CN110317583B - Magnetic intelligent controllable foam system and preparation method thereof - Google Patents

Magnetic intelligent controllable foam system and preparation method thereof Download PDF

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CN110317583B
CN110317583B CN201810271325.1A CN201810271325A CN110317583B CN 110317583 B CN110317583 B CN 110317583B CN 201810271325 A CN201810271325 A CN 201810271325A CN 110317583 B CN110317583 B CN 110317583B
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magnetic
foam
reaction
foam system
organic solvent
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CN110317583A (en
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武俊文
张汝生
苏建政
岑学齐
黄志文
陈瞰瞰
史爱萍
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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Abstract

The invention discloses a magnetic intelligent controllable foam system and a preparation method thereof, wherein the foam system comprises the following components in percentage by total weight of the magnetic intelligent controllable foam system: 0.05 to 2 weight percent of foaming agent main agent, 0.1 to 2.0 weight percent of foam stabilizing auxiliary agent and the balance of water; the foaming agent main agent is a magnetic-responsive ionic surfactant, and the foam stabilizing auxiliary agent is magnetic-responsive nano particles. The magnetic foam system is more stable under the action of a magnetic field than a common foam system, has a longer foam half-life period, can fully exert the function of foam fluid, can realize intelligent controllability of the magnetism of the foam fluid, is applied to the development link of the petroleum industry, realizes controllable recovery, and further reduces the environmental protection pressure.

Description

Magnetic intelligent controllable foam system and preparation method thereof
Technical Field
The invention belongs to the technical field of oilfield development, and particularly relates to a magnetic intelligent controllable foam system and a preparation method thereof.
Background
The foam fluid has the advantages of adjustable density, good compressibility, high viscosity, small frictional resistance, small liquid consumption, small damage to a reservoir, strong solid particle carrying capacity and the like, and is widely applied to various process links of the petroleum industry, such as acidification, fracturing, blockage removal, sand washing, well washing, water cone pressing, profile control, reservoir transformation and the like. In the actual production of oil fields, the foaming agent adopted by a foam system is generally an AES or LAS based surfactant, the salt resistance is poor, the biodegradability is poor, and the environmental protection pressure of foam flowback liquid in oil field operation is high. Since foams are thermodynamically unstable systems by their very nature, various means have been employed to increase foam stability. For example, the liquid film drainage time is prolonged by increasing the liquid phase viscosity by using a polymer foam stabilizer assistant such as polyacrylamide and the like, so that the foam stability is enhanced, but the added polymer foam stabilizer can be pyrolyzed under the high-temperature condition, and the generated organic matter residue can cause the damage of the stratum to a certain extent; part of the hydrophobic silicon dioxide nano particles can also be used as a foam stabilizing auxiliary agent, and the hydrophobic silicon dioxide nano particles are adsorbed on the surface of the liquid film, so that the strength of the liquid film can be greatly improved, and the foam stability is further improved; the foam system can adapt to underground complex oil reservoir conditions, and simultaneously, as the particle size of the nano particles is different from the pore throat size of the stratum in micron level by one order of magnitude, the particles fall off from the bubble wall after defoaming, and can be directly discharged from the stratum through subsequent displacement; meanwhile, the adopted silicon dioxide nano particles have good compatibility with the stratum, and the pollution degree of the foam to the stratum environment is greatly reduced compared with other types of foams; however, since the hydrophobic property is strong, the dispersibility of the system is poor and the utilization efficiency of the nanoparticles is low.
In conclusion, the foam system is widely applied to the petroleum industry, the existing foam system is limited by the structures of foaming agent molecules and foam stabilizing auxiliary agent molecules, and great pressure is brought to environmental protection while the yield is increased and the effect is promoted.
Disclosure of Invention
The invention aims to solve the environmental protection problem caused by a common foam system used in the current oil and gas development, and provides a magnetic intelligent controllable foam system and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a magnetic intelligent controllable foam system, comprising, based on the total weight of the magnetic intelligent controllable foam system: 0.05 to 2 weight percent of foaming agent main agent, 0.1 to 2.0 weight percent of foam stabilizing auxiliary agent and the balance of water; the foaming agent main agent is a magnetic-responsive ionic surfactant, and the foam stabilizing auxiliary agent is magnetic-responsive nano particles.
Preferably, the magnetic-responsive ionic surfactant is prepared by the complexation reaction of a f-region magnetic transition metal complex and a glycosyl cationic surfactant.
Preferably, the f-block magnetic transition metal is at least one of Fe, Gd, Ho and Ce.
Preferably, the f-block magnetic transition metal complex is FeCl3、GdCl3、HoCl3And CeCl3At least one of (1).
Preferably, the preparation method of the magnetic-responsive ionic surfactant comprises the following steps:
(1) under the existence of a first organic solvent and a nucleophilic substitution reaction regulator, carrying out contact reaction on N-methyl-D-glucosamine and halogenated alkane to obtain monoalkyl-methyl-D-glucosamine;
(2) carrying out contact reaction on monoalkyl-methyl-D-glucosamine and hydrochloric acid, then carrying out reduced pressure distillation to remove a solvent, and drying to obtain monoalkyl-methyl-D-glucosamine chloride;
(3) and in the presence of a second organic solvent, carrying out contact reaction on monoalkyl-methyl-D-glucosamine chloride and the f-region magnetic transition metal complex, removing the second organic solvent, and drying to obtain the magnetic-responsive ionic surfactant.
Preferably, in the step (1), after the reaction is finished, the first organic solvent and the unreacted N-methyl-D-glucosamine are removed, and then the monoalkyl-methyl-D-glucosamine is obtained after extraction, recrystallization and drying; the halogenated alkane is CnH2n+ 1Br, n-8, 12 or 16; the first organic solvent is methanol, and the nucleophilic substitution reaction regulator is sodium carbonate; the mass ratio of the N-methyl-D-glucose methylamine to the halogenated alkane is 3-5: 1, the reaction temperature is 40-60 ℃, and the reaction time is 30-40 h;
in the step (2), the reaction temperature is 20-30 ℃, and the reaction time is 5-10 h;
in the step (3), the second organic solvent is methanol, and the f-zone magnetic transition metal complex is FeCl3、GdCl3、HoCl3And CeCl3At least one of monoalkyl-methyl-D-chloroglucosamine and an f-block magnetic transition metal complex in a mass ratio of 1: 0.2 to 0.7, the reaction temperature is 20 to 30 ℃, and the reaction time is 10 to 25 hours.
Preferably, the preparation method of the magnetically responsive nanoparticles comprises the following steps:
(1) FeCl is added in the presence of a third organic solvent and a hydrolysis regulator3·6H2Carrying out hydrolysis reaction on O, cooling and washing to obtain Fe3O4A nanoparticle;
(2) in the presence of water and a first catalyst, Fe3O4The ethanol dispersion liquid of the nano particles and ethyl orthosilicate are subjected to contact reaction, and then the Fe is obtained after washing, filtering and drying3O4@SiO2Core-shell structured nanoparticles;
(3) and in the presence of a fourth organic solvent and a second catalyst, carrying out contact reaction on the ferroferric oxide silica core-shell structure nano particles and a silane coupling agent, and then carrying out centrifugal separation, washing, filtering and drying to obtain the magnetic response nano particles.
Preferably, in the step (1), the third organic solvent is ethylene glycol, the hydrolysis regulator is sodium acetate and polyethylene glycol, the reaction temperature is 150-250 ℃, and the reaction time is 10-25 h;
in the step (2), the first catalyst is ammonia water with the mass concentration of 25-28%, and the Fe3O4The volume ratio of the ethanol dispersion liquid of the nano particles to the tetraethoxysilane is 1: 0.05-0.2, the reaction temperature is 20-30 ℃, and the reaction time is 2-8 h;
in the step (3), the fourth organic solvent is ethanol, the second catalyst is ammonia water, and the Fe is3O4@SiO2The feed-liquid ratio of the core-shell structure nano-particles to the silane coupling agent is 1:1-3g/ml, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 h.
The second aspect of the present invention provides a preparation method of the above magnetic intelligent controllable foam system, which comprises: and mixing the foaming agent main agent, the foam stabilizing auxiliary agent and water to form a multiphase foam system, thereby obtaining the magnetic intelligent controllable foam system.
Preferably, the heterogeneous foam system is formed using the Roche foam pour method.
The technical scheme of the invention has the following advantages:
(1) according to the technical scheme, the foaming agent main agent is a designed and synthesized magnetic-response surfactant, the foam stabilizing auxiliary agent is magnetic-response nano particles, the foam system prepared from the two magnetic-response raw materials has magnetic response, so that reversible control over the magnetic foam system can be realized by using the existence or nonexistence of an external magnetic field, and due to the introduction of the magnetic surfactant, the magnetic surfactant has stronger surface tension reduction effect than that of a common surfactant under the action of the magnetic field, so that the formed magnetic foam system is more stable than the common foam system, has a longer foam half-life period, and can more fully exert the function of foam fluid.
(2) The magnetic foam system can be widely applied to various process links in the petroleum industry, such as acidification, fracturing, blockage removal, sand washing, well washing, water cone pressing, profile control, reservoir transformation and the like, and can realize intelligent and controllable magnetism of foam fluid and controllable recovery, thereby reducing the environmental protection pressure.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In a first aspect of the present invention, there is provided a magnetic intelligent controllable foam system, comprising, based on the total weight of the magnetic intelligent controllable foam system: 0.05 to 2 weight percent of foaming agent main agent, 0.1 to 2.0 weight percent of foam stabilizing auxiliary agent and the balance of water; the foaming agent main agent is a magnetic-responsive ionic surfactant, and the foam stabilizing auxiliary agent is magnetic-responsive nano particles.
According to the present invention, preferably, the magnetic-responsive ionic surfactant is prepared by a complex reaction of a f-region magnetic transition metal complex and a glycosyl cationic surfactant.
According to the present invention, preferably, the f-block magnetic transition metal is at least one of Fe, Gd, Ho and Ce.
According to the present invention, preferably, the f-block magnetic transition metal complex is FeCl3、GdCl3、HoCl3And CeCl3At least one of (1).
In order to overcome the defects of poor biocompatibility and strong irritation of the common quaternary ammonium salt cationic surfactant, the invention complexes f-region magnetic transition metal complexes such as Fe, Gd, Ho, Ce and the like into the glycosyl cationic surfactant to be used as the magnetic ionic surfactant and the foaming agent main agent. The surfactant is produced by using the carbohydrate, so that the raw materials are low in price and rich in resources, and the obtained product is mild, non-toxic, excellent in performance and good in environmental compatibility.
According to the present invention, preferably, the preparation method of the magnetically-responsive ionic surfactant comprises the steps of:
(1) under the existence of a first organic solvent and a nucleophilic substitution reaction regulator, carrying out contact reaction on N-methyl-D-glucosamine and halogenated alkane to obtain monoalkyl-methyl-D-glucosamine;
(2) carrying out contact reaction on monoalkyl-methyl-D-glucosamine and hydrochloric acid, then carrying out reduced pressure distillation to remove a solvent, and drying to obtain monoalkyl-methyl-D-glucosamine chloride;
(3) and in the presence of a second organic solvent, carrying out contact reaction on monoalkyl-methyl-D-glucosamine chloride and the f-region magnetic transition metal complex, removing the second organic solvent, and drying to obtain the magnetic-responsive ionic surfactant.
According to the invention, preferably, in the step (1), after the reaction is finished, the first organic solvent and unreacted N-methyl-D-glucosamine are removed, and then the monoalkyl-methyl-D-glucosamine is obtained after extraction, recrystallization and drying; the halogenated alkane is CnH2n+1Br, n-8, 12 or 16; the first organic solvent is methanol, and the nucleophilic substitution reaction regulator is sodium carbonate; the mass ratio of the N-methyl-D-glucose methylamine to the halogenated alkane is 3-5: 1, the reaction temperature is 40-60 ℃, and the reaction time is 30-40 h;
extraction and recrystallization any reagent suitable for the present invention may be selected, and preferably extraction with ethyl acetate and recrystallization with ethanol is performed.
In the step (2), the reaction temperature is 20-30 ℃, and the reaction time is 5-10 h; in the present invention, the hydrochloric acid used is preferably concentrated hydrochloric acid having a mass concentration of 35 to 40%.
In the step (3), the second organic solvent is methanol, and the f-zone magnetic transition metal complex is FeCl3、GdCl3、HoCl3And CeCl3At least one of monoalkyl-methyl-D-chloroglucosamine and an f-block magnetic transition metal complex in a mass ratio of 1: 0.2-0.7, reaction temperature of 20-30 ℃, and reaction timeIs 10-25 h.
The invention synthesizes Fe with a certain size by controlling the solution condition3O4Magnetic nanoparticles, and SiO2Coating and preparing Fe3O4@SiO2Core-shell magnetic nanoparticles, to Fe3O4@SiO2The core-shell type magnetic nano-particles are subjected to surface modification to improve the dispersion performance of the core-shell type magnetic nano-particles, the surfaces of the core-shell type magnetic nano-particles are adjusted to be appropriate hydrophilic and hydrophobic, the effect of stabilizing foams is achieved, and the modified Fe3O4@SiO2The core-shell type magnetic nano-particles are used as a foam stabilizing auxiliary agent.
According to the present invention, preferably, the method for preparing the magnetically responsive nanoparticles comprises the steps of:
(1) FeCl is added in the presence of a third organic solvent and a hydrolysis regulator3·6H2Carrying out hydrolysis reaction on O, cooling and washing to obtain Fe3O4A nanoparticle;
(2) in the presence of water and a first catalyst, Fe3O4The ethanol dispersion liquid of the nano particles and ethyl orthosilicate are subjected to contact reaction, and then the Fe is obtained after washing, filtering and drying3O4@SiO2Core-shell structured nanoparticles;
(3) and in the presence of a fourth organic solvent and a second catalyst, carrying out contact reaction on the ferroferric oxide silica core-shell structure nano particles and a silane coupling agent, and then carrying out centrifugal separation, washing, filtering and drying to obtain the magnetic response nano particles.
According to the invention, preferably, in the step (1), the third organic solvent is ethylene glycol, the hydrolysis regulator is sodium acetate and polyethylene glycol, the reaction temperature is 150-;
in the step (2), the first catalyst is ammonia water with the mass concentration of 25-28%, and the Fe3O4The volume ratio of the ethanol dispersion liquid of the nano particles to the tetraethoxysilane is 1: 0.05-0.2, the reaction temperature is 20-30 ℃, and the reaction time is 2-8 h;
in the step (3), the fourth organic solvent is ethanol,the second catalyst is ammonia water, and the Fe3O4@SiO2The feed-liquid ratio of the core-shell structure nano-particles to the silane coupling agent is 1:1-3g/ml, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 h.
The second aspect of the present invention provides a preparation method of the above magnetic intelligent controllable foam system, which comprises: and mixing the foaming agent main agent, the foam stabilizing auxiliary agent and water to form a multiphase foam system, thereby obtaining the magnetic intelligent controllable foam system.
Any suitable means for forming the multi-phase foam system may be selected, and preferably the multi-phase foam system is formed by means of a Roche foam pour method.
The invention is further illustrated by the following examples:
preparation examples 1 to 4 each provide a blowing agent master of the invention: the preparation method of the magnetic response ionic surfactant comprises the following steps:
preparation example 1
(1) Synthesis of monoalkyl-methyl-D-glucosamine (G-C)n)
Mixing 5.6g N-methyl-D-glucamine and 1.6g C12H25Adding Br into 130mL of methanol, adding 1.8g of sodium carbonate into the obtained solution, heating to 50 ℃ for reaction for 36h, then adding 300mL of methanol, and heating the system to 50 ℃ for reaction for 1 h; after the solvent methanol is removed from the reaction mixture by reduced pressure distillation, dispersing the obtained product in 350mL deionized water to remove unreacted N-methyl-D-glucosylmethylamine; adding 200mL of ethyl acetate into the solution, filtering to obtain solid powder, drying at room temperature, recrystallizing for 3 times by using ethanol, and drying in a vacuum drying oven at 60 ℃ for 3 hours to obtain a target product;
(2) synthesis of monoalkyl-methyl-D-chloroglucosamine ([ H-G-C)n]Cl)
Adding 3.2g of monoalkyl-methyl-D-glucosamine and 2mL of concentrated hydrochloric acid with the mass concentration of 38% into deionized water, reacting at room temperature for 8 hours after vigorous stirring, removing solvent water by reduced pressure distillation, and drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain a target product;
(3) synthesis of magnetically responsive ionic surfactants
3.0g of monoalkyl-methyl-D-chloroglucosamine and 1.1g of FeCl3Adding into 50mL methanol, stirring, reacting at room temperature for 18H, evaporating methanol, drying in 60 deg.C vacuum drying oven for 5H to obtain magnetic response ion surfactant [ H-G-C ]n]FeCl4。
Preparation example 2:
the difference between this preparation and preparation 1 is that in step (3), the f-block magnetic transition metal complex used is GdCl31.3g of the catalyst; the other reaction steps, the materials and amounts used, and the reaction conditions were the same as those in preparation example 1.
Preparation example 3:
the difference between this preparation and preparation 1 is that in step (3), the f-block magnetic transition metal complex used is HoCl31.6g of the catalyst; the other reaction steps, the materials and amounts used, and the reaction conditions were the same as those in preparation example 1.
Preparation example 4:
the difference between this preparation and preparation 1 is that in step (3), the f-block magnetic transition metal complex used is CeCl31.8g of the catalyst; the other reaction steps, the materials and amounts used, and the reaction conditions were the same as those in preparation example 1.
Preparation example 5
The preparation example provides the foam stabilizing additive magnetic-responsive nanoparticles, which are spherical, have the size of 10-80 nm, and have the following hydrophobic degree: the gas-liquid-solid three-phase contact angle is 30-90 degrees; the preparation method comprises the following steps:
(1)Fe3O4preparation of nanoparticles
0.95g FeCl3·6H2Adding O into 50mL of ethylene glycol, stirring and dissolving, then sequentially adding 1.98g of sodium acetate and 1.1g of ethylene glycol, stirring at normal temperature for 1h, then adding the mixed solution into a polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 18h, naturally cooling to room temperature, and then washing the obtained solid with deionized water for multiple times to obtain Fe3O4Dispersing the nano particles in 30mL of ethanol for later use;
(2)Fe3O4@SiO2preparation of core-shell structure nanoparticles
Mixing the above 30mL of Fe3O4Mixing ethanol dispersion of nano particles, 20mL of deionized water and 3.6mL of TEOS, then dropwise adding 5.5mL of concentrated ammonia water with the mass concentration of 27.6%, stirring and sealing for reaction for 5 hours, respectively washing obtained solid particles with deionized water for several times, filtering and drying to obtain Fe3O4@SiO2Core-shell structured nanoparticles.
(3) Magnetically responsive nanoparticles
1.5g of Fe3O4@SiO2And adding the core-shell structure nanoparticles into 30mL of ethanol, stirring for dispersing, heating to 100 ℃, adding 3mL of silane coupling agent into the obtained mixture, slowly dropwise adding 8mL of ammonia water into the mixture, heating and refluxing for 3h, centrifuging the obtained product, washing the product for several times by using ethanol, filtering and drying to obtain the magnetic response nanoparticles.
Example 1
The embodiment provides a magnetic intelligent controllable foam system, and the specific preparation method comprises the following steps:
0.2G of magnetic response ion surfactant [ H-G-C ] is added into 50mL of deionized watern]FeCl4(product of preparation 1) and 0.3g of magnetically responsive nanoparticles (product of preparation 5) were used to form a stable heterogeneous foam system by means of the Roche foam machine pour method.
Example 2
0.38G of magnetic response ion surfactant [ H-G-C ] is added into 50mL of deionized watern]GdCl4(product of preparation example 2) and 0.3g of magnetically responsive nanoparticles (product of preparation example 5) were poured into a stable heterogeneous foam system by means of a Roche foam apparatus.
Example 3
0.42G of magnetic response surfactant H-G-C is added into 50mL of deionized watern]HoCl4(product of preparation 3) and 0.3g of magnetically responsive nanoparticles (product of preparation 5) were used to form a stable heterogeneous foam system by means of the Roche foam machine pour method.
Example 4
50mL deionizationAdding 0.65G of magnetic response surfactant (H-G-C) into watern]CeCl4(product of preparation 4) and 0.3g of magnetically responsive nanoparticles (product of preparation 5) were used to form a stable heterogeneous foam system by means of Roche foam apparatus pouring.
Test example 1
The magnetic-responsive surfactants prepared in preparation examples 1 to 4 were subjected to surface tension test, in which the magnetic field strength was 0.9 tesla, the surface tension was measured by the pendant drop method, the mass concentration of the magnetic-responsive surfactant to be measured was 0.01%, and the specific test results are shown in table 1.
TABLE 1
Figure BDA0001612625220000101
As can be seen from the data in Table 1, the aqueous solution formed by the magnetic response surfactant has stronger capability of reducing the surface tension under the action of a magnetic field and shows magnetic response, and the lower the surface tension, the lower the surface energy of the foam system is, and the more stable the system is.
Test example 2
The magnetic intelligent controllable foam systems prepared in examples 1 to 4 and the common foam system of the comparative example were subjected to foam stability test (foam half-life is an important indicator of foam stability, and means that the foam height decays to half of the time, the more stable the foam is, the longer the half-life), and the specific test method was the roche foam method, and the specific test results are shown in table 2.
TABLE 2
Figure BDA0001612625220000111
As can be seen from the evaluation data in Table 2, the half-life period of the same foam system is obviously increased under the action of a magnetic field, the foam stability is obviously improved, and the same magnetic responsiveness is also shown.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (6)

1. A magnetic intelligent controllable foam system is characterized in that the foam system consists of the following components in percentage by weight of the total weight of the magnetic intelligent controllable foam system: 0.05 to 2 weight percent of foaming agent main agent, 0.1 to 2.0 weight percent of foam stabilizing auxiliary agent and the balance of water; the foaming agent main agent is a magnetic-responsive ionic surfactant, and the foam stabilizing auxiliary agent is magnetic-responsive nano particles;
the preparation method of the magnetic-responsive ionic surfactant comprises the following steps:
(1) under the existence of a first organic solvent and a nucleophilic substitution reaction regulator, carrying out contact reaction on N-methyl-D-glucosamine and halogenated alkane to obtain monoalkyl-methyl-D-glucosamine;
(2) carrying out contact reaction on monoalkyl-methyl-D-glucosamine and hydrochloric acid, then carrying out reduced pressure distillation to remove a solvent, and drying to obtain monoalkyl-methyl-D-glucosamine chloride;
(3) monoalkyl-methyl-D-chloroglucamine and f-block magnetic transition metal complex and/or FeCl in the presence of a second organic solvent3Carrying out contact reaction, then removing the second organic solvent, and drying to obtain the magnetic response ionic surfactant;
the halogenated alkane is CnH2n+1Br, n =8, 12 or 16;
the preparation method of the magnetic responsiveness nano particle comprises the following steps:
(1) FeCl is added in the presence of a third organic solvent and a hydrolysis regulator3·6H2Carrying out hydrolysis reaction on O, cooling and washing to obtain Fe3O4A nanoparticle;
(2) in the presence of water and a first catalyst, Fe3O4The ethanol dispersion liquid of the nano particles and the tetraethoxysilane are subjected to contact reaction, and then washing, filtering and drying are carried outThen obtaining Fe3O4@SiO2Core-shell structured nanoparticles;
(3) in the presence of a fourth organic solvent and a second catalyst, Fe3O4@SiO2And (3) carrying out contact reaction on the core-shell structure nanoparticles and a silane coupling agent, and then carrying out centrifugal separation, washing, filtering and drying to obtain the magnetic response nanoparticles.
2. The magnetic smart controllable foam system according to claim 1, wherein the f-block magnetic transition metal is at least one of Gd, Ho, and Ce.
3. The magnetic intelligent controllable foam system according to claim 1, wherein in step (1) of the preparation method of the magnetic responsive ionic surfactant, the first organic solvent and unreacted N-methyl-D-glucosamine are removed after the reaction is finished, and the monoalkyl-methyl-D-glucosamine is obtained after re-extraction, recrystallization and drying; the first organic solvent is methanol, and the nucleophilic substitution reaction regulator is sodium carbonate; the mass ratio of the N-methyl-D-glucosamine to the halogenated alkane is 3-5: 1, the reaction temperature is 40-60 ℃, and the reaction time is 30-40 h;
in the step (2) of the preparation method of the magnetic response ionic surfactant, the reaction temperature is 20-30 ℃, and the reaction time is 5-10 h;
in the step (3) of the process for producing a magnetically responsive ionic surfactant, the second organic solvent is methanol, and the f-block magnetic transition metal complex is GdCl3、HoCl3And CeCl3At least one of monoalkyl-methyl-D-chloroglucosamine and an f-block magnetic transition metal complex in a mass ratio of 1: 0.2 to 0.7, the reaction temperature is 20 to 30 ℃, and the reaction time is 10 to 25 hours.
4. The magnetic intelligent controllable foam system according to claim 1, wherein in step (1) of the preparation method of the magnetic-responsive nanoparticles, the third organic solvent is ethylene glycol, the hydrolysis regulator is sodium acetate and polyethylene glycol, the reaction temperature is 150 ℃ and 250 ℃, and the reaction time is 10-25 h;
in the step (2) of the preparation method of the magnetic responsiveness nano particles, the first catalyst is ammonia water with the mass concentration of 25-28%, and the Fe3O4The volume ratio of the ethanol dispersion liquid of the nano particles to the tetraethoxysilane is 1: 0.05-0.2, the reaction temperature is 20-30 ℃, and the reaction time is 2-8 h;
in the step (3) of the method for preparing the magnetic-responsive nanoparticles, the fourth organic solvent is ethanol, the second catalyst is ammonia water, and the Fe is3O4@SiO2The feed-liquid ratio of the core-shell structure nano-particles to the silane coupling agent is 1:1-3g/ml, the reaction temperature is 80-120 ℃, and the reaction time is 2-4 h.
5. A method of preparing a magnetic intelligent controllable foam system according to any of claims 1 to 4, characterized in that the method comprises: and mixing the foaming agent main agent, the foam stabilizing auxiliary agent and water to form a multiphase foam system, thereby obtaining the magnetic intelligent controllable foam system.
6. The production method according to claim 5, wherein the heterogeneous foam system is formed by means of a Roche foam machine pouring method.
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