CN108384573A - A kind of preparation method and application of hydrophilic magnetic Nano material - Google Patents
A kind of preparation method and application of hydrophilic magnetic Nano material Download PDFInfo
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- CN108384573A CN108384573A CN201810094676.XA CN201810094676A CN108384573A CN 108384573 A CN108384573 A CN 108384573A CN 201810094676 A CN201810094676 A CN 201810094676A CN 108384573 A CN108384573 A CN 108384573A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
Abstract
The invention belongs to technical field of nano material, relate generally to a kind of preparation method and application of hydrophilic magnetic Nano material, modification and application example of the synthesis, PEG modified silanes of modified γ (2, the 3 glycidoxy) propyl trimethoxy silicanes (KH560) of preparation, polyethylene glycol (PEG) including ferriferrous oxide nano fluid on ferroferric oxide nano granules surface.Its preparation process is simple for process, low production cost, and no coupling product generates, nano particle obtained about 16nm, has good homogeneous grain diameter, magnetic response, good hydrophilic property, nontoxic, advantages of environment protection.Oil water interfacial tension can be significantly reduced by the evenly dispersed obtained nano-fluid of nano particle is made, and solid mineral surface wettability can be improved, shows its applications well foreground in fields such as oily solid separation, tertiary oil recovery, pharmaceutical carrier and polymer displacement of reservoir oil.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to the preparation method of a kind of hydrophilic magnetic Nano material and
Application process.
Background technology
With the reduction of conventional fossil energy reserve in world wide, unconventional fossil energy accounts for energy proportion increasingly
Greatly, the method for the unconventional fossil energy of industrial utilization is mainly chemical reagent auxiliary WATER-WASHING METHOD at present.However traditional chemistry is auxiliary
It helps WATER-WASHING METHOD that can consume a large amount of thermal energy and chemical addition agent and the lotion for being difficult to handle later use can be generated.In order to reduce process
Energy consumption and water consume, new and effective method continue to bring out.Nano-fluid displacement process is with its low concentration, high stability, high activity etc.
Advantage causes more and more concerns.However nano particle is difficult to detach to be recycled with solution after displacement, this nothing
It doubts and affects the quality of product and the economy of process and industrialization.New material in recent years with two or more responses is continuous
It is developed, the property of multiple response enriches the flexibility for MAT'L recycling.Wherein nanometer magnetofluid be it is a kind of both
Advantageous property with nano-fluid is but also with the material of Magnetic Isolation property, the magnetic recycling that can be used for nano material
Process.
Nanometer magnetofluid refers to that the solid phase nanoscale that is formed in a solvent of magnetic nanoparticle dispersion, solid-liquid two-phase are uniform steady
Under gravitational field layering and precipitating does not occur for the soliquid mixed surely.It is a kind of mobility having both liquid and solid magnetic
A kind of new function material of the property material to the response characteristic in magnetic field.Therefore, it is widely used in chemical industry, biology and clinical doctor
Etc. multiple fields.And the core of nanometer magnetofluid is dispersed phase magnetic nanoparticle, and in numerous magnetic nanoparticles, four oxygen
Change three iron nano-particles have saturation magnetic strength it is big (>70emu/g), superparamagnetism is shown under room temperature, i.e., without coercivity and remanent magnetism
Property, thus as the hot spot of research.
However simple exposed ferriferrous oxide nano core is since its high-ratio surface energy is it occur frequently that agglomeration.In order to steady
Surely disperse nano-fluid, usually use the means such as ultrasound, surfactant compound, surface modification, wherein surface modification technology by
Modification group property can be flexibly selected while preventing ferroso-ferric oxide from being aoxidized in it and is concerned.Patent CN
107469796 A propose that a kind of modify Lignin phenolic to ferroso-ferric oxide surface using sour curing technology is made hud typed micro-
The technology of ball, the Dye Adsorption performance that lignin is had assign magnetic microsphere.107417914 A of patent CN use surface
Pyrrole monomer polymerize by polymerization in ferroso-ferric oxide, and magnetic composite obtained had both had the magnetism of ferroso-ferric oxide,
Have the excellent electrical properties of polypyrrole.
In order to strengthen heavy oil from mineral surfaces stripping process and delay ferroferric oxide nano granules oxidation process, select
It is crucial that one kind, which not only having had certain surface activity but also can improve the hydrophilic material of mineral surfaces,.Polyethylene glycol (PEG) relies on
Its good biocompatibility, wettability and oil-displacement capacity have been applied to the modification of biological medicine carrier surface and polymerization
Object strengthens the researchs such as tertiary oil recovery.
Invention content
The present invention provides a kind of preparation method and application of hydrophilic magnetic Nano material, and the present invention is aoxidized hydrophilic four for the first time
Three iron nano-particles are applied to oily solid separation process, have the property of Magnetic Isolation while ensureing good heavy oil organic efficiency
Matter.The hydrophilic magnetic Nano material that the present invention synthesizes not only has preferable magnetic response, and can strengthen mink cell focus from mine
Object sur-face peeling process has good application prospect to reduce operating cost.
The present invention realizes that the technical solution of purpose is as follows：
A kind of preparation method of hydrophilic magnetic Nano material, steps are as follows
(1) the preparation of ferriferrous oxide nano fluid：Containing Fe3+Salt and Fe2+Salt salt-mixture precursor solution 40-80 DEG C,
Precipitation solvent is slowly added dropwise under inert gas environment, precipitation 5-30min obtains product ferroferric oxide nano granules, product warp
Alcohol is washed, is washed each twice after magnet attracts, and is then dispersed in pH=8.5-9.5 lye, four oxidations are made in ultrasonic 10-30min
Three-iron nano-fluid；
(2) the addition of PEG and KH560：PEG first heats removal residual moisture under an inert atmosphere, then evenly spreads to
In acetonitrile solvent, acetic acid is added as catalyst, KH560 is added dropwise, reaction reflux obtains product, and product is at 120-125 DEG C
Lower distilling off solvent, catalyst and excess reactant obtain PEG modified silanes；
(3) modification of the PEG modified silanes on ferroferric oxide nano granules surface：First (2) silane is made in 10-30 in step
DEG C, 20-50min is hydrolyzed in pH=8.5-9.5 bucks, then hydrolysate is added dropwise in ferriferrous oxide nano fluid, instead
Magnet after a period of time is answered to detach, alcohol washes, wash and each is dried to obtain the hydrophilic magnetic Nano material of product acquisition twice.
Moreover, the Fe3+Salt and Fe2+The molar ratio of salt is 2.1:1-1.5:1.
Moreover, reaction solution final pH is 9.0-11.0.
Moreover, Fe in reaction raw materials3+From FeCl3·6H2O、Fe2(SO4)3In one kind；Fe2+From FeCl2·4H2O、
FeSO4·7H2O、Fe(NH4)2(SO4)2·6H2One kind in O.
Moreover, the precipitation solvent is one kind in ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution.
Moreover, (2) middle PEG and KH560 material molar ratios are 1 to the step:1.2-1:1.5.
Moreover, the PEG molecular weight is 200-2000.
Moreover, the step (2) in acetonitrile：Acetic acid volume ratio is 1000:1-500:1.
Moreover, the reaction temperature of step (2) is 88-92 DEG C.(2) the reaction time is 5-7h to step.
Moreover, (3) middle ferroso-ferric oxide, silane molar ratio are 1 to the step:1-1:1.5.
Moreover, (3) middle reaction temperature is 70-90 DEG C to the step, the reaction time of step (3) is 8-12h.
Hydrophilic magnetic Nano material is applied to the solid separation of oil, heavy oil extraction, water-oil separating or sand oil extracting oil.
Application process is as follows：Hydrophilic magnetic Nano material is distributed in the lye of pH=8.0-10.0, is made into nano-fluid,
Nano particle acts on oily liquid/solid interface and oil-water interfaces.
A kind of method of hydrophilic magnetic Nano material recycling heavy oil, steps are as follows：
(1) hydrophilic magnetic Nano material is distributed in the buck that pH is 8.0-10.0, and nano-fluid is made in ultrasonic disperse；
(2) (1) step is made nano-fluid and is stirred with heavy oil-raw mineral materials in flotation cell, is passed through after 10-15min
Isolated heavy oil froth flotation to solution surface is collected foam and analyzes the rate of recovery by gas；
(3) (2) step recycles nano particle in gained residual solution and tailings, and step is repeated (2) after washing is dry.
The advantages and positive effects of the present invention are as follows：
(1) the present invention modifies PEG to magnetic nanoparticle surface, obtains hydrophily and magnetic composite, composite material
Nano-fluid can be made after dispersion and the fields such as detach for oily solid separation, lotion；
(2) there is method provided by the invention easy to operate, mild condition, the high feature of reaction yield, hydrophily to be rung with magnetic
Ying Xingjun is good；
(3) the hydrophilic magnetic Nano material that prepared by the present invention can promote heavy oil from mineral surfaces stripping process, reduce heavy oil
Interfacial tension and recyclable recycling between water.
Description of the drawings
Fig. 1 is that this application involves reaction principle figures.
Fig. 2 is the application magnetic Nano material transmission electron microscope photo.
Fig. 3 is the application magnetic Nano material stereoscan photograph.
Fig. 4 is the application magnetic Nano material X-ray diffraction test result.
Fig. 5 is the application magnetic Nano material room temperature hysteresis loop.
Fig. 6 is the application magnetic Nano material product, ferroso-ferric oxide core and silane coupling agent nitrogen environment weight-loss curve.
Specific implementation mode
The present invention is explained by following examples, and however, it is not limited to this.
In order to enhance the interaction between PEG and ferroferric oxide nano granules, the present invention is by γ-(2,3- epoxies third
Oxygroup) propyl trimethoxy silicane (KH560) is bonded by glycidyl with hydroxyl ring-opening reaction with PEG, recycle silane water
Chemistry key connection is formed between solution and ferroso-ferric oxide to achieve the purpose that modify PEG on nano ferriferrous oxide surface.
The present invention develop it is a kind of be simple and efficient environmental-friendly chemical synthesis process, realize PEG in nano ferriferrous oxide
Hydrophilic ferroferric oxide nano granules are prepared in the modification on surface, and the specific method is as follows：
(1) by Fe3+Salt and Fe2+Salt is dissolved in deionized water, inert environments, mechanical agitation and at 50-80 DEG C slowly
Precipitation solvent is added dropwise, it is 9.0-11.0 to make solution final pH, and reaction 0.1-2h obtains ferroferric oxide nano granules.Product passes through
Alcohol is washed, washes each twice to remove excess reactant after magnet attracts, and is then dispersed in ultrasonic disperse in lye and four oxidations are made
Three-iron nano-fluid.Reaction principle is for example shown in the reaction 1. of attached drawing 1.
(2) measure PEG and heat removal residual moisture under an inert atmosphere, then evenly spread in acetonitrile solvent, be added
KH560 is added dropwise (with PEG molar ratios 1 as catalyst in 0.1% (volume fraction) acetic acid:1.2-1:1.5), at 88-92 DEG C
React 5-7h.Solution rotates removing acetonitrile, acetic acid, excess KH560 through vacuum and obtains target product PEG modified silanes (PEG-
KH560).Reaction principle is for example shown in the reaction 2. of attached drawing 1.
(3) the PEG-KH560 that (2) is step obtains fully hydrolyzed in buck first.Then four oxygen are added dropwise in hydrolysate
Change in three-iron nano-fluid, ferroso-ferric oxide, the control of silane molar ratio are 1:1-1:1.5, it is reacted under 70-90 DEG C of stirring in water bath
Magnet detaches after 8-12h, and alcohol, which washes, washes each twice is dried to obtain product.Reaction principle is for example shown in the reaction 3. of attached drawing 1.
PEG modifications nano ferriferrous oxide obtained above is as follows in the application of heavy oil removal process：
(1) PEG modification ferroferric oxide nano granules are distributed in the buck that pH is 8.0-10.0, ultrasonic disperse is made
Nano-fluid.
(2) (1) step is made nano-fluid and is stirred with heavy oil-raw mineral materials in flotation cell, is passed through after 10-15min
Isolated heavy oil froth flotation to solution surface is collected foam and analyzes the rate of recovery, oil is solid than (B/S) by gas.
(3) (2) step recycles nano particle in gained residual solution and tailings, and step is repeated (2) after washing is dry.
(4) PEG modifies nano particle and is tested for oil-water interfacial tension determination experiment and mineral surfaces contact angle determination.
The ferriferrous oxide nano composite material being prepared using the method for the present invention, 2 θ of powder x-ray diffraction angle=
18.27 ± 0.25,30.09 ± 0.25,35.42 ± 0.25,37.05 ± 0.25,43.05 ± 0.25,53.39 ± 0.25,56.94
± 0.25,62.52 ± 0.25,65.74 ± 0.25,70.92 ± 0.25,73.95 ± 0.25,74.96 ± 0.25,78.93 ±
There is characteristic peak at 0.25,86.7 ± 0.25,89.62 ± 0.25, as shown in Fig. 4.
The ferriferrous oxide nano composite material being prepared using the method for the present invention, saturation magnetic strength are reachable
49.36emu/g, average grain diameter 16nm, granularity is more uniform, and TGA tests are shown under nitrogen atmosphere in 200 DEG C of weightlessness 17% or so,
Test result is as shown in attached drawing 5,6.
The nano-fluid being made into using PEG modifications nano material can significantly improve heavy oil recovery rate, reduce oil phase containing solid
Rate.PEG modification nano particles can significantly reduce oil-water interfacial tension, improve mineral surfaces hydrophily.
Embodiment 1
A kind of synthetic method of PEG modifications nano ferriferrous oxide, steps are as follows:
(1) 0.86g FeCl are weighed2·4H2O and 2.34g FeCl3·6H2O is dissolved in 100mL water, adjusts solution temperature
It is 60 DEG C, 20mL ammonium hydroxide (5%) is slowly added dropwise under nitrogen atmosphere 500r/min stirrings, reacts 20min, obtains the oxidation of black four three
Iron nano-particle.Respectively twice to remove excess reactant, product is scattered in pH=for ethyl alcohol, washing after magnet detaches reaction product
In 9.0 lye, ultrasonic disperse 30min.
(2) 14.00g PEG600 are measured, and 90 DEG C of heating 3h remove residual moisture under an inert atmosphere, then evenly spread to
In 150mL acetonitrile solvents, 0.2mL acetic acid being added as catalyst, 5.90g KH560 are added dropwise, 6h is reacted in 90 DEG C of reflux,
Product distills 1h to remove acetonitrile, acetic acid and extra KH560 at 130 DEG C.
(3) measure 3.60g silane and be scattered in pH=9.0 bucks 30min at 20 DEG C to be fully hydrolyzed.Hydrolysate by
It is added dropwise in ferriferrous oxide nano fluid, it is 80 DEG C to adjust solution temperature, and 10h is stirred with 500r/min in nitrogen atmosphere.Production
Object is detached through magnet, and alcohol washes, washes that each dry 4h obtains product PEG modified magnetic nano materials at 100 DEG C twice.
Embodiment 2
A kind of synthetic method of PEG modifications nano ferriferrous oxide, steps are as follows:
(1) 0.84g Fe (NH are weighed4)2(SO4)2·6H2O and 0.86g Fe2(SO4)3It is dissolved in 100mL water, adjusts molten
Liquid temperature is 80 DEG C, and 15mL ammonium hydroxide (5%) is slowly added dropwise under nitrogen atmosphere 500r/min stirrings, reacts 20min, obtains black four
Fe 3 O nano particle.Respectively twice to remove excess reactant, product is scattered in for ethyl alcohol, washing after magnet detaches reaction product
In pH=9.0 lye, ultrasonic disperse 20min.
(2) 14.00g PEG600 are measured, and 90 DEG C of heating 3h remove residual moisture under an inert atmosphere, then evenly spread to
In 150mL acetonitrile solvents, 0.15mL acetic acid being added as catalyst, 5.90g KH560 are added dropwise, 7h is reacted in 90 DEG C of reflux,
Product distills 1h to remove acetonitrile, acetic acid and extra KH560 at 130 DEG C.
(3) measure 2.00g silane and be scattered in pH=9.0 bucks 30min at 20 DEG C to be fully hydrolyzed.Hydrolysate by
It is added dropwise in ferriferrous oxide nano fluid, it is 90 DEG C to adjust solution temperature, and 12h is stirred with 500r/min in nitrogen atmosphere.Production
Object is detached through magnet, and alcohol washes, washes that each dry 4h obtains product PEG modified magnetic nano materials at 100 DEG C twice.
Embodiment 3
A kind of synthetic method of PEG modifications nano ferriferrous oxide, steps are as follows：
(1) 0.43g FeCl are weighed2·4H2O and 1.17g FeCl3·6H2O is dissolved in 50mL water, adjusts solution temperature
It is 60 DEG C, 10mL NaOH (0.10mol/L) solution is slowly added dropwise under nitrogen atmosphere 350r/min stirrings, reacts 10min, obtains
Black ferroferric oxide nano particle.Methanol, washing are respectively twice to remove excess reactant, product after magnet detaches reaction product
It is scattered in pH=9.0 lye, ultrasonic disperse 10min.
(2) 6.00g PEG400 are measured, and 90 DEG C of heating 3h remove residual moisture under an inert atmosphere, then evenly spread to
In 120mL acetonitrile solvents, 0.15mL acetic acid being added as catalyst, 4.21g KH560 are added dropwise, 6h is reacted in 90 DEG C of reflux,
Product distills 1h to remove acetonitrile, acetic acid and extra KH560 at 130 DEG C.
(3) measure 1.40g silane and be scattered in pH=9.0 bucks 30min at 20 DEG C to be fully hydrolyzed.Hydrolysate by
It is added dropwise in ferriferrous oxide nano fluid, it is 80 DEG C to adjust solution temperature, and 12h is stirred with 350r/min in nitrogen atmosphere.Production
Object is detached through magnet, and alcohol washes, washes that each dry 4h obtains product PEG modified magnetic nano materials at 100 DEG C twice.
Embodiment 4
A kind of synthetic method of PEG modifications nano ferriferrous oxide, steps are as follows
(1) 0.60g FeSO are weighed4·7H2O and 0.86g Fe2(SO4)3It is dissolved in 100mL water, adjusting solution temperature is
80 DEG C, 15mL ammonium hydroxide (5%) is slowly added dropwise under nitrogen atmosphere 500r/min stirrings, reacts 20min, obtains black ferroferric oxide
Nano particle.Respectively twice to remove excess reactant, product is scattered in pH=9.0 for ethyl alcohol, washing after magnet detaches reaction product
In lye, ultrasonic disperse 20min.
(2) 45.00g PEG2000 are measured, and 90 DEG C of heating 3h remove residual moisture under an inert atmosphere, then evenly dispersed
Into 150mL acetonitrile solvents, 0.15mL acetic acid is added as catalyst, 5.90g KH560,90 DEG C of reflux, reaction is added dropwise
7h, product distill 1h to remove acetonitrile, acetic acid and extra KH560 at 130 DEG C.
(3) measure 2.00g silane and be scattered in pH=9.0 bucks 30min at 20 DEG C to be fully hydrolyzed.Hydrolysate by
It is added dropwise in ferriferrous oxide nano fluid, it is 90 DEG C to adjust solution temperature, and 11h is stirred with 500r/min in nitrogen atmosphere.Production
Object is detached through magnet, and alcohol washes, washes that each dry 4h obtains product PEG modified magnetic nano materials at 100 DEG C twice.
Embodiment 5
Application of the PEG modified magnetics nano material in heavy oil removal process：
Magnetic nanometer composite material is made into pH=8.5, the nano-fluid of mass fraction 0.2%, using industrial thermokalite
The Canadian oil-sand of WATER-WASHING METHOD operating process separation (Athabasca, Alberta, Canada), nano-fluid and oil-sand mass ratio
It is 2:1,35 DEG C of experimental temperature.Experimental result display addition nano particle can make bitumen recovery rate improve 25.0%, oily stereoplasm
Amount improves 0.5 than (B/S).
Embodiment 6
The recycling of PEG modified magnetic nano materials
Using 1T bar magnets close to solution and tailings, 80% nano particle, weight can be recycled after washing is dry
Newly 14.6% bitumen recovery rate can be improved by being made into nano-fluid still.
Embodiment 7
PEG modified magnetics nano material is in oil-water interface characteristic research
Magnetic nanometer composite material is made into pH=8.0, and the nano-fluid of mass fraction 0.2% measures addition nano particle
The interfacial tension of front and back solution and toluene (99.99%).Experimental result shows that addition nano particle can make water-toluene interface
Tension is down to 8.10mN/m from 14.40mN/m.
Embodiment 8
PEG modified magnetic nano materials change the research of mineral surfaces wettability
Magnetic nanometer composite material is made into pH=8.5, and the nano-fluid of mass fraction 0.1% measures addition nano particle
Contact angle of the front and back solution in quartz surfaces.Experimental result shows that addition nano particle can make nano-fluid in quartz surfaces
Contact angle be down to 33 ° by 91 °.
Magnetic nanometer composite material is made into pH=9.0, and the nano-fluid of mass fraction 0.1% measures addition nano particle
Contact angle of the front and back solution in Calcite Surface.Experimental result shows that addition nano particle can make nano-fluid in mineral table
The contact angle in face is down to 62 ° by 133 °.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of hydrophilic magnetic Nano material, it is characterised in that：Steps are as follows
(1) the preparation of ferriferrous oxide nano fluid：Containing Fe3+Salt and Fe2+Salt salt-mixture precursor solution is in 40-80 DEG C, indifferent gas
Precipitation solvent is slowly added dropwise under body environment, precipitation 5-30min obtains product ferroferric oxide nano granules, and product is inhaled through magnet
Draw rear alcohol to wash, wash, be then dispersed in pH=8.5-9.5 lye, ferriferrous oxide nano fluid is made in ultrasonic 10-30min；
(2) the addition of PEG and KH560：PEG first heats removal residual moisture under an inert atmosphere, then evenly spreads to acetonitrile
In solvent, acetic acid is added as catalyst, KH560 is added dropwise, reaction reflux obtains product, and product steams at 120-125 DEG C
It distillates solvent, catalyst and excess reactant and obtains PEG modified silanes；
(3) modification of the PEG modified silanes on ferroferric oxide nano granules surface：(2) silane is made at 10-30 DEG C in step, pH=
20-50min is hydrolyzed in 8.5-9.5 bucks, then hydrolysate is added dropwise in ferriferrous oxide nano fluid, when reacting one section
Between after magnet separation, alcohol washes, wash and each is dried to obtain the hydrophilic magnetic Nano material of product acquisition twice.
2. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：The Fe3+Salt and Fe2+
The molar ratio of salt is 2.1:1-1.5:1.
3. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：Reaction solution final pH
For 9.0-11.0.
4. the preparation method of hydrophilic magnetic Nano material according to claim 1 or 2, it is characterised in that：In reaction raw materials
Fe3+From FeCl3·6H2O、Fe2(SO4)3In one kind；Fe2+From FeCl2·4H2O、FeSO4·7H2O、Fe(NH4)2
(SO4)2·6H2One kind in O.
5. the preparation method of hydrophilic magnetic Nano material according to claim 1 or 3, it is characterised in that：The precipitation is molten
Agent is one kind in ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution.
6. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：The step (2) in
PEG is 1 with KH560 material molar ratios:1.2-1:1.5.
7. the preparation method of hydrophilic magnetic Nano material according to claim 1 or 6, it is characterised in that：The PEG molecules
Amount is 200-2000.
8. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：The step (2) in second
Nitrile：Acetic acid volume ratio is 1000:1-500:1.
9. the preparation method of the hydrophilic magnetic Nano material according to one of claim 1,6,7 or 8, it is characterised in that：Step
Suddenly reaction temperature (2) is 88-92 DEG C, and (2) the reaction time is 5-7h to step.
10. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：The step (3) in
Ferroso-ferric oxide, silane molar ratio are 1:1-1:1.5.
11. the preparation method of hydrophilic magnetic Nano material according to claim 1, it is characterised in that：The step (3) in
Reaction temperature is 70-90 DEG C, and the reaction time of step (3) is 8-12h.
12. hydrophilic magnetic Nano material prepared by the preparation method described in one of claim 1-11 is applied to, oil is solid to be detached, again
Oil extract, water-oil separating or sand oil extracting oil.
13. a kind of method that the hydrophilic magnetic Nano material prepared using claim 1 recycles heavy oil, it is characterised in that：Step
It is as follows：
(1) hydrophilic magnetic Nano material is distributed in the buck that pH is 8.0-10.0, and nano-fluid is made in ultrasonic disperse；
(2) (1) step is made nano-fluid and is stirred with heavy oil-raw mineral materials in flotation cell, and gas is passed through after 10-15min
By isolated heavy oil froth flotation to solution surface, collects foam and analyze the rate of recovery；
(3) (2) step recycles nano particle in gained residual solution and tailings, and step is repeated (2) after washing is dry.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109081394A (en) * | 2018-09-10 | 2018-12-25 | 苏州艾博迈尔新材料有限公司 | A kind of preparation method of the magnetic nanoparticle for sewage treatment |
| CN110105978A (en) * | 2019-04-18 | 2019-08-09 | 南方科技大学 | A kind of dual character magnetic-responsive particulate and the preparation method and application thereof |
| CN110373171A (en) * | 2019-07-10 | 2019-10-25 | 浙江海洋大学 | A kind of displacement of reservoir oil emulsion stable by magnetic nanoparticle |
| CN110439517A (en) * | 2019-07-12 | 2019-11-12 | 浙江海洋大学 | A kind of flooding method suitable for heavy crude reservoir |
| CN110776898A (en) * | 2019-11-22 | 2020-02-11 | 中国石油大学(华东) | Viscoelastic nano-magnetic fluid for improving crude oil recovery ratio of tight reservoir and preparation method thereof |
| CN112251206A (en) * | 2020-09-24 | 2021-01-22 | 南京师范大学 | Magnetic nano oil displacement agent with black phosphorus as matrix and preparation method thereof |
| CN112304998A (en) * | 2020-08-20 | 2021-02-02 | 成都理工大学 | Shale pore structure fluid flow channel tracer, preparation method and tracing method |
| CN112915592A (en) * | 2021-02-09 | 2021-06-08 | 天津大学 | Magnetic nano material and preparation method and application thereof |
| CN113546504A (en) * | 2021-07-20 | 2021-10-26 | 苏州西热节能环保技术有限公司 | Integrated method for decarburization and denitration by self-generated electricity |
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| CN109081394A (en) * | 2018-09-10 | 2018-12-25 | 苏州艾博迈尔新材料有限公司 | A kind of preparation method of the magnetic nanoparticle for sewage treatment |
| CN110105978B (en) * | 2019-04-18 | 2020-10-09 | 南方科技大学 | Two-sided magnetic response particle and preparation method and application thereof |
| CN110105978A (en) * | 2019-04-18 | 2019-08-09 | 南方科技大学 | A kind of dual character magnetic-responsive particulate and the preparation method and application thereof |
| CN110373171A (en) * | 2019-07-10 | 2019-10-25 | 浙江海洋大学 | A kind of displacement of reservoir oil emulsion stable by magnetic nanoparticle |
| CN110373171B (en) * | 2019-07-10 | 2021-07-13 | 浙江海洋大学 | Oil repellent emulsion stabilized by magnetic nanoparticles |
| CN110439517A (en) * | 2019-07-12 | 2019-11-12 | 浙江海洋大学 | A kind of flooding method suitable for heavy crude reservoir |
| CN110439517B (en) * | 2019-07-12 | 2021-09-17 | 浙江海洋大学 | Oil displacement method suitable for heavy oil reservoir |
| CN110776898A (en) * | 2019-11-22 | 2020-02-11 | 中国石油大学(华东) | Viscoelastic nano-magnetic fluid for improving crude oil recovery ratio of tight reservoir and preparation method thereof |
| CN110776898B (en) * | 2019-11-22 | 2022-02-01 | 中国石油大学(华东) | Viscoelastic nano-magnetic fluid for improving crude oil recovery ratio of tight reservoir and preparation method thereof |
| CN112304998A (en) * | 2020-08-20 | 2021-02-02 | 成都理工大学 | Shale pore structure fluid flow channel tracer, preparation method and tracing method |
| CN112251206A (en) * | 2020-09-24 | 2021-01-22 | 南京师范大学 | Magnetic nano oil displacement agent with black phosphorus as matrix and preparation method thereof |
| CN112915592A (en) * | 2021-02-09 | 2021-06-08 | 天津大学 | Magnetic nano material and preparation method and application thereof |
| CN113546504A (en) * | 2021-07-20 | 2021-10-26 | 苏州西热节能环保技术有限公司 | Integrated method for decarburization and denitration by self-generated electricity |
| CN113546504B (en) * | 2021-07-20 | 2023-08-15 | 苏州西热节能环保技术有限公司 | Self-generating electricity decarburization and denitration integrated method |
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