CN104014163A - Preparation method and application of aminoethyl aminopropyl modified ferroferric oxide - Google Patents
Preparation method and application of aminoethyl aminopropyl modified ferroferric oxide Download PDFInfo
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- CN104014163A CN104014163A CN201410276643.9A CN201410276643A CN104014163A CN 104014163 A CN104014163 A CN 104014163A CN 201410276643 A CN201410276643 A CN 201410276643A CN 104014163 A CN104014163 A CN 104014163A
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Abstract
The invention relates to a preparation method and application of aminoethyl aminopropyl modified ferroferric oxide. The method comprises the following steps: with divalent iron and ferric iron salts as raw materials, preparing nano ferroferric oxide by using a coprecipitation method; adding a surface modification material N-beta(aminoethyl)-gamma-aminopropyl trimethoxy silane with two amino groups at the later stage of the reaction, and binding silicon hydroxyl generated by utilizing hydrolysis of trimethoxy silane and the surface of ferroferric oxide, so that amino with positive charge is formed on the surface of ferroferric oxide, micro emulsion oil with negative charge and other pollutants in oilfield tertiary recovery sewage can be further adsorbed and combined, and an aim of separating the pollutants in the oilfield tertiary recovery sewage is achieved by utilizing a magnetic separation technology. The method can be applied to treating the oilfield tertiary recovery sewage and improving the oilfield tertiary recovery sewage treatment technology. The aminoethyl aminopropyl-modified oilfield tertiary recovery sewage subjected to ferroferric oxide treatment obtained by the method is obvious in oil-water separation effect and can reach the reinjection standard.
Description
Technical field
Invention belongs to environment, material, energy crossing domain, relates to a kind of tri-iron tetroxide preparation of aminoethyl aminopropyl modification and is applied to the separation that the micro emulsion oil in sewage is adopted in oil field three.
Background technology
Karamay oilfield tertiary oil recovery is progressively carried out, demand to water resource continues to increase, water content in crude oil constantly rises, oil-polluted water amount is increasing, in tertiary oil recovery process, added some surfactants as oil recovery auxiliary agent, make three oil of adopting in sewage become stable micro emulsion oil, thereby flocculation process is more difficult in wastewater treatment process, carry out, often need to strengthen flocculant consumption, produce more mud, this directly causes the processing of sewage to become difficult point with reuse.Disposing polluted water in oil reuse up to standard and to improve reusing sewage rate be oil field reasonable development, the effective way that improves water utilization rate and reduce production costs.
At present, the treatment process of three sewage in oil field mainly comprises gravity oil-removing-flocculating setting-depth-type filtration, and this technique mainly relies on oil slick, dispersed oil droplet in the separated water body of Flocculation Settling Process.This process not only needs to consume a large amount of flocculants, produces a large amount of unmanageable oily sludges simultaneously.Magnetic separation technique is very promising water technology, and this method is simple, economical and effective, separation and sedimentation fast, in more traditional flocculation separation technology in aspect such as occupation of land, energy consumption, operation, moisture percentage in sewage sludge, has a clear superiority in and special performance.
Magnetic separation technique is as a technology that has development prospect, and the relevant report that directly or indirectly utilizes magnetic technology to process oily waste water is increasing in recent years.Nanometer Fe
3o
4particle is modified rear surface through aminoethyl aminopropyl and is had a large amount of amino, easy and H in nearly neutral water
+in conjunction with making Fe
3o
4particle surface is positively charged, just can efficiently be combined with the three electronegative micro-droplet of oils of adopting in sewage, makes micro emulsion oil in sewage have magnetic, realizes the object that the micro-oil in sewage is adopted in magnetic separation three.
Summary of the invention
The object of the invention is, the processing method of adopting sewage in order to solve existing oil field three is not effectively problem, a kind of preparation method of nano ferriferrous oxide of aminoethyl aminopropyl modification is provided, the method is utilized the advantage of two amino functional groups of N-β (aminoethyl)-γ-aminopropyltrimethoxysilane band, as face finish material, first use coprecipitation to prepare nano ferriferrous oxide, in the one pot reaction later stage, add N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, the silicon hydroxyl and the tri-iron tetroxide surface conjunction that utilize trimethoxy silane hydrolysis to produce, make tri-iron tetroxide surface form positively charged amino, and then can adsorb in conjunction with oil field three and adopt micro emulsion wet goods pollutant electronegative in sewage, recycling magnetic separation technique reaches the object that micro emulsion oil in sewage is adopted in separated oil field three, administer oil field three and adopt sewage, improve oil field three and adopt sewage disposal technology.Sewage is adopted in oil field three after method of the present invention is processed, and oil-water separation is remarkable, can reach reinjection standard.
The preparation method of the nano ferriferrous oxide that aminoethyl aminopropyl of the present invention is modified, follows these steps to carry out:
A, take FeCl
36H
2o and FeSO
47H
2o is soluble in water under mechanical agitation, at non-oxidizing gas N
2, Ar, He protection under mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o:FeSO
47H
2the mass ratio of O is 1:0.2-5.1, FeCl
36H
2o: the mass ratio of water is 1:10-40;
B, ammoniacal liquor is added in the mixed solution of step a, be heated to 60-90 ℃, react after 0.5-2.5 hour, obtain the mixed solution of nano ferriferrous oxide, wherein the concentration of ammoniacal liquor is 5%-27%, and volume is 9-40mL;
C, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in the mixed solution of step b, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:10-40, keep after 0.5-2h, through washing, obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again.
Water described in step a is deionized water, distilled water, river or running water.
Washing described in step c is acetone deionized water, distilled water, river or running water washing.
The nano ferriferrous oxide that the aminoethyl aminopropyl that described method obtains is modified is adopted the purposes in sewage in separated oil field three.
The using dosage of the nano ferriferrous oxide that described aminoethyl aminopropyl in sewage is adopted in separated oil field three is modified is 0.1%-1.0%.
The occupation mode of the nano ferriferrous oxide that when sewage is adopted in described separation three, aminoethyl aminopropyl is modified is that permanent magnet or electromagnetic field are separated.
The disengaging time of the nano ferriferrous oxide that when sewage is adopted in described separation three, aminoethyl aminopropyl is modified is 3-30 minute.
The Preparation method and use of the nano ferriferrous oxide that aminoethyl aminopropyl of the present invention is modified, the method is to be easy to and silicon hydroxy combining based on tri-iron tetroxide surface, thereby aminoethyl aminopropyl is modified to ferriferrous oxide particles surface, aminoethyl aminopropyl is with two amino functional groups, therefore the nano ferriferrous oxide surface that aminoethyl aminopropyl is modified will show largely higher positive charge characteristic under nearly neutrallty condition, as the negative electrical charge micro emulsion oil droplet that is easy to adopt in sewage with oil field three is combined, realize the effect that sewage is adopted in isolation of purified oil field three.
Accompanying drawing explanation
Fig. 1 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4xRD figure, wherein 1 for before modifying, and 2 for after modifying, and test sample is powder;
Fig. 2 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4infrared spectrogram, wherein 1 for before modifying, and 2 for after modifying, and test sample is KBr pressed disc method;
Fig. 3 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4granularity graph, the Fe that wherein aminoethyl aminopropyl is modified
3o
4be scattered in water and test;
Fig. 4 is the surperficial Zeta potential figure that aminoethyl aminopropyl of the present invention is modified, the Fe that wherein aminoethyl aminopropyl is modified
3o
4be scattered in water and test;
Fig. 5 is the Zeta hysteresis curve figure that aminoethyl aminopropyl of the present invention is modified, the Fe that wherein aminoethyl aminopropyl is modified
3o
4sample is powder;
Fig. 6 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4the impact of using dosage on simulated oil water sample oil removal rate, wherein using dosage-■-1 is 0.067g/L ,-●-2 is 0.108g/L, and-▲-3 is 0.162g/L ,-▼-4 is 0.216g/L ,-◆-5 is the Fe that 0.270g/L aminoethyl aminopropyl is modified
3o
4;
Fig. 7 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4using dosage is adopted the impact of sewage degrease rate, wherein using dosage on Karamay oilfield three-and ■-1 is 1.08g/L ,-●-2 is 1.35g/L, and-▲-3 is 1.89g/L ,-▼-4 is 2.16g/L ,-◆-5 is the Fe that 2.70g/L aminoethyl aminopropyl is modified
3o
4;
Fig. 8 is the Fe that aminoethyl aminopropyl of the present invention is modified
3o
4using dosage is adopted the figure that affects of sewage water outlet oil content on Karamay oilfield three.
The specific embodiment
Embodiment 1
A, in mass ratio for 1:1 takes 4.7g FeCl
36H
2o and 4.7gFeSO
47H
2o is dissolved in deionized water under churned mechanically condition, under nitrogen protection, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:21;
B, the concentrated ammonia liquor that is 25% by concentration, volume is that 25mL adds in the mixed solution of step a, and heating water bath is to 80 ℃ of temperature, after 1 hour reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 4.935gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:20, keep after 1 hour, through running water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 0.04%, the magnetic that carries out permanent magnet is separated, disengaging time is 3 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 2
A, in mass ratio for 1:0.2 takes 6.5g FeCl
36H
2o and 0.13gFeSO
47H
2o is dissolved in distilled water under churned mechanically condition, under argon shield, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:3;
B, the ammoniacal liquor that is 6% by concentration, volume is that 50mL adds in the mixed solution of step b, and oil bath is heated to temperature 60 C, reacts after 0.5 hour, obtains the mixed solution of tri-iron tetroxide;
C, 6.5gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in the mixed solution of step b, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:3, after 1 hour retention time, through distilled water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 0.01%, carry out after the magnetic separation of electromagnetic field, disengaging time is 10 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 3
A, in mass ratio for 1:2 takes 2.35g FeCl
36H
2o and 4.7gFeSO
47H
2o is dissolved in river under churned mechanically condition, under He gas shield, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:21;
B, the ammoniacal liquor that is 5% by concentration, volume is that 15mL adds in the mixed solution of step a, and sand bath is heated to temperature 60 C, after 1.5 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 5gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:10, after 2 hours retention times, through deionized water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 1.0%, the magnetic that carries out permanent magnet is separated, disengaging time is 20 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 4
A, in mass ratio for 1:3 takes 4.7g FeCl
36H
2o and 14.3gFeSO
47H
2o is dissolved in running water under churned mechanically condition, under Ar gas shield, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:5;
B, the ammoniacal liquor that is 10% by concentration, volume is that 20mL adds in the mixed solution of step a, and air bath is heated to temperature 70 C, after 2 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 1.57gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:15, after 2 hours retention times, through river washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 4%, the magnetic that carries out electromagnetic field is separated, disengaging time is 30 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 5
A, in mass ratio for 1:4 takes 4.7g FeCl
36H
2o and 18.8gFeSO
47H
2o is dissolved in deionized water under churned mechanically condition, under Ar gas shield, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:25;
B, the ammoniacal liquor that is 20% by concentration, volume is that 30mL adds in the mixed solution of step a, and heating water bath is to 90 ℃ of temperature, after 2.5 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 4.7gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:25, keep after 2 hours, through running water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide of aminoethyl aminopropyl is 6.0%, the magnetic that carries out electromagnetic field is separated, disengaging time is 3 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 6
A, in mass ratio for 1:5.1 takes 4.7g FeCl
36H
2o and 24gFeSO
47H
2o is dissolved in deionized water under churned mechanically condition, at N
2under gas shield, mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:30;
B, the ammoniacal liquor that is 27% by concentration, volume is that 40mL adds in the mixed solution of step a, and heating water bath is to 65 ℃ of temperature, after 1.5 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 0.68gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:35, keep after 1.5 hours, through distilled water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 6.0%, the magnetic that carries out electromagnetic field is separated, disengaging time is 10 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 7
A, in mass ratio for 1:1.5 takes 4.7g FeCl
36H
2o and 7.05gFeSO
47H
2o is dissolved in distilled water under churned mechanically condition, at N
2under gas shield, mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:38;
B, the ammoniacal liquor that is 26% by concentration, volume is that 50mL adds in the mixed solution of step a, and is heated to 85 ℃ of temperature, after 2.5 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 4.7gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:38, keep after 1 hour, through running water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 5.0%, the magnetic that carries out electromagnetic field is separated, disengaging time is 20 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 8
A, in mass ratio for 1:2.5 takes 4.7g FeCl
36H
2o and 11.75gFeSO
47H
2o is dissolved in running water under churned mechanically condition, at N
2under gas shield, mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:25;
B, the ammoniacal liquor that is 8% by concentration, volume is that 12mL adds in the mixed solution of step a, and is heated to 65 ℃ of temperature, after 1 hour reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 14.7gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:8, after 1 hour retention time, through distilled water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 7.0%, the magnetic that carries out electromagnetic field is separated, disengaging time is 30 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 9
A, in mass ratio for 1:3.5 takes 4.7g FeCl
36H
2o and 16.45gFeSO
47H
2o is dissolved in river under churned mechanically condition, at N
2under carbon gas shield, mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:12;
B, the ammoniacal liquor that is 15% by concentration, volume is that 20mL adds in the mixed solution of step a, and is heated to 75 ℃ of temperature, after 2 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 2.82gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:20, after 1.5 hours retention times, through deionized water washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the aminoethyl aminopropyl of acquisition is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that aminoethyl aminopropyl is modified is 6.0%, the magnetic that carries out permanent magnet is separated, disengaging time is 15 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Embodiment 10
A, in mass ratio for 1:4.5 takes 4.7g FeCl
36H
2o and 21.15gFeSO
47H
2o is dissolved in deionized water under churned mechanically condition, under nitrogen gas protection, mixes, and obtains Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o: the mass ratio of water is 1:38;
B, the ammoniacal liquor that is 25% by concentration, volume is that 50mL adds in the mixed solution of step a, and is heated to 85 ℃ of temperature, after 2.5 hours reaction time, obtains the mixed solution of tri-iron tetroxide;
C, 6gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in step b mixed solution, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:30, keep after 1 hour, through river washing, can obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again;
The nano ferriferrous oxide that the N-β (aminoethyl) obtaining-γ-aminopropyltrimethoxysilane is modified is adopted sewage for the separated oil field three of magnetic, the using dosage of the nano ferriferrous oxide that N-β (aminoethyl)-γ-aminopropyltrimethoxysilane is modified is 8.0%, carry out electromagnetic field separation, disengaging time is 15 minutes, and oil field three is adopted sewage and presented transparent settled solution from opaque turbid solution.
Preparation method of the present invention, first use coprecipitation to prepare nano ferriferrous oxide, in the reaction later stage, add N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, the silicon hydroxyl and the tri-iron tetroxide surface conjunction that utilize trimethoxy silane hydrolysis to produce, make tri-iron tetroxide surface form positively charged amino, and then can adsorb and adopt micro emulsion wet goods pollutant electronegative in sewage in conjunction with three, recycling magnetic separation technique reaches separated three objects of adopting dirty water pollutant.Fig. 1 is the Fe that aminoethyl aminopropyl is modified
3o
4fe with unmodified
3o
4xRD figure, its diffraction maximum belongs to respectively Fe
3o
4(220) of face-centered cubic (fcc) spinel structure, (311), (400), (422), and (440) crystal face (511), both relatively, peak shape is all more sharp-pointed, illustrate that degree of crystallization is higher, before and after modifying, each diffraction maximum is in full accord, with Fe
3o
4standard x RD collection of illustrative plates is basically identical, and its crystal formation does not change before and after modifying, and shows not change Fe through the modification of silane coupler
3o
4crystalline structure, and belong to cubic system;
Fig. 2 FT-IR detects and has further shown that the nano ferriferrous oxide that aminoethyl aminopropyl is modified has successfully formed.The infrared spectrum of the nano ferriferrous oxide that the aminoethyl aminopropyl that obtains by method of the present invention is modified can find out, two kinds of magnetic nanoparticles are at 580cm
-1near have characteristic absorption peak, corresponding to Fe
3o
4the flexural vibrations absworption peak of particle Fe-O.Literalness Fe
3o
4in particle due to the existence of nanoparticle surface-OH, at 3380cm
-1there is an absworption peak in place, corresponds to Fe
3o
4surface-OH stretching vibration; At 1046cm
-1the asymmetric stretching vibration peak that near strong absworption peak is Si-O-Si; The Fe modifying at aminoethyl aminopropyl
3o
4iR figure in, at 3423cm
-1the characteristic peak occurring is-stretching vibration of NH, and 3380cm
-1-OH vibration peak disappear and-NH vibration peak occurs, shows successfully silane coupler to be modified to Fe
3o
4surface;
By particle size analyzer, recorded the nanometer Fe of the modification of aminoethyl aminopropyl modification
3o
4particle diameter be 190nm (Fig. 3), by Zeta, record aminoethyl aminopropyl and modify Fe
3o
4zeta potential be+34mV (Fig. 4), the Fe of unmodified
30
4for+5.48mV, the Fe of oleic acid modified
30
4for+1.66, the Fe of the co-modified modification of oleic acid amphoteric imidazoline
30
4for-7.73, the Fe that aminoethyl aminopropyl is modified
3o
4zeta potential the highest, and the Fe that empgen BB makes
3o
4zeta potential be minimumly-21.3mV.Test shows, silane coupler-Fe
3o
4oil removal rate to sewage is the highest, empgen BB-Fe
3o
4oil removal rate to sewage is minimum.This be because the micro emulsion oil of oil-containing is electronegative in three sewage-27.3mV, by Electrostatic Absorption, electronegative micro emulsion oil and positively charged Fe
3o
4combination preferably, adopts wastewater treatment efficiency thereby improved oil field three.
As shown in Figure 5, in magnetized process, along with the increase of externally-applied magnetic field intensity, the Fe that aminoethyl aminopropyl is modified
3o
4the intensity of magnetization (M) also increase thereupon, but be finally tending towards saturated; Apparent saturation magnetization is 72.8emug
-1, thering is good magnetic, the nano ferriferrous oxide that aminoethyl aminopropyl is modified is black.As can be seen from Figure 6 the Fe that, aminoethyl aminopropyl is modified
3o
4oil removal rate to simulation sewage can reach 95%, has using dosage little, the separated feature of (<10min) fast.The Fe modifying along with aminoethyl aminopropyl as can be seen from Figure 7
3o
4addition constantly increase, the Fe that aminoethyl aminopropyl is modified
3o
4the oil removal rate of Kelamayi three being adopted to sewage also constantly improves, and when using dosage is that 2.70g/L oil removal rate can reach 85%, water outlet oil content can reach 7.5mg/L (Fig. 8), reaches national reinjection standard.
Claims (7)
1. a preparation method for the tri-iron tetroxide that aminoethyl aminopropyl is modified, is characterized in that following these steps to carrying out:
A, take FeCl
36H
2o and FeSO
47H
2o is soluble in water under mechanical agitation, at non-oxidizing gas N
2, Ar, He protection under mix, obtain Fe
2+and Fe
3+mixed solution, FeCl wherein
36H
2o:FeSO
47H
2the mass ratio of O is 1:0.2-5.1, FeCl
36H
2o: the mass ratio of water is 1:10-40;
B, ammoniacal liquor is added in the mixed solution of step a, be heated to temperature 60-90 ℃, after reaction time 0.5-2.5 hour, obtain the mixed solution of nano ferriferrous oxide, wherein the concentration of ammoniacal liquor is 5%-27%, and volume is 9-40mL;
C, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane will be added in the mixed solution of step b, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane wherein: the mass ratio of water is 1:10-40, keep after 0.5-2h, through washing, obtain the nano ferriferrous oxide that aminoethyl aminopropyl is modified again.
2. method according to claim 1, is characterized in that the water described in step a is deionized water, distilled water, river or running water.
3. method according to claim 1, is characterized in that the washing described in step c is running water washing, river, distilled water washing or deionized water washing.
4. the nano ferriferrous oxide that the aminoethyl aminopropyl that method according to claim 1 obtains is modified is adopted the purposes in sewage in the separated oil field three of preparation.
5. purposes according to claim 4, is characterized in that the using dosage of the nano ferriferrous oxide that when sewage is adopted in separated oil field three, aminoethyl aminopropyl is modified is 0.01%-8%.
6. purposes according to claim 4, the occupation mode that it is characterized in that the nano ferriferrous oxide that when sewage is adopted in separated oil field three, aminoethyl aminopropyl is modified is that permanent magnet or electromagnetic field are separated.
7. purposes according to claim 4, is characterized in that the disengaging time of the nano ferriferrous oxide that when sewage is adopted in separated oil field three, aminoethyl aminopropyl is modified is 3-30 minute.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830431A (en) * | 2017-03-07 | 2017-06-13 | 同济大学 | A kind of method that magnetic nano-particle is combined treatment waste emulsion liquid with milipore filter |
| CN107381749A (en) * | 2017-08-29 | 2017-11-24 | 南京华淳环保股份有限公司 | A kind of magnetic flocculant and its preparation method and application |
| CN108636384A (en) * | 2018-05-25 | 2018-10-12 | 高阳 | A kind of preparation method of greasy dirt sorbing material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741207A (en) * | 2005-07-22 | 2006-03-01 | 南京工业大学 | Method for producing naon-magnetic liquid |
| CN102390880A (en) * | 2011-07-18 | 2012-03-28 | 中国科学院新疆理化技术研究所 | Method for performing ultrasonic separation on oily wastewater with oil-soluble ferroferric oxide nanoparticles |
| CN102423696A (en) * | 2011-09-02 | 2012-04-25 | 中国科学院新疆理化技术研究所 | Preparation method for humic acid-modified nano-ferroferric oxide, and use thereof |
-
2014
- 2014-06-19 CN CN201410276643.9A patent/CN104014163B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741207A (en) * | 2005-07-22 | 2006-03-01 | 南京工业大学 | Method for producing naon-magnetic liquid |
| CN102390880A (en) * | 2011-07-18 | 2012-03-28 | 中国科学院新疆理化技术研究所 | Method for performing ultrasonic separation on oily wastewater with oil-soluble ferroferric oxide nanoparticles |
| CN102423696A (en) * | 2011-09-02 | 2012-04-25 | 中国科学院新疆理化技术研究所 | Preparation method for humic acid-modified nano-ferroferric oxide, and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIUSHEN YE ET AL.: "Comparison of strontium and calcium adsorption onto composite magnetic particlesderived from Fe3O4 and bis(trimethoxysilylpropyl)amine", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》, vol. 330, 18 July 2008 (2008-07-18), pages 21 - 27, XP025535243, DOI: doi:10.1016/j.colsurfa.2008.07.019 * |
| ZHIJIAN WU ET AL.: "Organosilane-functionalized Fe3O4 composite particles as effective magnetic assisted adsorbents", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG.》, vol. 279, 31 January 2006 (2006-01-31), pages 167 - 174 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830431A (en) * | 2017-03-07 | 2017-06-13 | 同济大学 | A kind of method that magnetic nano-particle is combined treatment waste emulsion liquid with milipore filter |
| CN106830431B (en) * | 2017-03-07 | 2020-10-02 | 同济大学 | Method for treating waste emulsion by combining magnetic nanoparticles and ultrafiltration membrane |
| CN107381749A (en) * | 2017-08-29 | 2017-11-24 | 南京华淳环保股份有限公司 | A kind of magnetic flocculant and its preparation method and application |
| CN107381749B (en) * | 2017-08-29 | 2020-11-27 | 南京华淳环保股份有限公司 | Magnetic flocculant and preparation method and application thereof |
| CN108636384A (en) * | 2018-05-25 | 2018-10-12 | 高阳 | A kind of preparation method of greasy dirt sorbing material |
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