CN115261002A - Superparamagnetic graphene oxide oil displacement agent and preparation method thereof - Google Patents
Superparamagnetic graphene oxide oil displacement agent and preparation method thereof Download PDFInfo
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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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Abstract
The invention discloses a superparamagnetic graphene oxide oil-displacing agent and a preparation method thereof. The preparation method comprises the following steps: dispersing graphene oxide in N, N-dimethylformamide, and adding ethylenediamine for reaction to obtain aminated graphene oxide; subjecting the aminated graphene oxide, an iron source and NH3·H2O‑NH4NO3Mixing the solutions for reaction to obtain magnetic aminated graphene oxide; and adding the magnetic aminated graphene oxide, a surfactant and a polycarboxylic acid water reducing agent 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 surfactant material with the capability of bidirectional reversible regulation and control according to the change of an external magnetic field, and realizes the oil displacement surfactantThe full-flow intelligent control of the performance improves the salt resistance, further greatly improves the oil-water separation efficiency of produced liquid in the oil displacement 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 based on chemical flooding, but are limited by resource grade, oil reservoir conditions, high salinity of the oil reservoir and a development mode, and nearly 50% of crude oil remains underground in a residual oil mode after tertiary oil recovery. In view of the huge reserves of residual oil resources, if the residual oil can be effectively used, the contribution is no less than that of a plurality of newly discovered large oil fields, so the residual oil development is very important. Residual oil is scattered in distribution and the oil reservoir is heterogeneous and outstanding, the existing exploitation technology is difficult to effectively drive, and a main body replacement technology needs to be researched and developed urgently. The breakthrough of improving the recovery ratio of the residual oil can be obtained only by the breakthrough of innovative technology. More and more researches believe that emulsion flooding or microemulsion flooding is an important mechanism for greatly improving the recovery ratio of chemical flooding.
Surfactants with functions of reducing surface tension, improving medium wettability, emulsifying, permeating, improving salt resistance, foaming and the like are needed to solubilize hydrophobic organic substances and stabilize gas-liquid or liquid-liquid interfaces in many processes of oil and gas development (such as well drilling and completion, fracture acidizing, chemical combination flooding, gas well drainage and gas production, heavy oil chemical recovery, high-efficiency treatment of produced liquid, oil and gas gathering and transportation and the like). However, the conventional surfactant is often difficult to separate from the solubilized material after the conventional surfactant acts, resulting in high cost of subsequent treatment, difficult treatment of produced liquid, direct discharge, not only large amount of waste, but also serious environmental pollution. Research data show that if the surfactant can be effectively recycled, the operation cost can be saved by about 70%.
The magnetic response surfactant is a novel surfactant, and the surfactant is a nano particle with superparamagnetism. Superparamagnetism refers to a ferromagnetic substance with a single-domain structure when the particle size is smaller than a critical size, and the ferromagnetic substance has the paramagnetic characteristic when the temperature is lower than the Curie temperature and higher than the transition temperature, but the paramagnetic susceptibility of the ferromagnetic substance is far higher than that of a common paramagnetic material under the action of an external magnetic field. The magnetization curve of a superparamagnetic body is different from that of a ferromagnetic body, and has no hysteresis. When the external magnetic field is removed, the remanence disappears quickly. The magnetic particles can be used as an emulsion stabilizer to prepare Pickering emulsion (magnetic emulsion), and the magnetic emulsion can also be broken through magnetic response under the action of an external magnetic field. The interfacial activity can be bidirectionally regulated and controlled according to environmental changes. The active agent can change the aggregation behavior of the active agent in a solution under the external stimulation, thereby leading to the change of the rheological property of a system. The characteristics enable the surfactant to have wider application prospect, and intensive research and utilization are urgently needed. Graphene oxide is a two-dimensional carbon material with a large specific surface area and a large number of active reaction groups, and is an ideal carrier of a magnetic response surfactant.
Disclosure of Invention
Based on the background technology, the invention provides a superparamagnetic graphene oxide oil-displacing agent and a preparation method thereof. According to the invention, through the research on a molecular structure model, a novel surfactant material with a magnetic group structural unit is designed, so that the capability of bidirectional reversible regulation and control can be realized according to the change of an external magnetic field, the full-flow intelligent regulation and control of the performance of the oil displacement surfactant can be realized, the oil-water separation efficiency of produced liquid in the oil displacement process can be greatly improved, the production flow can be simplified, and the production cost can be reduced.
In order to achieve the purpose, the 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 for reaction to obtain aminated graphene oxide;
subjecting the aminated graphene oxide, an iron source and NH3·H2O-NH4NO3Mixing the solutions for reaction to obtain magnetic aminated graphene oxide;
and adding the magnetic aminated graphene oxide, a surfactant and a polycarboxylic acid water reducing agent into a solvent for reaction to obtain the superparamagnetic graphene oxide oil-displacing agent.
The invention prepares the self-breaking oil-displacing agent with a magnetic group structural unit, and the oil-displacing agent is a nano-scale particle with superparamagnetism. The preparation method can graft and modify the graphene oxide, the surfactant and the polycarboxylic acid water reducing agent under mild conditions, improve the salt resistance of the oil displacement agent and endow the oil displacement agent with superparamagnetism, can carry out bidirectional reversible regulation and control on the oil-water emulsification performance according to the change of an external magnetic field, can efficiently emulsify oil and water and can stably and quickly break emulsion under the condition of an external magnetic field, further greatly improve the oil-water separation efficiency of oil field produced liquid, simplify the production process, and can be recycled to reduce the cost, and finally realize the full-process regulation and control on the oil displacement surfactant performance.
According to the preparation method of the invention, preferably, the reactions in the preparation method are all carried out in an ultrasonic reactor; more preferably an ultrasonic magnetic storm wall breaking machine.
By using NH in the invention3·H2O-NH4NO3The solution replaces the traditional NaOH or NH3·H2Preparation of Fe from O solution3O4The microspheres can effectively reduce the corrosion effect on the ultrasonic reactor, stabilize the pH value of the system and keep the pH value of the system in the reaction process within 9.2-10.5 all the time, thereby effectively avoiding the problem of reduction of the alkalinity of the system and product quality due to 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, firstly, graphene oxide can be uniformly dispersed in a solution; secondly, the reaction solution can be ensured to go deep into the graphene oxide interlayer, so that the magnetic nano particles grow in the graphene oxide interlayer and can strut the graphene oxide, the contact area is larger, and the magnetic nano particles are ensured to be uniformly distributed and not agglomerated; and finally, the surfactant and the polycarboxylate superplasticizer can be uniformly and effectively grafted on the graphene oxide, and the oil-water emulsifying performance of the graphene oxide is ensured.
The preparation method of the invention can be divided into three steps of preparing aminated graphene oxide, preparing magnetic aminated graphene oxide, preparing oil displacement agent and the like, and each step is explained in detail below.
Preparing aminated graphene oxide: dispersing graphene oxide in N, N-dimethylformamide to obtain a graphene oxide dispersion liquid; and adding ethylenediamine into the graphene oxide dispersion liquid for reaction to obtain aminated graphene oxide.
According to the method, the graphene oxide has the functional group with extremely strong activity, namely amino, by utilizing the amino modified graphene oxide, and the surfactant and the polycarboxylic acid water reducing agent can be effectively grafted under a relatively mild condition, so that the problem that the oil-water emulsification effect of the graphene oil displacement agent is poor is solved.
According to the preparation method of the present invention, preferably, the step of preparing the aminated graphene oxide comprises:
dispersing graphene oxide in N, N-dimethylformamide, carrying out ultrasonic treatment for 45-60 min, adding ethylenediamine, heating to 40-60 ℃, carrying out ultrasonic treatment for 23-24 h, centrifuging, washing, and drying to obtain aminated graphene oxide.
For the purpose of ultrasonic treatment of graphene oxide in DMF, ethylenediamine was added for amination.
According to the preparation 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 dispersion liquid of the ethylenediamine to the graphene oxide 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 solvents are water and ethanol.
Preparing magnetic aminated graphene oxide: subjecting the aminated graphene oxide, an iron source and NH3·H2O-NH4NO3And mixing the solutions for reaction to obtain the magnetic aminated graphene oxide.
According to the preparation method of the present invention, preferably, the step of preparing the magnetically aminated graphene oxide comprises:
dispersing the aminated graphene oxide and an iron source in deionized water, ultrasonically heating to 40-70 ℃, keeping for 2h, and then adding NH3·H2O-NH4NO3And (3) heating the solution to the pH = 9.2-10.5 of the system, performing ultrasonic reaction at the temperature of 70-90 ℃ for 45-60 min, centrifuging and washing after the reaction is finished, and drying to obtain the magnetic aminated graphene oxide.
According to the preparation method of the present invention, preferably, the NH3·H2O-NH4NO3NH in solution3·H2O and NH4NO3The molar ratio of (a) is 2 to 4:1.
According to the preparation method of the 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 Fe3O4The mass meter of (1). When the dosage of the aminated graphene oxide is too high, the magnetism of the prepared magnetic aminated graphene oxide is low; when the amount of the aminated graphene oxide is too low, the grafted surfactant content is low, and the emulsifying performance 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 Fe)3O4Mass meter).
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 can be formed when the molar ratio is beyond the range2O3Affecting its magnetic and emulsifying effects. More preferably, the iron source comprises a ferrous salt and a ferric salt; the molar ratio of the ferrous salt to the ferric salt is 1:2.
according to the preparation method of the present invention, preferably, the ferrous salt is FeCl2Or FeSO4The trivalent ferric salt is FeCl3Or Fe2(SO4)3。
According to the preparation method of the present invention, preferably, in the step of preparing the magnetically aminated graphene oxide, the washing solvents are water and ethanol.
Preparing an oil displacement agent: and adding the magnetic aminated graphene oxide, a surfactant and a polycarboxylic acid water reducing agent into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent.
According to the preparation method of the present invention, preferably, the surfactant is selected from one or a combination of two or more of betaine surfactants.
According to the preparation method of the present invention, preferably, the betaine-type surfactant includes lauramidopropyl betaine, acid amidopropyl betaine, and lauryldimethyl 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 oil reservoirs with high salinity and high temperature.
According to the preparation method of the present invention, preferably, the polycarboxylic acid water reducing agent is one or a combination of two or more selected from polyacrylic acid water reducing agents.
According to the preparation method of the present invention, preferably, the polyacrylic acid-based water reducing agent includes polyacrylic acid, polymethacrylic acid and polyethylacrylate. Further preferably, the polycarboxylic acid water reducing agent is polyacrylic acid. The polyacrylic acid has salt resistance and alkali resistance, can effectively improve the salt resistance, and has good salt resistance for oil reservoirs with high salinity and high temperature.
According to the preparation method provided by the invention, preferably, the mass ratio of the magnetic aminated graphene oxide to the surfactant to the polycarboxylic acid water reducing agent 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 yield the product.
According to the preparation method of the invention, preferably, the reaction temperature in the step of preparing the oil displacement agent is 45-55 ℃, and the reaction time is 1-13 h. More preferably, the reaction temperature is 50 ℃ and the reaction time is 12h.
In a second aspect, the invention provides a superparamagnetic graphene oxide oil displacement agent obtained by the preparation method.
The prepared superparamagnetic graphene oxide oil-displacing agent is characterized and evaluated, and the superparamagnetic graphene oxide oil-displacing agent still has a nanosheet 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 surfactant lauramide propyl betaine, polycarboxylic acid water reducing agent polyacrylic acid and the like, thereby increasing the salt resistance of the oil displacement agent, efficiently emulsifying oil and water, and simultaneously rapidly demulsifying under the condition of an external magnetic field, and being expected to become a new generation of oil displacement agent for intelligent oil and gas field development.
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 magnetic hysteresis loop diagram of the superparamagnetic graphene oxide oil-displacing agent prepared in example 1.
FIG. 4a is a graph showing the emulsification and demulsification effects of the samples made in example 1.
FIG. 4b is a graph showing the emulsification and demulsification effects of the samples prepared in comparative example 1.
Figure 5 is a graph showing the emulsification effect of displacement fluids of different concentrations formulated from the samples made in example 1.
Figure 6 is a plot of the emulsion layer volumes for different concentrations of the displacement fluid formulated for the samples made in example 1.
Fig. 7 is a plot of emulsion layer volumes for different concentrations of displacement fluid formulated for the samples produced in example 3.
Figure 8 is a plot of the emulsion layer volumes for different concentrations of the displacement fluid formulated for the samples made in example 5.
Fig. 9 is a graph of the emulsion layer volumes for different concentrations of the displacement fluid formulated for the samples made in example 7.
FIG. 10 is a comparison graph of emulsion layer volumes of displacement fluids with different degrees of mineralization prepared from the magnetic graphene oxide oil displacement agent prepared in example 1 and comparative example 4,
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations herein (e.g., temperature, time, concentration, and weight, etc., including ranges for each) may generally be approximated as varied (+) or (-) in increments of 0.1 or 1.0, as appropriate. All numerical designations should 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:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
according to AGO, feSO4·7H2O and FeCl3·6H2And O, mixing AGO and FeSO according to a mass ratio of 14·7H2O and FeCl3·6H2O was dispersed in deionized water, ultrasonically (P = 400W) heated to 50 ℃ for 2h, and thenDropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
and (2) dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding lauramide propyl betaine (PALB) and polyacrylic acid (PAA), heating to 50 ℃, reacting for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of the MAGO to the PALB to the PAA is 1.
Example 2
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.3g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, heating to 50 ℃ by ultrasonic (P = 400W) for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ for reaction for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 2.
Example 3
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g GO in 100mL DMF solution, sonicating for 1h (P = 400W), adding 200mL EDA solution, warming to 45 ℃ and continuing sonication (P = 400W) for 24h, washing 3 times using water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeCl are added according to the mass ratio of 52·4H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 1.
Example 4
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
and (2) adding AGO and FeCl according to the mass ratio of 52·4H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3The solution was brought to pH =10, heated to 85 ℃ and subjected to ultrasonic (P = 600W) reaction for 45min to allow the reaction to proceedAnd (3) centrifuging and washing the mixture by using water and ethanol for 3 times, and freeze-drying the mixture to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 2.
Example 5
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
and (2) mixing AGO and FeSO in a mass ratio of 24·7H2O and Fe2(SO4)·H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
and (2) dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃, reacting for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 1.
Example 6
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
and (2) mixing AGO and FeSO in a mass ratio of 24·7H2O and Fe2(SO4)·H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 2.
Example 7
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeCl are mixed according to the mass ratio of 12·4H2O and Fe2(SO4)·H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO, the PALB and the PAA is 1.
Example 8
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.4g of GO in 100mL of DMF solution, sonicating for 1h (P = 400W), adding 200mL of EDA solution, warming to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol by centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeCl are mixed according to the mass ratio of 12·4H2O and Fe2(SO4)·H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the MAGO.
(3) Preparing a superparamagnetic graphene oxide oil displacement agent:
dispersing MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain MAGO-P. Wherein the mass ratio of the MAGO to the PALB to the PAA is 2.
Example 9
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding dodecyl dimethyl betaine (BS 12) and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MAGO-B). Wherein the mass ratio of the MAGO to the BS12 to the PAA is 1.
Example 10
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 50 ℃ and continuing sonication (P = 400W) for 23h, washing 3 times by centrifugation using water and ethanol, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 60 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 80 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 50min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: and (2) dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃, reacting for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MAGO-PEG). Wherein the mass ratio of the MAGO to the PALB to the PAA is 2.
Example 11
The preparation method of the superparamagnetic graphene oxide oil displacement agent comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ until the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, centrifuging and washing for 3 times, and performing freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 50 ℃ to react for 12h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of the MAGO to the PALB to the PAA is 1.
Example 12
The embodiment of the invention provides a superparamagnetic graphene oxide oil displacement agent, which comprises the following steps:
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And (3) heating the solution to 85 ℃ till the pH of the system is =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Aminated Graphene Oxide (MAGO).
(3) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing the MAGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding PALB and PAA, heating to 55 ℃ for reaction for 11h, performing centrifugal washing for 3 times by using water and ethanol, and performing freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MAGO-P). Wherein the mass ratio of the MAGO to the PALB to the PAA is 1.
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-displacing agent is still in a nanosheet structure, and the black color is a magnetic nanoparticle under high resolution; as can be seen from fig. 2, the superparamagnetic graphene oxide oil displacement agent possesses a functional group of graphene oxide and a functional group of lauramidopropyl betaine, as well as a functional group of polyacrylic acid; as can be seen from FIG. 3, the magnetic strength of the superparamagnetic graphene oxide oil-displacing agent can reach 22emu/g, which is close to the standard of a ferromagnetic material. The characterization of the products obtained in examples 2 to 12 is similar to this, and the invention is not described in detail here.
Example 13
In this embodiment, the superparamagnetic graphene oxide oil displacement agent obtained in example 1 is used for an emulsification effect test:
the samples prepared in example 1 were prepared into displacement fluid of 0.1%, 0.2%, 0.3%, 0.4% and 0.5% respectively for testing the emulsification effect, 5mL of displacement fluid and 5mL of white oil were put into a 20mL customized test tube, the test tube mouth was sealed and shaken up and down for 3 times, and the data was 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 increased emulsifying capacity with increasing concentration, and the emulsifying performance is improved most obviously when the concentration is 0.3%. The result in fig. 6 is the volume of the emulsion layer of the result in fig. 5, the emulsion effect is better with the increase of the concentration, and the emulsion performance is improved most obviously 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 performing an emulsification and emulsion breaking effect test:
the samples prepared in example 3 were prepared into 0.1%, 0.2%, 0.3%, 0.4%, and 0.5% of displacement solutions, respectively, and the emulsion effect was tested, and 5mL of displacement solution and 5mL of white oil were put into a 20mL custom test tube, and the test tube was sealed and shaken up and down for 3 times, and the data was recorded, thereby obtaining fig. 7 (volume chart of emulsion layer of displacement solution of different concentrations). 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 to perform an emulsification and emulsion breaking effect test:
the samples prepared in example 5 were prepared into 0.1%, 0.2%, 0.3%, 0.4%, and 0.5% of the displacement solution, respectively, and the emulsification effect was tested, and 5mL of the displacement solution and 5mL of the white oil were put into a 20mL customized test tube, and the mouth of the test tube was sealed and shaken up and down 3 times, and the data was recorded, to obtain fig. 8 (a volume graph of the emulsion layer of the displacement solution of different concentrations). 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 performing an emulsification and emulsion breaking effect test:
the samples prepared in example 7 were prepared into 0.1%, 0.2%, 0.3%, 0.4%, and 0.5% of displacement solutions, respectively, and the emulsion effect was tested, and 5mL of displacement solution and 5mL of white oil were put into a 20mL custom test tube, and the tube mouth was sealed and shaken up and down for 3 times, and the data was recorded, thereby obtaining fig. 9 (volume chart of emulsion layer of displacement solution of different concentrations). The results in fig. 9 show that the improvement in emulsifying performance 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 is performed, similar to the currently marketed product, but only by reacting graphene oxide with lauramidopropyl betaine and polyacrylic acid.
Dispersing 0.5g of graphene oxide in 300mL of methanol solution, carrying out ultrasonic treatment for 20min (P = 400W), adding 0.5g of lauramidopropyl betaine and 0.5g of polyacrylic acid, heating to 50 ℃, reacting for 12h, carrying out centrifugal washing for 3 times, and freeze-drying to obtain the nanosheet layer oil displacement agent.
When the nano lamellar oil-displacing agent prepared in comparative example 1 is tested, the nano lamellar oil-displacing agent can only emulsify oil and water but has limited emulsifying effect and cannot demulsify quickly.
The samples prepared in example 1 and comparative example 1 were subjected to the 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 samples obtained in example 1 exhibited stronger emulsification and demulsification effects than the samples obtained in comparative example 1. Therefore, the invention can effectively graft the surfactant such as lauramidopropyl betaine, so that the oil and water can be efficiently emulsified, and the emulsion can be rapidly broken under the condition of an external magnetic field.
Comparative example 2
Compared with example 1, comparative example 1 is different in that only magnetization modification is performed without amination, and then the magnetized graphene oxide is reacted with lauramidopropyl betaine and polyacrylic acid to obtain the graphene oxide.
(1) Preparing magnetic aminated graphene oxide:
and (2) mixing GO and FeSO according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And heating the solution to the pH =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Graphene Oxide (MGO).
(2) Preparing a superparamagnetic graphene oxide oil displacement agent: dispersing MGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding lauramidopropyl betaine (PALB) and polyacrylic acid (PAA), heating to 50 ℃, reacting for 12h, centrifuging and washing for 3 times by using water and ethanol, and freeze-drying to obtain the magnetic graphene oxide oil displacement agent (MGO-P). Wherein the mass ratio of MGO, PALB and PAA is 1.
The surfactant prepared by reacting the graphene oxide which is not aminated and is magnetized with lauramidopropyl betaine and polyacrylic acid is observed to emulsify and demulsify, so that the surfactant can be used for quickly demulsifying under the action of an external magnetic field, the salt resistance is improved, and the emulsifying effect is poor.
Comparative example 3
Compared with example 1, comparative example 1 is different in that amination modification is performed without magnetization modification, and then aminated graphene oxide is reacted with lauramidopropyl betaine and polyacrylic acid to prepare the graphene oxide.
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing a graphene oxide oil displacement agent: dispersing AGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding lauramidopropyl betaine (PALB) and a polycarboxylic acid water reducing agent (PAA), heating to 50 ℃, reacting for 12h, performing centrifugal 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 AGO, PALB and PAA is 1.
The surfactant prepared by reacting the graphene oxide which is not magnetized and is only aminated, laurylamidopropyl betaine and polyacrylic acid is observed to have good emulsifying effect and enhanced salt resistance, but has poor demulsifying capability under the action of an external magnetic field.
Comparative example 4
Comparative example 1 is different from example 1 in that amination modification and magnetization modification are performed without grafting polyacrylic acid, and graphene oxide magnetized with amino groups is obtained by reacting only lauramidopropyl betaine.
(1) Preparing aminated graphene oxide:
dispersing 0.2g of Graphene Oxide (GO) in 100mL of n, n-Dimethylformamide (DMF) solution, sonicating for 1h (P = 400W), adding 200mL of Ethylenediamine (EDA) solution, heating to 45 ℃ and continuing to sonicate (P = 400W) for 24h, washing 3 times with water and ethanol centrifugation, and lyophilizing to obtain Aminated Graphene Oxide (AGO).
(2) Preparing magnetic aminated graphene oxide:
AGO and FeSO are mixed according to the mass ratio of 14·7H2O and FeCl3·6H2Dispersing O in deionized water, ultrasonically heating (P = 400W) to 50 ℃, preserving heat for 2h, and then dropwise adding NH3·H2O-NH4NO3And heating the solution to the pH =10, performing ultrasonic (P = 600W) reaction for 45min, performing centrifugal washing 3 times by using water and ethanol, and performing freeze-drying to obtain the Magnetic Graphene Oxide (MGO).
(3) Preparing a graphene oxide oil displacement agent: dispersing AGO in a methanol solution, performing ultrasonic treatment for 20min (P = 400W), adding lauramidopropyl betaine (PALB), heating to 50 ℃ for reaction for 12h, performing centrifugal 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 AGO to PALB is 1:1.
Fig. 10 is a volume contrast diagram of an emulsion layer of the displacement fluid prepared by the magnetic graphene oxide oil displacement agent prepared in example 1 and the magnetic graphene oxide oil displacement agent prepared in the present comparative example, and it can be seen from fig. 10 that the magnetic graphene oxide oil displacement agent prepared in the present comparative example has a poor emulsification effect in a high-salt-content oil reservoir because of no grafted polycarboxylic acid.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (17)
1. A preparation method of a superparamagnetic graphene oxide oil displacement agent comprises the following steps:
dispersing graphene oxide in N, N-dimethylformamide to obtain a graphene oxide dispersion liquid; adding ethylenediamine into the graphene oxide dispersion liquid for reaction to obtain aminated graphene oxide;
subjecting the aminated graphene oxide, an iron source and NH3·H2O-NH4NO3Mixing the solutions for reaction to obtain magnetic aminated graphene oxide;
and adding the magnetic aminated graphene oxide, a surfactant and a polycarboxylic acid water reducing agent into a solvent for reaction to obtain the superparamagnetic graphene oxide oil displacement agent.
2. The production method according to claim 1, wherein the reactions in the production method are all carried out in an ultrasonic reactor.
3. The preparation method according to claim 1, wherein the step of adding ethylenediamine to the graphene oxide dispersion liquid for reaction to obtain aminated graphene oxide comprises:
and (3) carrying out ultrasonic treatment on the graphene oxide dispersion liquid for 45-60 min, adding ethylenediamine, heating to 40-60 ℃, carrying out continuous ultrasonic treatment for 23-24 h, centrifuging, washing, and drying to obtain the aminated graphene oxide.
4. The production method according to claim 1, wherein the ratio of the graphene oxide to 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.
5. the preparation method according to claim 1, wherein the aminated graphene oxide, iron source and NH are subjected to the reaction3·H2O-NH4NO3The method for mixing the solutions to react to obtain the magnetic aminated graphene oxide comprises the following steps:
dispersing the aminated graphene oxide and an iron source in deionized water, ultrasonically heating to 40-70 ℃, keeping for 2h, and then adding NH3·H2O-NH4NO3And (3) heating the solution to the pH = 9.2-10.5 of the system, performing ultrasonic reaction at the temperature of 70-90 ℃ for 45-60 min, centrifuging and washing after the reaction is finished, and drying to obtain the magnetic aminated graphene oxide.
6. The method of claim 1, wherein the NH3·H2O-NH4NO3NH in solution3·H2O and NH4NO3The molar ratio of (A) is 2-4:1.
7. The preparation method according to claim 5, wherein the mass ratio of the aminated graphene oxide to the iron source is 1 (0.8-1.2), and the mass of the iron source is Fe3O4The mass meter of (1).
8. The production method according to claim 7, wherein 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).
9. The method according to claim 8, wherein the ferrous salt is FeCl2Or FeSO4The trivalent ferric salt is FeCl3Or Fe2(SO4)3。
10. The production method according to claim 1, wherein the surfactant is one or a combination of two or more selected from betaine surfactants.
11. The production method according to claim 10, wherein the betaine-type surfactant includes lauramidopropyl betaine, erucamamidopropyl betaine, and lauryldimethyl betaine.
12. The production method according to claim 1, wherein the polycarboxylic acid water reducing agent is selected from one or a combination of two or more of polyacrylic acid water reducing agents.
13. The production method according to claim 12, wherein the polyacrylic acid-based water reducing agent includes polyacrylic acid, polymethacrylic acid, and polyethylacrylate.
14. The preparation method of claim 1, wherein the mass ratio of the magnetic aminated graphene oxide to the surfactant to the polycarboxylic acid water reducer is 2 (1-3): (1-3).
15. The preparation method according to claim 1, wherein the solvent in the step of adding the magnetic aminated graphene oxide, the surfactant and the polycarboxylic acid water reducer to a solvent for reaction is methanol or DMF.
16. The preparation method according to claim 1, wherein the reaction temperature in the step of adding the magnetic aminated graphene oxide, the surfactant and the polycarboxylic acid water reducer into the solvent for reaction is 45-55 ℃, and the reaction time is 11-13 h.
17. A superparamagnetic graphene oxide oil displacement agent obtained by the preparation method of any one of claims 1 to 16.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037507A1 (en) * | 2014-09-12 | 2016-03-17 | 陕西科技大学 | Method for preparing polyacrylate/amino-modified graphene oxide composite leather finishing agent by using ultrasonic-assisted method |
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN108793134A (en) * | 2018-08-07 | 2018-11-13 | 高维佳 | A kind of preparation method of graphene |
| CN109250711A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of preparation method of amination graphene oxide |
| CN109251741A (en) * | 2017-07-12 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of magnetic Nano oil displacement agent and preparation method thereof |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
| CN109837080A (en) * | 2019-04-12 | 2019-06-04 | 中国石油大学(华东) | A kind of viscosity reduction system and preparation method thereof for microwave heavy crude producing |
-
2021
- 2021-04-30 CN CN202110489157.5A patent/CN115261002B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037507A1 (en) * | 2014-09-12 | 2016-03-17 | 陕西科技大学 | Method for preparing polyacrylate/amino-modified graphene oxide composite leather finishing agent by using ultrasonic-assisted method |
| CN106219669A (en) * | 2016-08-01 | 2016-12-14 | 山东交通学院 | A kind of preparation method of magnetic oxygenated Graphene demulsifier |
| CN109251741A (en) * | 2017-07-12 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of magnetic Nano oil displacement agent and preparation method thereof |
| CN109250711A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of preparation method of amination graphene oxide |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
| CN108793134A (en) * | 2018-08-07 | 2018-11-13 | 高维佳 | A kind of preparation method of graphene |
| CN109837080A (en) * | 2019-04-12 | 2019-06-04 | 中国石油大学(华东) | A kind of viscosity reduction system and preparation method thereof for microwave heavy crude producing |
| WO2020206869A1 (en) * | 2019-04-12 | 2020-10-15 | 中国石油大学(华东) | Viscosity reduction system for microwave exploitation of heavy oil and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 田浩;刘卫东;庞丽玲;孙灵辉;陈品;丛苏男;: "PAM/GO复合材料制备及驱油性能研究", 材料导报, no. 1, pages 364 - 368 * |
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