CN114574238B - Magnetic graphene oxide surfactant and preparation method thereof - Google Patents

Magnetic graphene oxide surfactant and preparation method thereof Download PDF

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CN114574238B
CN114574238B CN202011392611.7A CN202011392611A CN114574238B CN 114574238 B CN114574238 B CN 114574238B CN 202011392611 A CN202011392611 A CN 202011392611A CN 114574238 B CN114574238 B CN 114574238B
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graphene oxide
surfactant
magnetic graphene
magnetic
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CN114574238A (en
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侯庆锋
王源源
王哲
彭宝亮
郑晓波
管保山
李雪凝
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Petrochina Co Ltd
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • 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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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract

The invention discloses a magnetic graphene oxide surfactant and a preparation method thereof. The preparation method comprises the following steps: s1, graphene oxide, an iron source and NH 3 ·H 2 O‑NH 4 NO 3 Mixing the solutions to react to obtain the magnetic graphene oxide; s2, dispersing the magnetic graphene oxide in deionized water, and adding EDC and polyethylene glycol for reaction to obtain polyethylene glycol-coated magnetic graphene oxide; and S3, adding the polyethylene glycol-coated magnetic graphene oxide and a surfactant into a solvent for reaction to obtain the magnetic graphene oxide surfactant. According to the invention, graphene oxide and a surfactant can be subjected to grafting modification under a milder condition, superparamagnetism and interfacial activity are endowed, so that oil-water emulsification can be realized, and the emulsion can be rapidly broken under an externally applied magnetic field condition, and a certain adsorption effect on metal ions in oilfield produced liquid can be realized.

Description

Magnetic graphene oxide surfactant and preparation method thereof
Technical Field
The invention relates to the field of oilfield chemistry and nano materials, in particular to a magnetic graphene oxide surfactant and a preparation method thereof.
Background
With the rapid development of industry, the water pollution problem is serious, and the sustainable development of economy and the improvement of life quality of people are seriously affected. Wherein, toxic substances such as organic solvent, heavy metal ions and the like have serious damage to water quality. In the field of oil and gas field development, as the oil field enters a high-water-content development stage, chemical compound flooding is popularized and applied as an effective oil extraction technology, but one of bottleneck problems restricting development of the chemical compound flooding is difficult treatment of produced liquid, high cost is high, and particularly oil-water demulsification is a large neck problem. Crude oil reserves suitable for chemical compound flooding technology development in China are about 8.3 multiplied by 10 9 t, where only Daqing oil field has almost 1.4X10 9 t, the development potential of the chemical compound flooding is huge, and the chemical compound flooding is one of main attack directions for improving the crude oil recovery efficiency in China. At present, about 1X 10 of the treatment is needed in China every year 9 m 3 The total amount of the oil field produced liquid is 2.3 multiplied by 10 8 m 3 Oilfield produced fluid treatment has become a dual task for oilfield ground engineering and ecological environmental protection.
The water quality of the chemical compound flooding produced liquid is particularly complex, and mainly contains crude oil, suspended matters, inorganic salt ions and other impurity components. When the oil content in the produced liquid is high, the produced liquid can block the stratum during reinjection, and the produced liquid can cause environmental pollution during discharge. When the content of alkali, surfactant and polymer in the produced liquid is high, the viscosity of the produced liquid is increased, the emulsification degree is increased, and the oil-water sedimentation demulsification separation is difficult. Therefore, the problem of treatment of the produced liquid is a key problem to be solved in the promotion of chemical compound flooding technology.
Graphene oxide is a two-dimensional carbon material with a large specific surface area and a large number of active reactive groups, has a strong adsorption capacity on a large number of organic solvents and heavy metal ions, and is considered as one of important materials for removing toxic substances (crude oil, heavy metal ions and the like) in water and purifying water quality. However, pure graphene oxide has a strong adsorption capacity, but has low interfacial activity and a small size, so that the graphene oxide cannot be recycled. The ferroferric oxide modified graphene oxide is endowed with superparamagnetism and high interfacial activity, and is an effective means for solving the problems of rapid demulsification of oil and water of produced liquid of the oil field, adsorption of heavy metal ions and recovery and reuse of surfactant. Therefore, the development of the superparamagnetic graphene oxide with the interfacial activity has important practical significance in the fields of low-cost diving and environmental protection of high-water-content old oil fields.
The surfactant is a compound which can obviously reduce the interfacial tension of a solution system when being added with very low concentration, and is widely applied to the field of oil gas development. The molecules are composed of polar hydrophilic groups and nonpolar and oleophilic hydrophobic groups, and after the molecules act, the molecules are difficult to separate from solubilizing substances, so that the subsequent treatment cost of oilfield produced liquid is high, and serious environmental pollution is caused. Self-breaking emulsifiers have become an important research direction for chemical flooding and treatment of produced fluids.
Graphene oxide has abundant active functional groups and a typical lamellar structure, and is an excellent functional carrier. Studies have shown that: the nano material can change the wettability of oil layer rock, reduce oil-water seepage resistance and further improve the recovery ratio of crude oil.
In the petroleum field, there are few oil displacement agents which use graphene oxide as a functional carrier, and surfactant products which endow graphene oxide materials with magnetism, self-demulsification performance and metal ion adsorption performance do not appear.
Disclosure of Invention
Based on the above background, a first object of the present invention is to provide a preparation method of magnetic graphene oxide surface activity.
The second object of the present invention is to provide the magnetic graphene oxide surface activity obtained by the above preparation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a magnetic graphene oxide surface active agent, the method comprising the steps of:
s1, graphene Oxide (GO), an iron source and NH 3 ·H 2 O-NH 4 NO 3 Mixing the solutions to react to obtain the magnetic graphene oxide;
s2, dispersing the magnetic graphene oxide in deionized water, and adding EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and polyethylene glycol to react to obtain polyethylene glycol-coated magnetic graphene oxide;
and S3, adding the polyethylene glycol-coated magnetic graphene oxide and a surfactant into a solvent for reaction to obtain the magnetic graphene oxide surfactant.
The preparation method can graft-modify graphene oxide and a surfactant under milder conditions, endow superparamagnetism and interfacial activity, enable oil-water emulsification and rapid demulsification under the condition of an externally applied magnetic field, and have a certain adsorption effect on metal ions in oilfield produced liquid.
Each step is described in detail below.
S1, 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 graphene oxide.
In the process of synthesizing the magnetic graphene oxide, the stable pH value is critical to the product quality and the product stability of the magnetic graphene oxide. In the traditional preparation of magnetic graphene oxide, most of people use NaOH or NH 3 ·H 2 O maintains necessary alkaline conditions, but during the synthesis process, the pH value of the system is reduced due to continuous consumption of hydroxyl ions, so that the quality degradation of the magnetic graphene oxide and the instability of the product performance are caused, and the magnetic graphene oxide is manufacturedThe industrial production is difficult to implement.
At present, the ultrasonic means are used in the synthesis of the magnetic graphene oxide by the technicians in the field, but the ultrasonic is continuously carried out before the ferroferric oxide is loaded on the graphite oxide, the effect of the ultrasonic means is only to a certain extent, the dispersion and dissociation effects of the graphene oxide are improved, and the method is only a simple physical dispersion and dissociation method, so that the chemical modification or poor modification effect of the ferroferric oxide on the graphene oxide can not be realized. In addition, at present, the ultrasonic wall breaking machine still has a plurality of problems, such as corrosion damage of the reaction liquid to the probe of the ultrasonic wall breaking machine, continuous dripping of raw materials and other open systems for maintaining the pH of the reaction liquid, and the need of an external heat source for regulating and controlling the reaction temperature.
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 probe of the ultrasonic wall breaking machine, but also can stabilize the pH value of the system, so that the pH value of the system can be always kept within 9.2-10.5 in the reaction process, thereby effectively solving the problem of product quality degradation caused by continuous reduction of the alkalinity of the system due to continuous consumption of hydroxyl ions in the reaction process.
According to the preparation method, preferably, the whole preparation process of the magnetic graphene oxide surfactant is carried out in an ultrasonic reactor, and an ultrasonic magnetic explosion wall breaking machine is specifically adopted. Firstly, graphene oxide can be uniformly dispersed in a solution; secondly, ensuring that the reaction solution enters between graphene oxide sheets, so that magnetic nanoparticles grow between graphene oxide sheets and can prop open graphene oxide, so that the contact area is increased, and ensuring that the magnetic nanoparticles are uniformly distributed and are not agglomerated; finally, the surfactant can be uniformly and effectively grafted on the graphene oxide, so that the emulsifying property of the graphene oxide is obviously enhanced.
According to the preparation method of the present invention, preferably, S1 specifically includes: dispersing graphene oxide and an iron source in deionized water, and dropwise adding NH 3 ·H 2 O-NH 4 NO 3 Solution toAnd (3) performing reaction at pH=9.2-10.5, centrifuging and washing after the reaction is finished, and drying to obtain the magnetic 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 graphene oxide and the iron source are as follows 3 O 4 The mass ratio of (2) is 1: (0.8-1.2), preferably 1:1. The high magnetic performance of GO is lower, and the low grafted surfactant content of GO affects the emulsifying performance less, so the graphene oxide and the iron source are preferably selected according to the graphene oxide and the Fe 3 O 4 The mass ratio of (2) is 1: (0.8-1.2).
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). The molar ratio of ferrous salt to ferric salt exceeding 1 (1-3) can form excessive Fe 2 O 3 Affecting its magnetic and emulsifying effects.
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, the temperature of the reaction in S1 is 70 to 90℃and the reaction time is 45 to 60 minutes.
S2, dispersing the magnetic graphene oxide in deionized water, and adding EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and polyethylene glycol to react to obtain polyethylene glycol-coated magnetic graphene oxide.
Polyethylene glycol (PEG) is an easily available environment-friendly material, is nontoxic and easily degradable, and has good amphipathic characteristics. Modification with PEG can overcome some of the drawbacks of graphene oxide. Because the PEG fragments are positioned on the surfaces of the particles and extend into water to swing in the water, on one hand, enough repulsive force is generated among the particles to overcome the action of van der Waals attraction, so that the particles have good stability without aggregation; on the other hand, the adsorption of graphene oxide and oil reservoir rocks can be prevented. Therefore, the PEG modified graphene oxide can enhance the dispersibility of the graphene oxide in water and improve the use efficiency of the oil displacement surfactant.
According to the preparation method of the present invention, preferably, the polyethylene glycol is PEG-6000. In the research and development process of the invention, if the chain length of the selected polyethylene glycol is too short, the grafting of the surfactant is influenced, and if the chain length of the selected polyethylene glycol is too long, the grafting effect is too bad, so that the PEG-6000 is preferably adopted in the invention.
According to the preparation method of the invention, preferably, the mass ratio of the magnetic graphene oxide, EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and polyethylene glycol in S2 is 5 (1.8-2.2) to 3.5-4.5. More preferably 5:2:4. The EDC is an activator, the effect of the dosage is small, and the subsequent grafting efficiency is affected by excessive dosage of polyethylene glycol.
According to the preparation method of the present invention, preferably, the temperature of the reaction in S2 is 80 to 90℃and the reaction time is 3 to 5 hours. More preferably, the temperature of the reaction described in S2 is 80 ℃ and the reaction time is 4h.
And S3, adding the polyethylene glycol-coated magnetic graphene oxide and a surfactant into a solvent for reaction to obtain the magnetic graphene oxide surfactant.
According to the preparation method of the invention, preferably, the mass ratio of the polyethylene glycol-coated magnetic graphene oxide to the surfactant in the S3 is 4 (4-5); the ratio range ensures that as much surfactant as possible is grafted in the case of magnetism.
According to the preparation method of the present invention, preferably, the surfactant is a betaine-type surfactant.
According to the preparation method of the present invention, preferably, the betaine-type surfactant includes one or a combination of two or more of dodecyl dimethyl betaine, lauramidopropyl betaine, erucamidopropyl betaine, and the like. More preferably, the surfactant is dodecyl dimethyl betaine, wherein the price is lower.
According to the preparation method of the invention, preferably, the temperature of the reaction in S3 is 48-55 ℃, and the reaction time is 12-14 h; too high a temperature may affect the activity of functional groups on graphene oxide, and too low a temperature may affect the reaction efficiency. More preferably, the reaction temperature described in S3 is 50 ℃ and the reaction time is 12h.
According to the preparation method of the present invention, preferably, the solvent in S3 is methanol or DMF. More preferably methanol, can be more conveniently removed from the system to yield the product.
According to the preparation method of the invention, preferably, the reaction in the preparation method is carried out in an ultrasonic magnetic storm wall breaking machine, and after the reaction is finished, the product of each step is obtained by centrifugal washing and drying. More preferably, the washing is performed with water and ethanol, the ethanol can be used as a precipitant to facilitate centrifugation, the water can remove the raw solvent and unreacted reactants, and the drying is performed with freeze-drying, which can protect the properties of the product from being changed as much as possible.
In a second aspect, the invention provides a magnetic graphene oxide surfactant obtained by the preparation method. The magnetic graphene oxide surfactant has the remarkable advantages that polyethylene glycol is utilized to modify the magnetic graphene oxide, and the magnetic graphene oxide surfactant has a certain adsorption effect on metal ions in oilfield sewage. The active functional group grafted surfactant of the graphene oxide has the performance of emulsification and rapid demulsification by externally adding magnetism, and is a multifunctional surfactant and oilfield sewage treatment agent which have adsorption effect on metal ions, can be efficiently emulsified and rapidly demulsified under an externally adding magnetic field, and can be recycled.
The magnetic graphene oxide surfactant disclosed by the invention takes a graphene oxide material as a carrier, so that superparamagnetism, self-demulsification performance and metal ion adsorption performance are endowed. The characterization result proves that the magnetic graphene oxide surfactant has a nano lamellar structure and has functional groups of graphene oxide, polyethylene glycol and a grafted surfactant (such as dodecyl dimethyl betaine); the magnetic strength of the magnetic graphene oxide surfactant is 13emu/g and is close to that of a strong magnetic material.
The magnetic graphene oxide surfactant disclosed by the invention is a multifunctional surfactant and an oilfield sewage treatment agent, wherein the multifunctional surfactant has an adsorption effect on metal ions, can be efficiently emulsified, can be rapidly demulsified under an external magnetic field, and can be recycled. The device has the capability of bidirectional reversible regulation and control according to the change of the external environment, thereby greatly improving the oil-water separation efficiency of the produced liquid of the oil field and simplifying the production flow. Compared with the prior art, the invention has the beneficial effects that:
1) The polyethylene glycol modified graphene oxide is utilized, so that the graphene oxide can be better in dispersibility in water, the oil reservoir adsorption loss is small, and the agent utilization efficiency is higher.
2) The graphene oxide, the magnetic nanoparticles and the PEG are utilized to have a good adsorption effect on metal ions in sewage.
3) Superparamagnetism and high interfacial activity are endowed to the oil displacement surfactant, so that the oil displacement surfactant can be rapidly demulsified under the condition of an externally applied magnetic field and can be effectively recovered, the demulsification problem of produced liquid is solved, and the oil displacement surfactant can be recovered and reused to reduce cost.
Drawings
Fig. 1 is an atomic force microscope photograph of the magnetic graphene oxide surfactant prepared in example 1.
Fig. 2 is an infrared spectrum of the magnetic graphene oxide surfactant prepared in example 1.
Fig. 3 is a hysteresis loop diagram of the magnetic graphene oxide surfactant prepared in example 1.
Fig. 4a and 4b are graphs showing the emulsification and demulsification effects of the surfactants obtained in example 1 and comparative example 1, respectively.
Fig. 5 is a plot of the emulsion layer volumes of displacement fluids of different concentrations formulated with the magnetic graphene oxide surfactant of example 1 in example 13.
Fig. 6 is a plot of the emulsion layer volumes of displacement fluids of different concentrations formulated with the magnetic graphene oxide surfactant obtained in example 5 in example 14.
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 magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:1 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feSO 4 ·7H 2 O and FeCl 3 ·6H 2 O is dispersed in deionized water, ultrasonic (P=400W) is heated to 50 ℃, the purpose of ultrasonic is to enable graphene oxide to be more dispersed, ionic solution can enter between graphene oxide layers to enable magnetic nano particles to grow and combine between the graphene oxide layers more stably, and NH is added dropwise after 2 hours 3 ·H 2 O-NH 4 NO 3 The solution is heated to 85 ℃ by ultrasonic (P=600W) until the pH value is 10, the 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 by freeze-drying. Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparation of polyethylene glycol coated magnetic graphene oxide (MGO-PEG):
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 (dodecyl dimethyl betaine) with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 2
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:1 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feSO 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, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Aminated Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 4:5 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 3
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 5:5:7 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 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 Solution to pH =10, heating to 85 ℃, performing ultrasonic (P=600W) reaction for 45min, centrifugally washing 3 times by using water and ethanol, and freeze-drying to obtain the Magnetic Amino Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 4
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 5:5:7 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 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, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Aminated Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 2:3.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 5
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 2:2:3 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feSO 4 ·7H 2 O and Fe 2 (SO 4 )·H 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, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Aminated Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:1.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 6
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 2:2:3 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feSO 4 ·7H 2 O andFe 2 (SO 4 )·H 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, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Aminated Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 2:1.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 4:5 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 7
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:2 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 2 O and Fe 2 (SO 4 )·H 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, 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). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 8
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:2 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 2 O and Fe 2 (SO 4 )·H 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, 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). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 4:5 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 9
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
the mass ratio of the catalyst is 1:1:1 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feSO 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C with ultrasound (P=400W), and adding NH dropwise after 2 hr 3 ·H 2 O-NH 4 NO 3 The solution is heated to 85 ℃ by ultrasonic (P=600W) until the pH value is 10, the 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 by freeze-drying. Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparation of polyethylene glycol coated magnetic graphene oxide (MGO-PEG):
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and LAPB (lauramidopropyl betaine) with a mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing (water and ethanol), and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-LAPB).
Example 10
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:1 (GO and Fe 3 O 4 Mass ratio 1:1.2) GO, feSO 4 ·7H 2 O and FeCl 3 ·6H 2 Dispersing O in deionized water, heating to 50deg.C with ultrasound (P=400W), and adding NH dropwise after 2 hr 3 ·H 2 O-NH 4 NO 3 The solution is heated to 85 ℃ by ultrasonic (P=600W) until the pH value is 10, the 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 by freeze-drying. Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparation of polyethylene glycol coated magnetic graphene oxide (MGO-PEG):
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and EAB (erucamide propyl betaine) with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-EAB).
Example 11
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 5:5:7 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 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, warmed to 85 ℃, reacted by ultrasound (p=600w) for 45min, washed 3 times with water and ethanol by centrifugation, and lyophilized to obtain Magnetic Aminated Graphene Oxide (MAGO). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2.2:4.5, carrying out low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
Example 12
The preparation method of the magnetic graphene oxide surfactant comprises the following steps:
(1) Preparing magnetic graphene oxide:
the mass ratio of the catalyst is 1:1:2 (GO and Fe 3 O 4 Mass ratio 1:1) GO, feCl 2 ·4H 2 O and Fe 2 (SO 4 )·H 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, 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). Wherein FeSO 4 ·7H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
(2) Preparing polyethylene glycol-coated magnetic graphene oxide:
dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 90 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
(3) Magnetic graphene oxide surfactant:
dispersing MGO-PEG and BS12 with the mass ratio of 1:1 in methanol, heating to 55 ℃ for reaction for 14h, centrifugally washing with water and ethanol, and freeze-drying to obtain the novel magnetic graphene oxide surfactant (MGO-PEG-BS 12).
The magnetic graphene oxide surfactant prepared in example 1 was characterized, and the obtained results are shown in fig. 1 and 2. FIG. 1 is an atomic force microscope photograph, and as can be seen from FIG. 1, magnetic graphene oxide has formed a two-dimensional lamellar structure through oxidation and magnetization; fig. 2 is an infrared spectrum, and as can be seen from fig. 2, most of the graphene oxide has been exfoliated into a lamellar structure, and the magnetic ferroferric oxide nanoparticle has been successfully loaded on the graphene oxide. Fig. 3 is a hysteresis loop diagram, and as can be seen from fig. 3, the magnetic strength is 13emu/g, which is close to that of a ferromagnetic material. The characterization of the magnetic graphene oxide surfactant prepared in other embodiments is similar to that, and the description of the present invention is omitted.
Example 13
In this example, the emulsification effect test was performed using the magnetic graphene oxide surfactant obtained in example 1:
the samples prepared in example 1 were prepared into 0.1%, 0.15%, 0.2%, 0.25%, 0.3% and 0.35% of displacement fluid respectively, and the emulsification effect was tested, 5mL of displacement fluid and 5mL of white oil were put into a 20mL custom test tube, the tube mouth was closed and vibrated up and down for 3 times, and data were recorded, so that fig. 5 (emulsion layer volume diagram of displacement fluid with different concentrations) was obtained.
Example 14
In this example, the emulsification effect test was performed using the magnetic graphene oxide surfactant obtained in example 5:
the samples prepared in example 5 were prepared into 0.1%, 0.15%, 0.2%, 0.25%, 0.3% and 0.35% of displacement fluid respectively, and the emulsification effect was tested, 5mL of displacement fluid and 5mL of white oil were put into a 20mL custom test tube, the tube mouth was closed and the tube mouth was oscillated up and down for 3 times, and the data were recorded, to obtain fig. 6 (emulsion layer volume diagram of displacement fluid with different concentrations).
Both fig. 5 and 6 show that the emulsification performance improvement is most pronounced at a surfactant concentration of 0.25%.
Example 15
In this example, the magnetic graphene oxide surfactant obtained in example 1 was used for oilfield sewage treatment test:
after oil removal, suspended matter removal and sterilization treatment of Daqing oilfield sewage, the Daqing oilfield sewage is subjected to adsorption treatment by using the sample prepared in the example 1, the water quality before and after the treatment is respectively tested by ICP, and data are recorded as shown in Table 1. Table 1 shows that the surfactant has a certain adsorption effect on metal ions in oilfield sewage.
TABLE 1
Element(s) Content before adsorption (mg/L) Post-adsorption content (mg/L)
Sodium salt 5683.68 4935.31
Calcium 1236.12 865.32
Magnesium (Mg) 453.14 236.56
Copper (Cu) 2.16 1.54
Manganese (Mn) 3.15 0.48
Strontium (strontium) 1.69 0.83
Chromium (Cr) 0.09 0.04
Nickel (Ni) 0.26 0.05
Iron (Fe) 1.39 0.86
Zinc alloy 0.28 0.11
Comparative example 1
Comparative example 1 differs from example 1 in that no magnetization modification was performed, similar to the products currently on the market, and was prepared by reacting only graphene oxide with dodecyl dimethyl betaine.
Dispersing 0.5g of graphene oxide in 300mL of methanol solution, adding 0.5g of dodecyl dimethyl betaine 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 surfactant.
The nano-lamellar surfactant prepared in comparative example 1 was tested and found to be only capable of emulsification but limited in emulsification effect and not capable of rapid demulsification.
Fig. 4a and 4b are graphs showing the emulsification and demulsification effects of the surfactants obtained in example 1 and comparative example 1, respectively, and it can be seen from fig. 4a and 4b that the emulsification effect of the surfactant oil-water in example 1 and the demulsification effect under an external magnetic field are both stronger than those in comparative example 1.
Therefore, the invention can effectively graft betaine surfactant, so that oil-water is efficiently emulsified, and the emulsion can be rapidly and stably broken under the condition of an externally applied magnetic field, and can also have a certain adsorption effect on metal ions in oilfield sewage.
Comparative example 2
Comparative example 2 was prepared by dispersing only magnetic graphene oxide and polyethylene glycol in an aqueous solution, as compared with example 2.
Dispersing MGO, EDC, PEG-6000 in deionized water according to a mass ratio of 5:2:4, performing low-temperature ultrasonic treatment for 30min, and then heating to 80 ℃ and stirring for 4h. Cooling to room temperature, centrifuging with water and ethanol, washing, and lyophilizing to obtain MGO-PEG powder.
Dispersing the MGO-PEG in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the magnetic graphene oxide surfactant (MGO-PEG).
The surfactant obtained by directly dispersing MGO-PEG in methanol without adding BS-12 has good emulsifying effect, but is easy to agglomerate under the condition of high mineralization degree.
Comparative example 3
Comparative example 2 differs from example 2 in that only magnetic graphene oxide was used with dodecyl dimethyl betaine.
Dispersing MGO and BS12 with the mass ratio of 4:5 in methanol, heating to 50 ℃ for reaction for 12 hours, centrifugally washing with water and ethanol, and freeze-drying to obtain the magnetic graphene oxide surfactant (MGO-BS 12).
The emulsion breaking effect of the surfactant obtained by dispersing the magnetic graphene oxide which is not coated by PEG and BS12 in methanol is observed, and the surfactant is not easy to agglomerate, but the emulsion breaking effect is poor.
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 (10)

1. The preparation method of the magnetic graphene oxide surfactant is characterized by comprising the following steps of:
s1, graphene oxide, an iron source and NH 3 ·H 2 O-NH 4 NO 3 Mixing the solutions to react to obtain the magnetic graphene oxide, wherein the graphene oxide and an iron source are prepared according to the following steps of graphene oxide and Fe 3 O 4 The mass ratio of the iron source package is 1:0.8-1.2Including ferrous salts and ferric salts; the molar ratio of the ferrous salt to the ferric salt is 1:1-3;
s2, dispersing the magnetic graphene oxide in deionized water, and adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and polyethylene glycol to react to obtain polyethylene glycol-coated magnetic graphene oxide, wherein the mass ratio of the magnetic graphene oxide to the polyethylene glycol is (3.5-4.5);
and S3, adding the polyethylene glycol-coated magnetic graphene oxide and a surfactant into a solvent for reaction to obtain the magnetic graphene oxide surfactant.
2. The method of claim 1, wherein the reactions in the method are all performed in an ultrasonic reactor.
3. The preparation method according to claim 1, wherein S1 specifically comprises:
dispersing graphene oxide and an iron source in deionized water, and dropwise adding NH 3 ·H 2 O-NH 4 NO 3 And (3) reacting the solution until the pH value is=9.2-10.5, centrifuging and washing after the reaction is finished, and drying to obtain the magnetic graphene oxide.
4. A method of preparation according to claim 3, 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).
5. The process according to claim 3, wherein the reaction in S1 is carried out at a temperature of 70 to 90℃for a period of 45 to 60 minutes.
6. The preparation method of claim 1, wherein the mass ratio of the polyethylene glycol-coated magnetic graphene oxide to the surfactant in S3 is 4 (4-5).
7. The method according to claim 1, wherein the surfactant is a betaine-type surfactant.
8. The method according to claim 7, wherein the betaine surfactant comprises one or a combination of two or more of dodecyl dimethyl betaine, lauramidopropyl betaine, and erucamidopropyl betaine.
9. The preparation method according to claim 1, wherein the reaction temperature in S2 is 80-90 ℃ and the reaction time is 3-5 h;
the reaction temperature in the step S3 is 48-55 ℃, and the reaction time is 12-14 h;
the solvent in S3 is methanol or DMF.
10. A magnetic graphene oxide surfactant obtainable by the process of any one of claims 1 to 9.
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