agent can change aggregation behavior in a solution under external stimulus, so as to change rheological property of a system. The characteristics lead the surfactant to have wider application prospect, and intensive research and utilization are needed. Graphene oxide is a two-dimensional carbon material with a large specific surface area and a large number of active reactive groups, and is an ideal carrier of a magnetically responsive surfactant.
Disclosure of Invention
Based on the background technology, the invention provides a superparamagnetic graphene oxide oil displacement agent and a preparation method thereof. According to the invention, through researching a molecular structure model, a novel surfactant material with a magnetic group structural unit is designed, the capability of bidirectional reversible regulation and control according to the change of an external magnetic field is endowed, the full-flow intelligent regulation and control of the performance of the oil-displacing surfactant is realized, the oil-water separation efficiency of produced liquid in the oil-displacing process is greatly improved, the production flow is simplified, and the production cost is reduced.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a superparamagnetic graphene oxide oil displacement agent, which comprises the following steps:
dispersing graphene oxide in N, N-dimethylformamide to obtain graphene oxide dispersion liquid; adding ethylenediamine into the graphene oxide dispersion liquid to react to obtain aminated graphene oxide;
combining the aminated graphene oxide, an iron source and NH 3 ·H 2 O-NH 4 NO 3 Mixing the solutions to react to obtain the magnetic amination graphene oxide;
and adding the magnetic amination graphene oxide, a surfactant and a polycarboxylate water reducer into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent.
The invention prepares the self-demulsification type oil displacement agent with magnetic group structural units, and the oil displacement agent is a nano-scale particle with superparamagnetism. According to the preparation method disclosed by the invention, graphene oxide, a surfactant and a polycarboxylate water reducer can be subjected to grafting modification under milder conditions, so that the salt resistance of an oil displacement agent is improved, superparamagnetism is endowed, the oil-water emulsification performance can be bidirectionally and reversibly regulated and controlled according to the change of an external magnetic field, the oil-water can be efficiently emulsified, and the oil-water separation efficiency of oil field produced liquid can be greatly improved, the production flow is simplified, the oil displacement agent can be recycled and reused, the cost is reduced, and the full-flow regulation and control of the oil displacement surfactant performance is finally realized.
According to the production method of the present invention, preferably, the reactions in the production method are all carried out in an ultrasonic reactor; more preferably an ultrasonic magnetic storm wall breaking machine.
The invention adopts NH 3 ·H 2 O-NH 4 NO 3 The solution replaces the traditional NaOH or NH 3 ·H 2 Preparation of Fe from O solution 3 O 4 The microsphere not only can effectively reduce the corrosion to the ultrasonic reactor, but also can stabilize the pH value of the system, so that the pH value of the system in the reaction process can be always kept within the range of 9.2-10.5, thereby effectively avoiding the problem of continuous reduction of the alkalinity of the system and product quality reduction caused by continuous consumption of hydroxyl ions in the reaction process.
In the ultrasonic process, an ultrasonic magnetic storm wall breaking machine is used as an ultrasonic reactor: the whole preparation process of the superparamagnetic graphene oil displacement agent is carried out under the ultrasonic condition. In this way, graphene oxide can be uniformly dispersed in a solution first; secondly, the reaction solution can be ensured to penetrate into the graphene oxide sheet layers, so that the magnetic nanoparticles grow between the graphene oxide sheet layers and can prop open the graphene oxide, the contact area is larger, and the magnetic nanoparticles are ensured to be uniformly distributed and not to agglomerate; finally, the surfactant and the polycarboxylate water reducer can be uniformly and effectively grafted on the graphene oxide, and the oil-water emulsification performance of the graphene oxide is ensured.
The preparation method of the invention can be divided into three steps of preparing the amination graphene oxide, preparing the magnetic amination graphene oxide, preparing the oil displacement agent and the like, and each step is described in detail below.
Preparing aminated graphene oxide: dispersing graphene oxide in N, N-dimethylformamide to obtain graphene oxide dispersion liquid; and adding ethylenediamine into the graphene oxide dispersion liquid to react, so as to obtain the aminated graphene oxide.
According to the method, the amino modified graphene oxide is utilized to enable the graphene oxide to have a functional group with extremely strong activity, namely amino, the surfactant and the polycarboxylate superplasticizer can be effectively grafted under mild conditions, so that the problem of poor oil-water emulsification effect of the graphene oil displacement agent is solved.
According to the preparation method of the present invention, preferably, the step of preparing the aminated graphene oxide includes:
dispersing graphene oxide in N, N-dimethylformamide, adding ethylenediamine after ultrasonic treatment for 45-60 min, heating to 40-60 ℃ and continuing ultrasonic treatment for 23-24 h, centrifuging, washing, and drying to obtain the aminated graphene oxide.
The purpose of ultrasonic treatment of graphene oxide in DMF is to better disperse, and ethylenediamine is added for amination.
According to the production method of the present invention, preferably, the ratio of the graphene oxide to the N, N-dimethylformamide is (0.2 to 0.4) g:100mL; the volume ratio of the ethylenediamine to the graphene oxide dispersion liquid is (1.5-2.5): 1, more preferably 2:1.
According to the preparation method of the present invention, preferably, in the step of preparing the aminated graphene oxide, the washed solvent is water and ethanol.
Preparing magnetic amination graphene oxide: combining the aminated graphene oxide, an iron source and NH 3 ·H 2 O-NH 4 NO 3 And mixing the solutions to react to obtain the magnetic amination graphene oxide.
According to the preparation method of the present invention, preferably, the step of preparing the magnetic aminated graphene oxide includes:
dispersing the amination graphene oxide and an iron source in deionized water, ultrasonically heating to 40-70 ℃ for 2h, and then adding NH 3 ·H 2 O-NH 4 NO 3 The pH value of the solution to the system is=9.2-10.5, the temperature is raised to 70-90 ℃ for ultrasonic reaction for 45-60 min, and the reaction is carried outAnd after finishing, centrifuging and washing, and then drying to obtain the magnetic amination graphene oxide.
According to the preparation method of the present invention, preferably, the NH 3 ·H 2 O-NH 4 NO 3 NH in solution 3 ·H 2 O and NH 4 NO 3 The molar ratio of (2) to (4) to (1).
According to the preparation method of the present invention, preferably, the mass ratio of the aminated graphene oxide to the iron source is 1: (0.8-1.2), wherein the mass of the iron source is Fe 3 O 4 Is a mass of (c) a (c). When the dosage of the amination graphene oxide is too high, the prepared magnetic amination graphene oxide has lower magnetism; when the amount of the aminated graphene oxide is too low, the grafted surfactant content is low, so that the emulsifying property is affected. More preferably, the mass ratio of the aminated graphene oxide to the iron source is 1:1 (the mass of the iron source is calculated as Fe 3 O 4 Mass meter of (c).
According to the production method of the present invention, preferably, the iron source includes a ferrous salt and a ferric salt; the molar ratio of the ferrous salt to the ferric salt is 1 (1-3), and excessive Fe is formed when the ratio exceeds the range 2 O 3 Affecting its magnetic and emulsifying effects. More preferably, the iron source comprises ferrous and ferric salts; the molar ratio of the ferrous salt to the ferric salt is 1:2.
according to the production method of the present invention, preferably, the divalent iron salt is FeCl 2 Or FeSO 4 The ferric salt is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 。
According to the preparation method of the present invention, preferably, in the step of preparing the magnetic aminated graphene oxide, the washed solvent is water and ethanol.
And (3) preparing an oil displacement agent: and adding the magnetic amination graphene oxide, a surfactant and a polycarboxylate water reducer into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent.
According to the production method of the present invention, preferably, the surfactant is selected from one or a combination of two or more of betaine-type surfactants.
According to the preparation method of the present invention, preferably, the betaine-type surfactant includes lauramidopropyl betaine, amidopropyl betaine, and dodecyl dimethyl betaine. More preferably, the surfactant is lauramidopropyl betaine. The lauramidopropyl betaine has the properties of salt resistance and high temperature resistance, can effectively reduce the interfacial tension between oil and water, and has good interfacial emulsification performance for high-mineralization and high-temperature oil reservoirs.
According to the preparation method of the present invention, preferably, the polycarboxylic acid water reducing agent is selected from one or a combination of two or more of polyacrylic acid water reducing agents.
According to the preparation method of the present invention, preferably, the polyacrylic water reducing agent includes polyacrylic acid, polymethacrylic acid and polyethyl acrylate. Further preferably, the polycarboxylate water reducer is polyacrylic acid. The polyacrylic acid has the properties of salt resistance and alkali resistance, can effectively improve the salt resistance, and shows good salt resistance for high-mineralization and high-temperature oil reservoirs.
According to the preparation method of the invention, preferably, the mass ratio of the magnetic amination graphene oxide, the surfactant and the polycarboxylate superplasticizer is 2 (1-3): (1-3); more preferably 1:1:1.
according to the preparation method of the present invention, preferably, the solvent used in the step of preparing the oil-displacing agent is methanol or DMF. More preferably methanol; methanol can be more conveniently removed from the system to obtain the product.
According to the preparation method of the present invention, preferably, the reaction temperature in the step of preparing the oil-displacing agent is 45-55 ℃, and the reaction time is 1-13 h. More preferably, the temperature of the reaction is 50 ℃ and the reaction time is 12 hours.
In a second aspect, the invention provides a superparamagnetic graphene oxide oil displacement agent obtained by the preparation method.
According to the invention, the prepared superparamagnetic graphene oxide oil displacement agent is subjected to characterization evaluation, and the superparamagnetic graphene oxide oil displacement agent is still in a nano lamellar structure; the superparamagnetic graphene oxide oil displacement agent has a functional group of graphene oxide and a functional group of a grafted surfactant; the magnetization intensity of the magnetic graphene oxide oil displacement agent can reach 22emu/g, and the magnetic graphene oxide oil displacement agent belongs to a strong magnetic material. The invention can effectively graft the surfactant lauramidopropyl betaine, the polycarboxylic acid water reducer polyacrylic acid and the like, thereby increasing the salt resistance of the oil displacement agent, enabling oil-water to be emulsified efficiently, and simultaneously being capable of rapidly breaking emulsion under the condition of an externally applied magnetic field, and being expected to become an intelligent oil displacement agent for oil-gas field development of a new generation.
Drawings
Fig. 1 is a TEM photograph of the superparamagnetic graphene oxide oil-displacing agent prepared in example 1.
Fig. 2 is an infrared spectrum of the superparamagnetic graphene oxide oil-displacing agent prepared in example 1.
Fig. 3 is a hysteresis loop diagram of the superparamagnetic graphene oxide displacement agent prepared in example 1.
FIG. 4a is a graph showing the emulsion and demulsification effects of the samples prepared in example 1.
FIG. 4b is a graph showing the emulsion and demulsification effects of the samples prepared in comparative example 1.
Fig. 5 is a graph showing the emulsification effect of displacement fluids of different concentrations formulated for the samples prepared in example 1.
Fig. 6 is a plot of emulsion layer volumes for displacement fluids of different concentrations formulated for samples prepared in example 1.
Fig. 7 is a plot of emulsion layer volumes for displacement fluids of different concentrations formulated for samples prepared in example 3.
Fig. 8 is a plot of emulsion layer volumes for displacement fluids of different concentrations formulated for samples prepared in example 5.
Fig. 9 is a plot of emulsion layer volumes for displacement fluids of different concentrations formulated for samples prepared in example 7.
FIG. 10 is a graph showing the volume of the emulsion layer of displacement fluids prepared by the magnetic graphene oxide displacement agents prepared in example 1 and comparative example 4,
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about".
Example 1
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
according to AGO, feSO 4 ·7H 2 O and FeCl 3 ·6H 2 O is prepared by mixing AGO and FeSO according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C with ultrasound (P=400W) for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The pH of the solution to the system is=10, the temperature is raised to 85 ℃, the ultrasonic (P=600W) reaction is carried out for 45min, the solution is centrifugally washed for 3 times by using water and ethanol, and the Magnetic Aminated Graphene Oxide (MAGO) is obtained through freeze-drying.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding lauramidopropyl betaine (PALB) and polyacrylic acid (PAA) after ultrasonic treatment for 20min (P=400W), heating to 50deg.C for reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of MAGO, PALB and PAA is 1:1:1.
Example 2
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.3g GO was dispersed in 100mL DMF solution, after 1h of sonication (P=400W) 200mL EDA solution was added, the temperature was raised to 45℃and sonication (P=400W) continued for 24h, washed 3 times with water and ethanol centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C with ultrasound (P=400W) for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 2:1:1.
Example 3
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeCl are added according to the mass ratio of 5:5:7 2 ·4H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 SolutionTo the ph=10 of the system, the temperature is raised to 85 ℃, the ultrasonic (p=600w) reaction is carried out for 45min, the centrifugal washing is carried out for 3 times by using water and ethanol, and the MAGO is obtained after freeze-drying.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 1:1:1.
Example 4
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeCl are added according to the mass ratio of 5:5:7 2 ·4H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 2:3:3.
Example 5
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 2:2:3 4 ·7H 2 O and Fe 2 (SO 4 )·H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 1:1:1.
Example 6
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 2:2:3 4 ·7H 2 O and Fe 2 (SO 4 )·H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 2:1:1.
Example 7
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeCl are added according to the mass ratio of 1:1:2 2 ·4H 2 O and Fe 2 (SO 4 )·H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO to PALB to PAA is 1:1:1.
Example 8
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.4g GO was dispersed in 100mL DMF solution, sonicated for 1h (P=400W), 200mL EDA solution was added, warmed to 45℃and sonicated for 24h (P=400W), washed 3 times with water and ethanol by centrifugation, and lyophilized to give Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeCl are added according to the mass ratio of 1:1:2 2 ·4H 2 O and Fe 2 (SO 4 )·H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10 of the system, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation and lyophilized to obtain MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain MAGO-P. Wherein the mass ratio of MAGO, PALB and PAA is 2:1:2.
Example 9
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The pH of the solution to the system is=10, the temperature is raised to 85 ℃, the ultrasonic (P=600W) reaction is carried out for 45min, the solution is centrifugally washed for 3 times by using water and ethanol, and the Magnetic Aminated Graphene Oxide (MAGO) is obtained through freeze-drying.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MAGO in methanol solution, adding dodecyl dimethyl betaine (BS 12) and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C for reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MAGO-B). Wherein the mass ratio of MAGO, BS12 and PAA is 1:1:1.
Example 10
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) is dispersed in 100mL of N, N-Dimethylformamide (DMF), after 1h of ultrasound (P=400W), 200mL of Ethylenediamine (EDA) solution is added, the temperature is raised to 50 ℃ and ultrasound (P=400W) is continued for 23h, the mixture is centrifugally washed 3 times with water and ethanol, and the mixture is freeze-dried to obtain the Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 60deg.C with ultrasound (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The pH value of the solution to the system is=10, the temperature is raised to 80 ℃, the ultrasonic (P=600W) reaction is carried out for 50min, the solution is centrifugally washed for 3 times by using water and ethanol, and the Magnetic Aminated Graphene Oxide (MAGO) is obtained through freeze-drying.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MAGO-PEG). Wherein the mass ratio of MAGO, PALB and PAA is 2:1:3.
Example 11
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 And (3) heating the solution to the pH of the system of 10, heating to 85 ℃, performing ultrasonic (P=600W) reaction for 45min, centrifugally washing for 3 times, and freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 50deg.C, reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of MAGO, PALB and PAA is 1:1:1.
Example 12
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The pH of the solution to the system is=10, the temperature is raised to 85 ℃, the ultrasonic (P=600W) reaction is carried out for 45min, the solution is centrifugally washed for 3 times by using water and ethanol, and the Magnetic Aminated Graphene Oxide (MAGO) is obtained through freeze-drying.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MAGO in methanol solution, adding PALB and PAA after ultrasonic treatment for 20min (P=400W), heating to 55deg.C, reacting for 11h, centrifuging with water and ethanol, washing for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of MAGO, PALB and PAA is 1:2:3.
The superparamagnetic graphene oxide oil displacement agent prepared in example 1 is characterized, and the obtained results are shown in fig. 1, fig. 2 and fig. 3. As can be seen from fig. 1, the superparamagnetic graphene oxide oil displacement agent is still in a nano lamellar structure, and the black is magnetic nano particles under high resolution; as can be seen from fig. 2, the superparamagnetic graphene oxide oil displacement agent has graphene oxide functional groups and lauramidopropyl betaine functional groups and polyacrylic acid functional groups; as can be seen from FIG. 3, the magnetic strength of the superparamagnetic graphene oxide oil displacement agent can reach 22emu/g, which is close to the standard of strong magnetic materials. The characterization of the products obtained in examples 2-12 is similar and the invention is not described in detail here.
Example 13
In this embodiment, the emulsification effect test is performed by using the superparamagnetic graphene oxide oil displacement agent obtained in embodiment 1:
the samples prepared in example 1 are respectively prepared into 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of displacement liquid for emulsification effect test, 5mL of displacement liquid and 5mL of white oil are respectively taken and put into a 20mL customized test tube, a tube mouth is sealed, the test tube is vibrated up and down for 3 times, and data are recorded. The emulsification effect is shown in figure 5. As can be seen from fig. 5, the displacement fluid prepared from the sample prepared in example 1 has an increased emulsifying capacity with an increase in concentration, and the improvement in emulsifying performance is most remarkable when the concentration is 0.3%. The result in FIG. 6 is the emulsion layer volume of the result in FIG. 5, and the emulsion effect is better with increasing concentration, and the improvement of the emulsion performance is most obvious when the concentration is 0.3%.
Example 14
In this embodiment, the superparamagnetic graphene oxide oil displacement agent obtained in example 3 is used for emulsification and demulsification effect test:
the samples prepared in example 3 were prepared into 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of displacement fluid respectively for emulsification effect test, 5mL of displacement fluid and 5mL of white oil were respectively taken and put into a 20mL custom test tube, the tube mouth was sealed and vibrated up and down for 3 times, and data were recorded, so that fig. 7 (emulsion layer volume diagram of displacement fluid with different concentrations) was obtained. The results in FIG. 7 show that the improvement in emulsifying properties is most pronounced at a concentration of 0.2%.
Example 15
In this embodiment, the superparamagnetic graphene oxide oil displacement agent obtained in example 5 is used for emulsification and demulsification effect test:
the samples prepared in example 5 were prepared into 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of displacement fluid respectively for emulsification effect test, 5mL of displacement fluid and 5mL of white oil were respectively taken and put into a 20mL custom test tube, the tube mouth was sealed and vibrated up and down for 3 times, and data were recorded, so that fig. 8 (emulsion layer volume diagram of displacement fluid with different concentrations) was obtained. The results in FIG. 8 show that the improvement in emulsifying properties is most pronounced at a concentration of 0.3%.
Example 16
In this embodiment, the superparamagnetic graphene oxide oil displacement agent obtained in example 7 is used for emulsification and demulsification effect test:
the samples prepared in example 7 were prepared into 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of displacement fluid respectively for emulsification effect test, 5mL of displacement fluid and 5mL of white oil were respectively taken and put into a 20mL custom test tube, the tube mouth was sealed and vibrated up and down for 3 times, and data were recorded, so that fig. 9 (emulsion layer volume diagram of displacement fluid with different concentrations) was obtained. The results in FIG. 9 show that the improvement in emulsifying properties is most pronounced at a concentration of 0.3%.
Comparative example 1
Comparative example 1 differs from example 1 in that no amination and magnetization modification were performed, similar to the products currently on the market, using only graphene oxide with lauramidopropyl betaine and polyacrylic acid.
Dispersing 0.5g of graphene oxide in 300mL of methanol solution, adding 0.5g of lauramidopropyl betaine and 0.5g of polyacrylic acid after ultrasonic treatment for 20min (P=400W), raising the temperature to 50 ℃ for reaction for 12h, centrifugally washing for 3 times, and freeze-drying to obtain the nano lamellar oil displacement agent.
The nano-lamellar oil displacement agent prepared in comparative example 1 was tested, and found that the nano-lamellar oil displacement agent can only emulsify oil and water, but has limited emulsification effect, and cannot quickly break emulsion.
The samples prepared in example 1 and comparative example 1 were subjected to emulsification and demulsification effect tests, respectively, and the results are shown in fig. 4a and 4 b. As can be seen from FIGS. 4a and 4b, the oil-water emulsification effect and the demulsification effect of the sample prepared in example 1 are both stronger than those of the sample prepared in comparative example 1. Therefore, the invention can effectively graft the surfactant such as lauramidopropyl betaine, thereby not only enabling oil-water to be emulsified efficiently, but also enabling the oil-water to be demulsified rapidly under the condition of an externally applied magnetic field.
Comparative example 2
In comparison with example 1, comparative example 1 was different in that no amination was performed and only magnetization modification was performed, and then the magnetized graphene oxide was reacted with lauramidopropyl betaine and polyacrylic acid.
(1) Preparing magnetic amination graphene oxide:
GO and FeSO are mixed according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Graphene Oxide (MGO).
(2) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MGO in methanol solution, adding lauramidopropyl betaine (PALB) and polyacrylic acid (PAA) after ultrasonic treatment for 20min (P=400W), heating to 50deg.C for reacting for 12h, centrifuging with water and ethanol for 3 times, and lyophilizing to obtain magnetic graphene oxide oil displacement agent (MGO-P). Wherein the mass ratio of MGO, PALB and PAA is 1:1:1.
The surfactant prepared by the reaction of the oxidized graphene which is not aminated and is only magnetized with lauramidopropyl betaine and polyacrylic acid is observed to be emulsified and demulsified, so that the surfactant can be demulsified rapidly under the action of an external magnetic field, has improved salt resistance, but has poor emulsification effect.
Comparative example 3
Comparative example 1 was different from example 1 in that the amination modification was performed without magnetization modification, and then the aminated graphene oxide was reacted with lauramidopropyl betaine and polyacrylic acid.
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing a graphene oxide oil displacement agent: dispersing the AGO in a methanol solution, adding lauramidopropyl betaine (PALB) and a polycarboxylate water reducer (PAA) after ultrasonic treatment for 20min (P=400W), raising the temperature to 50 ℃ for reaction for 12h, centrifugally washing for 3 times by using water and ethanol, and freeze-drying to obtain the magnetic graphene oxide oil displacement agent (AGO-PEG). Wherein the mass ratio of the AGO to the PALB to the PAA is 1:1:1.
The surfactant prepared by the reaction of the oxidized graphene which is not magnetized and is only aminated, the lauramidopropyl betaine and the polyacrylic acid is good in emulsification effect and enhanced in salt resistance, but poor in demulsification capability under the action of an external magnetic field.
Comparative example 4
In comparison with example 1, comparative example 1 was different in that amination modification and magnetization modification were performed without grafting polyacrylic acid, and graphene oxide magnetized with an amino group was prepared by reacting only lauramidopropyl betaine.
(1) Preparing aminated graphene oxide:
0.2g of Graphene Oxide (GO) was dispersed in 100mL of n, n-Dimethylformamide (DMF) solution, after 1h of sonication (p=400W), 200mL of Ethylenediamine (EDA) solution was added, the temperature was raised to 45 ℃ and sonication was continued for 24h (p=400W), and the resulting mixture was washed 3 times with water and ethanol by centrifugation, and freeze-dried to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic amination graphene oxide:
AGO and FeSO are added according to the mass ratio of 1:1:1 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C by ultrasonic wave (P=400W), maintaining for 2 hr, and adding NH dropwise 3 ·H 2 O-NH 4 NO 3 The solution was brought to ph=10, warmed to 85 ℃, sonicated (p=600w) And (3) reacting for 45min, centrifugally washing for 3 times by using water and ethanol, and freeze-drying to obtain the Magnetic Graphene Oxide (MGO).
(3) Preparing a graphene oxide oil displacement agent: dispersing the AGO in a methanol solution, adding lauramidopropyl betaine (PALB) after ultrasonic treatment for 20min (P=400W), heating to 50 ℃ for reaction for 12h, centrifugally washing for 3 times by using water and ethanol, and freeze-drying to obtain the magnetic graphene oxide oil displacement agent (AGO-PALB). Wherein the mass ratio of the AGO to the PALB is 1:1.
Fig. 10 is a graph showing the volume comparison of the emulsion layers of displacement fluids prepared by preparing the magnetic graphene oxide oil-displacing agent prepared in example 1 and the magnetic graphene oxide oil-displacing agent prepared in this comparative example into different mineralization degrees, and as can be seen from fig. 10, the magnetic graphene oxide oil-displacing agent prepared in this comparative example has poor emulsification effect under a high-salt-content oil reservoir due to ungrafted polycarboxylic acid.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (6)
1. A preparation method of a superparamagnetic graphene oxide oil displacement agent, wherein the preparation method comprises the following steps:
dispersing graphene oxide in N, N-dimethylformamide to obtain graphene oxide dispersion liquid; the ratio of the graphene oxide to the N, N-dimethylformamide is (0.2-0.4) g:100mL;
adding ethylenediamine into the graphene oxide dispersion liquid after ultrasonic treatment for 45-60 min, heating to 40-60 ℃ and continuing ultrasonic treatment for 23 h-24 h, centrifuging, washing, and drying to obtain aminated graphene oxide; the volume ratio of ethylenediamine to graphene oxide dispersion liquid is (1.5-2.5): 1, a step of;
dispersing the aminated graphene oxide and the iron source in deionized water, and ultrasonically heating to 40-70 ℃ for preservationHolding 2h, then adding NH 3 ·H 2 O-NH 4 NO 3 The pH value of the solution is controlled to be 9.2-10.5, the temperature is increased to 70-90 ℃ for ultrasonic reaction for 45-60 min, after the reaction is finished, the solution is centrifuged and washed, and then the solution is dried to obtain the magnetic aminated graphene oxide; adding the magnetic amination graphene oxide, a surfactant and a polycarboxylate water reducer into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent; the reaction temperature is 45-55 ℃, and the reaction time is 11 h-13 h;
the mass ratio of the amination graphene oxide to the iron source is 1 (0.8-1.2), wherein the mass of the iron source is Fe 3 O 4 Is a mass meter of (2); the iron source comprises ferrous salts and ferric salts; the molar ratio of the ferrous salt to the ferric salt is 1 (1-3);
the surfactant is selected from one or a combination of more than two of betaine surfactants, wherein the betaine surfactants comprise lauramidopropyl betaine, erucamidopropyl betaine and dodecyl dimethyl betaine;
the polycarboxylate water reducer is one or a combination of more than two of polyacrylic water reducers, and the polyacrylic water reducer comprises polyacrylic acid, polymethacrylic acid and polyethyl acrylate;
the mass ratio of the magnetic amination graphene oxide, the surfactant and the polycarboxylate superplasticizer is 2 (1-3): (1-3).
2. The preparation method according to claim 1, wherein the reactions in the preparation method are all carried out in an ultrasonic reactor.
3. The method of claim 1, wherein the NH 3 ·H 2 O-NH 4 NO 3 NH in solution 3 ·H 2 O and NH 4 NO 3 The molar ratio of (2) to (4) to (1).
4. The method of claim 1, wherein the ferrous salt isIs FeCl 2 Or FeSO 4 The ferric salt is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 。
5. The preparation method according to claim 1, wherein the solvent in the step of adding the magnetic aminated graphene oxide, a surfactant and a polycarboxylate water reducer to a solvent for reaction is methanol or DMF.
6. A superparamagnetic graphene oxide oil displacement agent obtained by the preparation method of any one of claims 1 to 5.
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