CN1151074C - Process for preparin dispersive nano Fe3O4 particles - Google Patents

Process for preparin dispersive nano Fe3O4 particles Download PDF

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CN1151074C
CN1151074C CNB01107440XA CN01107440A CN1151074C CN 1151074 C CN1151074 C CN 1151074C CN B01107440X A CNB01107440X A CN B01107440XA CN 01107440 A CN01107440 A CN 01107440A CN 1151074 C CN1151074 C CN 1151074C
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particle
dispersion
preparation
particulate preparation
mineral oil
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CN1365951A (en
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辉 沈
沈辉
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The present invention relates to a preparation method of high-dispersion nanometer Fe3O4 granules. The preparation method optimizes the synthesis technology and modification technology of Fe3O4 granules, particularly standardizes the technologies of raw material proportioning, reaction process, granule modification, dispersion, etc. Thus, the preparation method can save production cost, and simplify production technology, the prepared Fe3O4 granules can achieve the optimal granule dispersion effect, and high-dispersion magnetic granules can be provided for small-scale and standardization production of magnetic liquid with wide application. The preparation method of high-dispersion nanometer Fe3O4 granules has the advantages of convenience, praticality as well as obvious social benefits and economic benefits.

Description

Dispersing nanometer Fe 3O 4The particulate preparation method
Affiliated technical field
The present invention is a kind of high-dispersion nano Fe 3O 4The particulate preparation method belongs to Fe 3O 4Particulate preparation method's innovative technology.
Background technology
Existing Fe 3O 4The particulate preparation method generally is to use FeCl 2With FeCl 3Mixed solution and NaOH solution reaction and make Fe 3O 4Particle, the shortcoming of its existence is FeCl 2Price is expensive, production cost height, and the Na that gets involved in preparation process +Be difficult to clean, reaction needs to carry out complex manufacturing under the situation of heating in addition; In addition, it does not adopt magnetic and cleans process combined and gas shield technology, the Fe of generation in preparation process 3O 4Particle is not kept in the mineral oil yet, therefore, and the Fe that makes 3O 4The particles dispersed effect of the inaccessible the best of particle.
Summary of the invention
The object of the present invention is to provide a kind ofly not only can save production cost, and can simplify production technique, and the Fe that makes 3O 4Particle can reach the high-dispersion nano Fe of the particles dispersed effect of the best 3O 4The particulate preparation method.
Preparation method of the present invention carries out as follows:
(1) is equipped with Fe 2+With Fe 3+Mixed solution
Allot near saturated FeSO according to envrionment temperature 4And FeCl 3The aqueous solution, Fe in molar ratio 2+: Fe 3+With two kind solution mixing systems become Fe at=1: 1.5～2 2+With Fe 3+Mixed solution;
(2) reaction generates Fe 3O 4
The method that employing is worked along both lines is Fe in molar ratio 2+: Fe 3+: OH -=1: 1.5～1.8: 12～16 proportionlity adds mixed solution and ammoniacal liquor, and high-speed stirring is controlled stirring velocity greater than 1200 rev/mins simultaneously, adds distilled water immediately after 1～3 minute;
(3) clean
Reacted solution adopts magnetic and stirs the method that matches and clean repeatedly, cleans repeatedly more than 4 times with distilled water at least, removes Cl -, SO 4 2-Impurity obtains fresh particle surface;
(4) granule modified
1: 3 by volume～5 add ammoniacal liquor and distilled water in cleaned particle; keep pH value 9～10; heating while stirring; and the volume ratio of pressing particle and higher fatty acid mixture concerns 1: 1.5～3 addings; maintain the temperature between 70～90 ℃; and blanketing with inert gas, continue 40～60 minutes.
Above-mentioned steps (4) resulting granules can adopt following method to disperse and store for future use: earlier with acetone, ethanol or methanol dehydration, at 50～70 ℃ of vacuum dryings, then stir or ultrasonication under it is dispersed in the mineral oil.
Above-mentioned steps (4) resulting granules also can adopt following method to disperse and store for future use: directly it is dispersed in the mineral oil, and replacement dewatering repeatedly, last available whizzer is with prepared mineral oil based Fe 3O 4Magnetic liquid is made centrifugal treating, keeps rotating speed to be higher than 5000 rev/mins, removes macrobead, to guarantee Fe 3O 4Nano particle high dispersing ground stably stored is in selected mineral oil.
Used rare gas element is argon gas or nitrogen in the above-mentioned steps (4).
The present invention compares with traditional method has following advantage:
1. Fe 2+And Fe 3+Concentration is pressed the rational proportion preparation, has avoided Fe 2+Or Fe 3+The phenomenon of folk prescription surplus, and use low-cost FeSO 4Replace FeCl 2With FeCl 3Reaction has not only obtained same effect, and has saved production cost;
2. at Fe 3O 4With the traditional NaOH solution of aqueous ammonia to replace, at first be to avoid Na in the granules preparation process +Intervention, and the NH in the solution 4 +Be easy to generate NH 3Vapor away, be easy to clean; Reaction is carried out at normal temperatures in addition, need not heat, and has simplified production technique;
3. generating Fe 3O 4Before particle and the surface modification, increase magnetic and cleaned process combined and gas shield technology, prevented to remain in the Cl in the solution on the one hand -, SO 4 2-Be adsorbed on particle surface, influence next step oleic acid radical ion at Fe 3O 4Particulate absorption has prevented oleic acid oxidation on the other hand;
4. the mixture of using two kinds of senior fatty esters to guarantee forming the attached layer of the comparatively fine and close unit molecule bag of one deck at particle surface, reaches best particles dispersed effect as tensio-active agent;
5. in dehydration, clean, outside the vacuum-drying traditional technology, adopt the octane replacing process, can slough wherein moisture more fully, and make Fe except acetone or alcohol 3O 4Particle obtains disperseing more fully; Particle after the dehydration is kept in the mineral oil by the method for peptization, obtains the Fe of grain diameter in 5～15nm, high dispersing 3O 4Particle.
The present invention is to Fe 3O 4During synthetic the and modified technique of particulate row optimization, particularly technologies such as proportioning raw materials, reaction process, granule modified and dispersion have been carried out standardization processing.Therefore, not only can save production cost, and can simplify production technique with preparation method of the present invention, and the Fe that makes 3O 4Particle can reach best particles dispersed effect, can be on a small scale also standardization and produces the magnetic-particle that the magnetic liquid with extensive use provides high dispersive.The present invention is a kind of convenient and practical, and social benefit and economic benefit are all than significant high-dispersion nano Fe 3O 4The particulate preparation method.
Example I
Preparation method of the present invention carries out as follows:
(1) is equipped with Fe 2+With Fe 3+Mixed solution
Get 100 gram FeSO 47H 2O is made into 20% FeSO 4Solution, according to pressing Fe 2+: Fe + 3=1: 1.7 proportionings are considered Fe 2+Partial oxidation, weighing 180 gram FeCl 36H 2O is made into 15% FeCl 3Solution is lysed FeSO 4Solution and FeCl 3Solution mixing system becomes Fe 2+With Fe 3+Mixed solution;
(2) reaction generates Fe 3O 4
Get 340ml concentration and be 25% ammoniacal liquor, the mode that mixed solution and ammoniacal liquor are taked to work along both lines is in proportion injected there-necked flask, high-speed stirring is regulated 1300 rev/mins of rotating speeds simultaneously, stirs 2 minutes reaction generation Fe 3O 4After, add the distilled water of 400ml immediately, assemble and grow up to avoid nanocrystal, and play cooling and be beneficial to effect such as stirring;
(3) clean
Reacted solution adopts magnetic and stirs the method that matches and clean repeatedly, to wherein adding distilled water, cleans repeatedly 6 times under agitation condition, and each adding distil water 500ml stirs 10 minutes time length, and 400 rev/mins of stirring velocitys are to remove Cl -, SO 4 2-Deng impurity, obtain fresh particle surface;
(4) granule modified
Added ammoniacal liquor and distilled water in 1: 4 by volume in cleaned particle, regulating pH value is 9.5, while stirring heating; about 400 rev/mins of stirring velocity adds oleic acid and stearic acid mixture 15ml, maintains the temperature at 85 ℃; continue 50 minutes, whole process is led to argon shield.
Above-mentioned steps (4) resulting granules can adopt following method to disperse and store for future use:
Earlier under the effect in magnetic field, make Fe 3O 4Particle sinks, and removes top moisture, adds acetone 500ml then therein, stirs, and makes Fe again under the effect in magnetic field 3O 4Particle sinks, and removes the mixture of top most of acetone and water, then the Fe after the acetone dehydration 3O 4Particle vacuum-drying keeps 60 ℃ of temperature, up to removing wherein moisture, it is distributed in the octane of 500ml; To be distributed to Fe in the mineral oil with whizzer 3O 4Particle is made centrifugal treating, keeps rotating speed greater than 5000 rev/mins, removes macrobead, obtains the Fe of high dispersing 3O 4Nano particle.
Embodiment 2
Preparation method of the present invention carries out as follows:
(1) is equipped with Fe 2+With Fe 3+Mixed solution
Get 100 gram FeSO 47H 2O is made into 20% FeSO 4Solution, according to pressing Fe 2+: Fe 3+=1: 1.7 proportionings are considered Fe 2+Partial oxidation, weighing 180 gram FeCl 36H 2O is made into 15% FeCl 3Solution is lysed FeSO 4Solution and FeCl 3Solution mixing system becomes Fe 2+With Fe 3+Mixed solution;
(2) reaction generates Fe 3O 4
Get 360ml concentration and be 25% ammoniacal liquor, the mode that mixed solution and ammoniacal liquor are taked to work along both lines is in proportion injected there-necked flask.High-speed stirring is regulated 1350 rev/mins of rotating speeds simultaneously, stirs reaction in 3 minutes and generates Fe 3O 4After, add the distilled water of 430ml immediately, assemble and grow up to avoid nanocrystal, and play cooling and be beneficial to effect such as stirring;
(3) clean
Reacted solution adopts magnetic and stirs the method that matches and clean repeatedly, to wherein adding distilled water, cleans repeatedly 5 times under agitation condition, and each adding distil water 520ml stirs 10 minutes time length, and 420 rev/mins of stirring velocitys are to remove Cl -, SO 4 2-Deng impurity, obtain fresh particle surface;
(4) granule modified
Added ammoniacal liquor and distilled water in 1: 4 by volume in cleaned particle, regulating pH value is 9.5, adds to stir limit heating, about 420 rev/mins of stirring velocity.Add oleic acid and hard ester acid mixture 18ml, maintain the temperature at 80 ℃, continue 55 minutes, whole process is led to nitrogen protection.
Above-mentioned steps (4) resulting granules can adopt following method to disperse and store for future use:
Under the effect in magnetic field, make Fe 3O 4Particle sinks, and removes top moisture, the Fe that still contains water 3O 4Particle directly is distributed in the octane of 520ml, removes remaining water with separating funnel; To be distributed to Fe in the mineral oil with whizzer again 3O 4Particle is made centrifugal treating, keeps rotating speed greater than 5000 rev/mins, removes macrobead, obtains the Fe of high dispersing 3O 4Nano particle.

Claims (7)

1, high-dispersion nano Fe 3O 4The particulate preparation method is characterized in that carrying out as follows:
(1) is equipped with Fe 2+With Fe 3+Mixed solution
Allot near saturated FeSO according to envrionment temperature 4And FeCl 3The aqueous solution, Fe in molar ratio 2+: Fe 3+With two kind solution mixing systems become Fe at=1: 1.5～2 2+With Fe 3+Mixed solution;
(2) reaction generates Fe 3O 4
The method that employing is worked along both lines is Fe in molar ratio 2+: Fe 3+: OH -=1: 1.5～1.8: 12～16 proportionlity adds mixed solution and ammoniacal liquor, and high-speed stirring is controlled stirring velocity greater than 1200 rev/mins simultaneously, adds distilled water immediately after 1～3 minute;
(3) clean
Reacted solution adopts magnetic and stirs the method that matches and clean repeatedly, cleans repeatedly more than 4 times with distilled water at least, removes Cl -, SO 4 2-Impurity obtains fresh particle surface;
(4) granule modified
1: 3 by volume～5 add ammoniacal liquor and distilled water in cleaned particle; keep pH value 9～10; heating while stirring; and the volume ratio of pressing particle and higher fatty acid mixture concerns 1: 1.5～3 addings; maintain the temperature between 70～90 ℃; and blanketing with inert gas, continue 40～60 minutes.
2, according to the described high-dispersion nano Fe of claim 1 3O 4The particulate preparation method, it is characterized in that above-mentioned steps (4) resulting granules can adopt following method to disperse and store for future use: earlier with acetone, ethanol or methanol dehydration, at 50～70 ℃ of vacuum dryings, under stirring or ultrasonication, it is dispersed in the mineral oil then.
3, high-dispersion nano Fe according to claim 1 3O 4The particulate preparation method is characterized in that above-mentioned steps (4) resulting granules can adopt following method to disperse and store for future use: directly it is dispersed in the mineral oil, and replacement dewatering repeatedly, last available whizzer is with prepared mineral oil based Fe 3O 4Magnetic liquid is made centrifugal treating, keeps rotating speed to be higher than 5000 rev/mins, removes macrobead, to guarantee Fe 3O 4Nano particle high dispersing ground stably stored is in selected mineral oil.
4, according to claim 2 or 3 described high-dispersion nano Fe 3O 4The particulate preparation method is characterized in that above-mentioned mineral oil is octane, hexanaphthene, industrial naptha or kerosene.
5, high-dispersion nano Fe according to claim 4 3O 4The particulate preparation method is characterized in that the number of times that distilled water cleans repeatedly in the above-mentioned steps (3) is 5～6 times.
6, high-dispersion nano Fe according to claim 4 3O 4The particulate preparation method is characterized in that in the above-mentioned steps (1) Fe in molar ratio 2+: Fe 3+=1: 1.5～1.8 with FeSO 4And FeCl 3Two kinds of aqueous solution are made Fe 2+With Fe 3+Mixed solution.
7, high-dispersion nano Fe according to claim 4 3O 4The particulate preparation method is characterized in that rare gas element used in the above-mentioned steps (4) is argon gas or nitrogen.
CNB01107440XA 2001-01-15 2001-01-15 Process for preparin dispersive nano Fe3O4 particles Expired - Fee Related CN1151074C (en)

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CN100355661C (en) * 2005-12-01 2007-12-19 上海交通大学 Method for preparing polar solvent soluble nano ferriferrous oxide granule
CN101100315B (en) * 2007-06-15 2010-06-02 清华大学 Preparation method for Fe3O4 nano particles
CN101445674B (en) * 2008-12-08 2011-12-07 温州大学 Magnetic pearlescent pigment and preparation method thereof
CN102126760B (en) * 2011-04-12 2012-12-05 东华大学 Method for preparing hyperstable ferroferric oxide nanoparticles by adopting oil-water interfaces
CN102344170B (en) * 2011-08-28 2013-08-07 山东理工大学 Method for preparing water-based Fe3O4 magnetic fluid by using polyamide-amine dendrimer as template
CN102674469B (en) * 2012-05-08 2015-09-30 清华大学 Nanometer magnetic iron oxide and preparation method thereof and application
CN104341010B (en) * 2013-07-25 2016-05-18 同济大学 A kind of method of synthetic SPIO nanometer sheet
CN106395914B (en) * 2016-08-31 2019-01-22 上海美吉生物医药科技有限公司 The super-paramagnetism nano Fe of oleic acid package3O4And preparation method thereof
CN106335987B (en) * 2016-10-23 2020-03-27 中海油天津化工研究设计院有限公司 In-situ preparation method of composite magnetic water treatment material
CN110655117A (en) * 2019-09-30 2020-01-07 天津大学 Method for preparing ferroferric oxide with different sizes and good dispersibility

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