CN1230472C - Method for preparing nano iron oxide red - Google Patents

Method for preparing nano iron oxide red Download PDF

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CN1230472C
CN1230472C CN 02155680 CN02155680A CN1230472C CN 1230472 C CN1230472 C CN 1230472C CN 02155680 CN02155680 CN 02155680 CN 02155680 A CN02155680 A CN 02155680A CN 1230472 C CN1230472 C CN 1230472C
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particle
iron oxide
oxide red
salt solution
solution
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CN1508192A (en
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樊红雷
宋宝珍
刘菊花
仰振求
李巧霞
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to a method for preparing nanometer iron oxide red. The method comprises the steps: a crystal form transforming agent is thoroughly mixed with alkali liquid under the conditions of a normal temperature and normal pressure; then, a soluble ferric iron salt solution or a product formed by the oxidation of a soluble ferrous iron salt solution is added at the time of stirring so as to form gel; a buffer solution is added, the pH value of the mixed solution is kept from 8 to 12; the mixed solution is heated, and the reaction temperature is kept within the range of 85 DEG C to 110 DEG C; an ageing reaction is carried out for 5 minutes to 20 minutes; the suspension is centrifugally extracted by a centrifugal pump and is washed for three to five times; the suspension is dried for 1.5 hours to 3 hours at the temperature of 25 DEG C to 50 DEG C; and after grinding, monodisperse nanometer alpha-Fe2O3 particles are obtained. The present invention has the advantages that the particle diameter of each of the obtained monodisperse nanometer alpha-Fe2O3 particles can be controlled between 10 nm and 100 nm; the particle diameters are uniformly distributed, and the size difference is about 10 nm; the shape of the particles can be regulated to be in a spherical shape or a cubic shape, and the dispersibility of the particles is good. The present invention has the advantages of simple production process, short production periodicity and high yield.

Description

A kind of nanometer iron oxide red preparation method
Technical field
The present invention relates to the field of production of red iron oxide, particularly a kind of dispersed nano red iron oxide particle α-Fe 2O 3The preparation method.
Background technology
α-Fe 2O 3Ferriferous oxide for a kind of stable crystal phase structure.Because it possesses the performance of many excellences, therefore be widely used in pigment and fields such as coating, catalyzer, function ceramics, magneticsubstance, gas sensor, photochromics, makeup and biological medicine.α-Fe 2O 3After the size nanometer of particle, many special physicochemical property have been produced, as to ultraviolet ray, ultrared strong absorption etc.Because the special physico-chemical property of nanoparticle and size, pattern and the internal structure of particle are closely bound up, therefore become the focus for preparing nanometer iron oxide red particle for size how to regulate and control nanoparticle and pattern.
In technical paper report, the preparation method of common monodisperse nanoparticle has that solvent-thermal method, microwave hydrothermal are synthetic, gel sol method, forced hydrolysis method, chelating molysite thermal decomposition method etc.Calendar year 2001 DehongChen etc. form gel earlier with trivalent soluble ferric iron salt and alkaline reaction, add organic solvent again to change over to together in the autoclave, obtain the iron oxide red particle of 50-100nm under certain temperature, pressure.Calendar year 2001 Hiroaki Katsuki etc. under microwave radiation, keep 100-160 ℃ of temperature of reaction with trivalent iron salt and certain density mixed in hydrochloric acid, and mixed liquid transfers the iron oxide red particle that median size is 31nm to after 2 hours, and productive rate is 18.9%.Tadao Sugimoto in 1998 etc. utilize the gel sol method, earlier preparation α-Fe 2O 3Crystal seed, crystal seed is added in the ironic hydroxide gel according to a certain percentage, can make the particle that median size is 30nm, its production cycle often needs several days consuming time.Nineteen eighty-two
Figure C0215568000031
Deng adopting the dilute solution forced hydrolysis, the preparation monodisperse particle has been carried out fruitful trial, but its production cycle is long, particle is bigger.Adopt the thermolysis process of chelated mineral salt in addition, its advantage is the size of particles homogeneous, but the agent that is chelated easily pollutes, and particle is big and be easy to reunite simultaneously.
And monodisperse nanoparticle refers to the nanoparticle of particle homogeneous on size, pattern and internal structure.Because the physico-chemical property homogeneous of monodisperse nanoparticle, and its physico-chemical property changes along with the change of particle diameter and particle morphology, therefore, just seems particularly important for the preparation of dispersed nano iron oxide red particle with to the regulation and control of size of particles and particle morphology.
Up to now, the publication of relevant dispersed nano iron oxide red particle is less both at home and abroad.Chinese patent publication number CN1310206A discloses nanometer alpha-Fe 2O 3The preparation method, its technical characterstic is to add alkali in iron salt solutions, generates the ironic hydroxide gel, adds one step of little amount of catalyst down at 90-100 ℃ then and transforms and directly prepare α-Fe 2O 3Nano-powder finally obtains the spherical particle that median size is 70nm.But this invention does not relate to the regulation and control to particle shape, does not relate to problem dispersed between the size-grade distribution of particle and particle yet.The disclosed a kind of liquid phase of Chinese patent publication number CN1312224A is synthesized α-Fe 2O 3Nano-powder, this method also are to generate earlier the ironic hydroxide gel, then under the catalyzer existence condition, utilize microwave heating to 105 ℃ to be converted into α-Fe fast 2O 3Nano-powder, the median size of powder crystal grain is between 20-100nm.This method is utilized microwave preparation nanometer iron oxide red, and its complex manufacturing is difficult to accomplish scale production, and production cost is higher, the also unexposed regulation and control that how to solve size of particles, pattern, and how to solve agglomeration traits between the particle.Chinese patent publication number CN1364730A discloses liquid phase synthesis of nano α-Fe 2O 3, this method is that molysite, alkali are mixed simultaneously with complexing agent, and 70-100 ℃ of following reaction, 100-120 ℃ was descended dry 5 hours, and can make median size is the iron oxide red particle of 12nm.From the disclosed technical scheme of this method is following dry 5 hours at 120 ℃ when preparing nano-powder, on the one hand drying temperature too high and time of drying of the long particle that makes easily produces hard aggregation, and this method prepares nano-powder dispersed bad (Fig. 1 TEM photo) as shown in Figure 1; On the other hand, time of drying is long, has just prolonged the cycle of producing widely, has increased production cost.
Summary of the invention
The objective of the invention is to be difficult to regulation and control at the particle diameter and the shape that exist particle among the existing preparation method, and the particle dispersiveness is bad, easy problem such as reunion between particle, and exist complex process among the existing preparation method, productive rate is low, cost is high and the production cycle is long shortcoming, thereby the dispersed nano α-Fe of a kind of particle diameter at 10-100nm is provided 2O 3The preparation method of the red iron oxide particle of particle.
The object of the present invention is achieved like this:
The preparation method of a kind of nanometer iron oxide red particle provided by the invention is characterized in that, may further comprise the steps:
1. the alkali lye that with compound modifying agent and concentration is 0.1-3M at first at normal temperatures and pressures fully stirs evenly mixed; Wherein compound modifying agent add-on and Fe 3+Mol ratio is 1: 50-200; The mol ratio of alkali lye and molysite is that 1-10 prepares burden;
2. when continuing stirring, adding concentration in mixing solutions is the solubility ferric salt solution of 0.1-3M or the product behind the solubility divalent iron salt solution oxide, produces gel, and adding concentration again is 10 -4-10 -3The buffered soln of M, add buffered soln and Fe 3+Mol ratio be 10 -3-10 -2, keeping the pH value of mixed solution is 8-12; Heat then and keep temperature 85-110 ℃, aging reaction 5-20 minute, obtain suspension liquid;
3. with the suspension liquid centrifugation of step (2) gained, and then with deionized water wash 3-5 time, and 25-50 ℃ dry 1.5-3 hour down, after being ground into powder, promptly obtain the dispersed nano α-Fe of particle diameter at 10-100nm 2O 3Particle, the pattern of particle are spherical or cubic.
Described compound modifying agent comprises: contain C 2～C 6Ester, formic anhydride, diacetyl oxide or propionic anhydride; Methane amide, any one in the ethanamide; Citric acid, lactic acid, tartrate, Sodium dodecylbenzene sulfonate or sodium oleate.
Described alkali lye comprises: sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, ammoniacal liquor, urea, bicarbonate of ammonia or volatile salt.
Described solubility ferric salt solution comprises: FeCl 3, Fe (NO 3) 3Or Fe 2(SO 4) 3Solution.
Product behind the described solubility divalent iron salt solution oxide is that wherein solubility divalent iron salt solution comprises: FeCl the product of gained after the oxidation of solubility divalent iron salt solution usefulness oxygenant 2Or FeSO 4Solution; Oxygenant comprises: airborne oxygen, hydrogen peroxide, chlorine or hypochlorous acid.
Described buffered soln comprises: SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
Advantage of the present invention is:
(1) preparation method provided by the invention has been owing to added compound modifying agent, and this compound modifying agent and hydrated iron ionic complexing action can be quickened the rapid phase transition of gel, so impels α-Fe 2O 3The quick generation of particle; On the other hand, because α-Fe 2O 3Particle surface has adsorbed a large amount of charged ions, and for example: hydroxyl or ammonium radical ion make nanometer α-Fe 2O 3Particle is uniformly dispersed good.
(2) the present invention prepares nanometer iron oxide red particle α-Fe 2O 3Method be by regulating rotating speed, the pH value of mixed solution and the mol ratio of molysite and alkali lye of agitator, thereby reach the purpose of the particle diameter of regulation and control particle, the size of particle can be controlled between the 10-100nm, size of particles is even, and the size deviation is about 10nm; And by the kind of control alkali, the shape of iron oxide red particle can be regulated to spherically or cubic, obtain the nanometer iron oxide red particle of good dispersion property simultaneously.
(3) whole process of preparation is to finish in a step, has avoided growing up and reuniting of crystal grain that the thermal treatment phase transformation causes effectively.Fig. 3-6 compared to Figure 1 illustrates that dispersion of particles of the present invention is functional.
(4) because drying temperature is lower,, avoided producing hard aggregation between particle, made the dispersion of particles better performances less than 50 ℃.
(5) preparation technology is simple, and processing parameter is controlled easily, and time of drying is short to have shortened the production cycle widely, thereby has reduced production cost and productive rate can reach 90%-99%.
Description of drawings
Fig. 1 Chinese patent publication number CN1364730A makes spherical nanometer α-Fe 2O 3The TEM photo of particle samples duplicates figure
Fig. 2 the present invention makes sample α-Fe 2O 3XRD figure (annotate: X-coordinate 20 is the X-ray diffraction angle, and ordinate zou I is a diffraction peak intensity)
Fig. 3 embodiment 1 makes spherical nanometer α-Fe that the sample average particle diameter is 60nm 2O 3The TEM photo of particle samples
Fig. 4 embodiment 2 makes cubic nanometer α-Fe that median size is 42nm 2O 3The TEM photo of particle samples
Fig. 5 embodiment 3 makes cubic nanometer α-Fe that median size is 35nm 2O 3The TEM photo of particle samples
Fig. 6 embodiment 4 makes spherical nanometer α-Fe that median size is 10nm 2O 3The TEM photo of particle samples
The process flow sheet of Fig. 7 method of the present invention
Concrete embodiment
Embodiment 1
The preparation flow of present embodiment as shown in Figure 7.With the 31.8g anhydrous Na 2CO 3Be dissolved in the 300ml deionized water and be made into alkali lye, add the 0.05ml ethyl acetate under violent stirring (600 rev/mins) condition, make solution evenly mixed, adding 300ml concentration under continuing to stir is the FeCl of 0.1mol/1 36H 2O solution forms gel, and adding 30ml concentration again is 1 * 10 -4The sodium dihydrogen phosphate of mol/l, the pH value of mixed solution are 9; 85 ℃ aging 5 minutes down, obtain red suspension liquid, separate with centrifugal pump and centrifugal again, through deionized water wash 3 times, 25 ℃ dry 1.5 hours down, obtain globular-Fe that median size is 60nm after the grinding 2O 3Particle, grain size is disperseed near single, and its TEM photo is seen Fig. 3.
Embodiment 2
The preparation flow of present embodiment as shown in Figure 7.With 95g anhydrous Na HCO 3Be dissolved in the 300ml deionized water and be made into alkali lye, (1000 rev/mins) add the 0.3g citric acid under agitation condition then, make solution fully mixed.With FeSO 47H 2(0.3mol/l) solution 1000ml of O oxidation 0.5 hour in air is added to the product after the oxidation in the above-mentioned mixed liquid under continuing to stir and forms gel, and adding 3000ml concentration again is 1 * 10 -3The sodium dihydrogen phosphate of mol/l, the pH value of mixed solution are 8; Wore out 20 minutes down at 110 ℃, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 5 times, drying is 3 hours under 50 ℃, and obtaining median size after the grinding is cubic α-Fe of 42nm 2O 3Particle, grain size is disperseed near single, and its TEM photo is seen Fig. 4.
Embodiment 3
The preparation flow of present embodiment as shown in Figure 7.With 45mlNH 3H 2It is mixed that the diacetyl oxide of O (25%, mass ratio) and 11ml fully stirs (1100 rev/mins), is the Fe (NO of 1 * 1mol/l continuing to add 300ml concentration under the stirring 3) 39H 2O solution forms gel, and adding 60ml concentration again is 1 * 10 -4The sodium dihydrogen phosphate of mol/l, the pH value of mixed solution are 10; Wore out 20 minutes down at 105 ℃, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 3 times, drying is 1.5 hours under 45 ℃, and obtaining median size after the grinding is cubic α-Fe of 35nm 2O 3Particle, grain size is disperseed near single, and its TEM photo is seen Fig. 5.
Embodiment 4
The preparation flow of present embodiment as shown in Figure 7.1.2g anhydrous Na OH is dissolved in the 300ml deionized water is made into alkali lye, to be that 0.5% sodium oleate fully stirs (2000 rev/mins) evenly mixed with the 100ml mass ratio then, continues to stir that to add 300ml concentration down be the FeCl of 0.05mol/l again 36H 2O solution forms gel, and adding 50ml concentration again is 1 * 10 -4The SODIUM PHOSPHATE, MONOBASIC of mol/l is towards solution, and the pH value of mixed solution is 12; 105 ℃ aging 10 minutes down, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 4 times, 30 ℃ of dryings 2 hours, obtaining median size after the grinding was spherical nanometer α-Fe of 10nm 2O 3Particle, grain size is disperseed near single, and its TEM photo is seen Fig. 6.
Embodiment 5
The preparation flow of present embodiment as shown in Figure 7.54g urea is dissolved in the 300ml deionized water is made into alkali lye, add 8 gram ethanamides then, fully stir (1500 rev/mins) and make solution evenly mixed, continuing to stir bar again, to add 300ml concentration down be the Fe of 3mol/l 2(SO 4) 3XH 2O solution forms gel, and adding 100ml concentration again is 1 * 10 -4The potassium dihydrogen phosphate of mol/l, the pH value of mixed solution are 11; Wore out 15 minutes down at 100 ℃, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 3 times, drying is 2 hours under 45 ℃, and obtaining particle diameter after the grinding is 25nm globular-Fe 2O 3Particle, grain size is disperseed near single.
Embodiment 6
The preparation flow of present embodiment as shown in Figure 7.The 54g ammonium hydrogencarbonate is dissolved in the 300ml deionized water is made into alkali lye, fully stir (1000 rev/mins) then with the 1ml ethyl acetate evenly mixed, continues to stir that to add 300ml concentration down be the Fe of 2mol/l again 2(SO 4) 3XH 2O solution forms gel, and adding 45ml concentration again is 1 * 10 -4The potassium dihydrogen phosphate of mol/l, the pH value of mixed solution are 10; Wore out 20 minutes down at 100 ℃, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 5 times, drying is 1.5 hours under 50 ℃, and obtaining particle diameter after the grinding is cubic α-Fe of 50nm 2O 3Particle, grain size is disperseed near single.
Embodiment 7
The preparation flow of present embodiment as shown in Figure 7.67.2 gram KOH are dissolved in the 300ml deionized water and are made into alkali lye, and adding the 80ml mass percent then is 0.5% sodium oleate, and it is evenly mixed fully to stir (600 rev/mins).Speed with 10ml/min is the FeCl of 1mol/l to 300ml concentration 2.xH 2Feed chlorine among the O, react after 0.5 hour, under agitation, the iron salt solutions after the oxidation is added in the mixed solution of above-mentioned KOH and sodium oleate and form gel, adding 60ml concentration again is 10 -4The potassium dihydrogen phosphate of mol/l, the pH value of mixed solution are 8; Wore out 10 minutes down at 100 ℃, obtain red suspension liquid, after separating with centrifugal pump and centrifugal, use deionized water wash again 4 times, drying is 2 hours under 30 ℃, and obtaining particle diameter after the grinding is cubic α-Fe of 80nm 2O 3Particle, grain size is disperseed near single.

Claims (6)

1. a nanometer iron oxide red preparation method is characterized in that, may further comprise the steps:
(1) be that the alkali lye of 0.1-3M fully stirs evenly mixed at first at normal temperatures and pressures with compound modifying agent and concentration; Wherein compound modifying agent add-on and Fe 3+Mol ratio is 1: 50-200, and the mol ratio of alkali lye and molysite is that 1-10 prepares burden;
(2) continue to stir simultaneously, adding concentration in mixing solutions is the solubility ferric salt solution of 0.1-3M or the product behind the solubility divalent iron salt solution oxide, produces gel, adds the buffered soln that concentration is 10-4-10-3M again, add buffered soln and Fe 3+Mol ratio be 10 -3-10 -2, keeping the pH value of mixed solution is 8-12; Heat then and keep temperature 85-110 ℃, aging reaction 5-20 minute, obtain suspension liquid;
(3) with the suspension liquid centrifugation of step (2) gained, and then with deionized water wash 3-5 time, and 25-50 ℃ dry 1.5-3 hour down, after being ground into powder, promptly obtain the dispersed nano α-Fe of particle diameter at 10-100nm 2O 3Particle, the pattern of particle are spherical or cubic.
2, nanometer iron oxide red preparation method as claimed in claim 1 is characterized in that, described compound modifying agent comprises: contain C 2～C 6Ester, formic anhydride, diacetyl oxide or propionic anhydride; Methane amide or ethanamide; Citric acid, lactic acid, tartrate, Sodium dodecylbenzene sulfonate or sodium oleate.
3, nanometer iron oxide red preparation method as claimed in claim 1 is characterized in that, described alkali lye comprises: sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, ammoniacal liquor, urea, bicarbonate of ammonia or volatile salt.
4, nanometer iron oxide red preparation method as claimed in claim 1 is characterized in that, described solubility ferric salt solution comprises: FeCl 3, Fe (NO 3) 3Or Fe 2(SO 4) 3Solution.
5, nanometer iron oxide red preparation method as claimed in claim 1, it is characterized in that, product behind the described solubility divalent iron salt solution oxide is that wherein solubility divalent iron salt solution comprises: FeCl the product of gained after the oxidation of solubility divalent iron salt solution usefulness oxygenant 2Or FeSO 4Solution; Oxygenant comprises: airborne oxygen, hydrogen peroxide, chlorine or hypochlorous acid.
6, nanometer iron oxide red preparation method as claimed in claim 1 is characterized in that, described buffered soln comprises: SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
CN 02155680 2002-12-13 2002-12-13 Method for preparing nano iron oxide red Expired - Fee Related CN1230472C (en)

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Publication number Priority date Publication date Assignee Title
CN101633522B (en) * 2009-08-25 2011-05-18 陕西科技大学 Method for preparing alpha-iron oxide nano-powder
CN101786669B (en) * 2010-03-26 2011-11-09 北京理工大学 Alpha-ferric oxide mesoscopic crystal preparation method
CN102220638B (en) * 2011-04-29 2013-02-13 中国科学院合肥物质科学研究院 Preparation method of cubic iron trioxide monocrystal
CN102659186A (en) * 2012-05-03 2012-09-12 西北工业大学 Room temperature liquid phase synthesis method of porous flower-shaped superstructural iron oxide nano material
CN102659188A (en) * 2012-05-22 2012-09-12 中北大学 Magnetic ferric oxide micrometer flower material with multi-stage structure and preparation method thereof
CN102634241B (en) * 2012-05-30 2014-01-29 沈阳化工大学 Composite modified iron oxide red dye and preparation method
CN102910683A (en) * 2012-10-19 2013-02-06 南通宝聚颜料有限公司 Production method for synthesizing nanoscale oxide iron red through full-wet method
CN104922702A (en) * 2015-05-19 2015-09-23 中国科学院过程工程研究所 Superparamagnetic nano-particle and preparation method and application thereof
CN105694539B (en) * 2016-02-29 2018-05-08 中国科学院兰州化学物理研究所 A kind of method that iron oxide red hybrid pigment is prepared using clay mineral
WO2018212712A1 (en) 2017-05-18 2018-11-22 Agency For Science, Technology And Research Composite structure and method of forming the same
CN111477857A (en) * 2020-04-28 2020-07-31 浙江理工大学 Hollow core-shell structure FeS2Preparation method and application of @ C nanocomposite
CN112480444B (en) * 2020-10-27 2022-07-05 南京工业大学 rGO-MoS2-Fe2O3Preparation method and application of ternary composite nano antibacterial membrane material
CN116601118A (en) 2020-12-09 2023-08-15 Dic株式会社 Iron oxide particles and method for producing iron oxide particles

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