CN102838172B - Method for preparing nanometer alpha-Fe2O3 material - Google Patents
Method for preparing nanometer alpha-Fe2O3 material Download PDFInfo
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- CN102838172B CN102838172B CN201210358084.7A CN201210358084A CN102838172B CN 102838172 B CN102838172 B CN 102838172B CN 201210358084 A CN201210358084 A CN 201210358084A CN 102838172 B CN102838172 B CN 102838172B
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- feooh
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- crystal seed
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 14
- 229910003145 α-Fe2O3 Inorganic materials 0.000 title abstract 4
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000084 colloidal system Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910006540 α-FeOOH Inorganic materials 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 141
- 239000000243 solution Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000047 product Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000007701 flash-distillation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005021 gait Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 sensor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for preparing a nanometer alpha-Fe2O3 material. The method comprises the steps of: (1) adding a strong oxidant in a Fe<2+> solution to oxidize Fe<2+> to Fe<3+>, and adding a strong alkali solution after activation of the Fe<3+> until the pH value is 6.0-11.0 so as to generate a Fe(OH)3 seed crystal colloid; (2) heating the Fe(OH)3 seed crystal colloid to be at 80-90 DEG C, adding the Fe<2+>, the Fe<3+> and Fe<0> in sequence, and reacting at a temperature of 80-90 DEG C for 8-12h to enable the Fe(OH)3 seed crystal colloid to grow to form nanometer alpha-FeOOH, wherein the destination pH value of the reaction is 3.5-6.0; and (3) filtering and washing the nanometer alpha-FeOOH to obtain an alpha-FeOOH filter cake, drying and crushing the alpha-FeOOH filter cake, and then calcining at a temperature of 300-400 DEG C to obtain the nanometer alpha-Fe2O3 powder material. The alpha-Fe2O3 prepared by using the method is small in particle size, good in dispersion, and narrow and even in distribution.
Description
Technical field
The present invention relates to mineral compound preparation technology field, be specifically related to one and prepare nanometer α-Fe
2o
3the method of material.
Background technology
Nano material is due to its small-size effect having, quantum effect, macro quanta tunnel effect, surface and interface effect etc., in physics, chemistry, mechanical property, there is difference very significantly with macroscopic particle material, and there is very good character, obtained application more and more widely in recent years.
Nanometer α-Fe
2o
3it is a kind of spindle shape particle, particle diameter is less than 0.1nm, because thering is well weathering resistance, photostabilization, magnetic and ultraviolet ray being had and absorbed well and shielding effect, can be widely used in the major domains such as luster coating, sensor, plastics, leather, automobile finish, electronics, high magnetic recording material and catalyzer, nanometer α-Fe
2o
3dispersion is widely applied, and domestic market begins to take shape, and the market requirement progressively expands.
Have in the world at present German BASF and U.S. LOOKWOOD at production nanometer α-Fe
2o
3, domestic also have some units to study nanometer α-Fe
2o
3preparation, for example, the Chinese invention patent application that publication number is CN1310206A discloses a kind of nanometer level iron oxide red powder and its technical characteristics of preparation method is Fe
3+solution adds alkali and forms ironic hydroxide gel, and then under Micro Phases conversion catalyst exists, low temperature rapid conversion is α-Fe
2o
3nanoparticle.
Notification number is that the Chinese invention patent of CN 1315734C discloses a kind of one dimension alpha-feooh and α-Fe
2o
3method for producing nano material, the method is carried out as follows: a., being dissolved with in ferrous soluble salt solution, adds solubility strong base-weak acid salt, is stirred to generation yellow mercury oxide; Then b. inserts reactor, and under heating, reaction is cooled to room temperature after finishing; C., through washing and dry, obtains one dimension alpha-FeOOH nano material again.One dimension alpha-FeOOH nano material is calcined to 1.5-2.5 hour at 240-360 ℃, obtain one dimension α-Fe
2o
3nano material.
Notification number is that the Chinese invention patent of CN 101423257B discloses a kind of nano grade iron oxide red preparation method, comprise: by the water-soluble alkaline matter basic solution of making, mix with chemical additives, get in the ferrum sulfuricum oxydatum solutum that a certain amount of above-mentioned mixing solutions adds to 30～50 ℃, to pH value 8～10, be warming up to again 65～75 ℃ of reactions, generate colloid, prepare crystal seed, regulate pH value to 2～5, add a certain amount of copperas solution, be warming up to 85～110 ℃, aging reaction 3～9 hours, after filtration by filter cake water rinse, dry, pulverize and obtain transparent ferric oxide bloom, through 280～400 ℃ of calcinings, dry, pulverizing makes nano transparent red iron oxide.
Nanometer α-Fe that Germany BASF and U.S. LOOKWOOD produce
2o
3, other the nanometer α-Fe that comprises some domestic companies' productions
2o
3, because its dispersed index can not be resolved, be difficult to carry out real suitability for industrialized production, and be very limited in application.BASF and LOOKWOOD have adopted lyophilize on dry.Lyophilize, because it is high to equipment and technology requirement, fund input amount is large, and other company is difficult to invention and makes.Up to the present, relate to preparation nanometer α-Fe
2o
3the method of patent, never relates to the method for the drying process adopting because of dispersed index.
Summary of the invention
The invention provides one and prepare nanometer α-Fe
2o
3the method of material, the α-Fe preparing
2o
3particle diameter is little, scattered, narrowly distributing and evenly.
One is prepared nanometer α-Fe
2o
3the method of material, comprising:
(1) to Fe
2+in solution, add strong oxidizer, by Fe
2+be oxidized to Fe
3+, Fe
3+activated rear interpolation strong base solution, to pH value 6.0-11.0, generates Fe (OH)
3crystal seed colloid;
(2) by described Fe (OH)
3crystal seed colloid is warming up to 80-90 ℃, adds successively Fe
2+, Fe
3+and Fe
0, under 80-90 ℃ of condition, react 8-12 hour, make Fe (OH)
3seeded growth becomes nano α-FeOOH, and reaction end pH value is 3.5-6.0;
(3) described nano α-FeOOH is filtered, is washed alpha-feooh filter cake, described alpha-feooh filtration cakes torrefaction, obtain nanometer α-Fe through 300-400 ℃ of calcining after pulverizing
2o
3material.
Described Fe
2+solution is preferably the refining green vitriol (FeSO that purifies
47H
2o) the aqueous solution, described strong base solution is preferably the NaOH aqueous solution or the KOH aqueous solution, and described strong oxidizer is preferably NaClO
3or KClO
3, described oxidizing reaction is carried out under acidic conditions; The Fe adding in step (2)
2+, Fe
3+and Fe
0respectively with FeSO
47H
2o, Fe
2(SO
4)
3add with the form of iron sheet, the inventive method main chemical reactions formula is as follows:
(1) ferric sulphate preparation is Fe
2+be oxidized to Fe
3+
FeSO
4+H
2SO
4+NaClO
3→Fe
2(SO
4)
3+NaCl+Na
2SO
4
(2) crystal seed colloid preparation
Fe
2(SO
4)
3+NaOH→Fe(OH)
3+Na
2SO
4
(3) Fe
2(SO
4)
3hydrolysis and seeded growth
Fe
2(SO
4)
3+H
2O→α-FeOOH+H
2SO
4
(4) nano α-FeOOH dehydration reaction
2α-FeOOH→2α-Fe
2O
3
In the present invention at Fe
2+be oxidized to Fe
3+afterwards to Fe
3+activate, control the growth of the stable and crystal seed of crystal seed colloid, especially can control the ratio of semi-minor axis length of crystal seed, the crystal after growth becomes acicular structure, has better dispersiveness.
Preferably, described in step (1), the method for activation is:
Under 50-60 ℃ of condition, add mixed additive, react 5～10 hours, described mixed additive is at least one in polyvinylpyrrolidone (PVP), Sodium dodecylbenzene sulfonate, sodium oleate, sodium naphthalene sulfonate and alkyl polyoxyethylene ether.
More preferably, described mixed additive is the mixture of polyvinylpyrrolidone, Sodium dodecylbenzene sulfonate, sodium oleate and sodium naphthalene sulfonate, and the addition of described polyvinylpyrrolidone is Fe in step (1)
2+0.1～0.3% of quality, the addition of Sodium dodecylbenzene sulfonate is Fe in step (1)
2+1～3% of quality, the addition of sodium naphthalene sulfonate is Fe in step (1)
2+0.1～0.3% of quality, the addition of sodium oleate is Fe in step (1)
2+0.1～0.3% of quality.
Most preferably, the addition of described polyvinylpyrrolidone is Fe in step (1)
2+0.1% of quality, the addition of Sodium dodecylbenzene sulfonate is Fe in step (1)
2+1% of quality, the addition of sodium naphthalene sulfonate is Fe in step (1)
2+0.1% of quality, the addition of sodium oleate is Fe in step (1)
2+0.1% of quality.
In step (1), add strong base solution to pH value 8.5-9.5, generate Fe (OH)
3crystal seed colloid.At Fe (OH)
3in crystal seed colloid generative process, pH value is high, and the crystal seed of generation is larger, is conducive to the growth of crystal seed, and crystal seed is larger, and growth is just faster, and last product dispersiveness is better, and therefore, in the present invention, this pH value selects 6～11, is preferably 8.5-9.5.
The present invention is at Fe (OH)
3crystal seed colloid adds a certain amount of Fe after generating
3+(Fe
2(SO
4)
3) and Fe
0(iron sheet), Fe
2(SO
4)
3hydrolysis is at Fe (OH)
3crystal seed colloid surface generates alpha-feooh, due to Fe
3+before generating crystal seed, be activated the effectively speed of inhibited oxidation reduction reaction, simultaneously FeSO
4add and make the Zeta electric potential of system further become large, make on the one hand Fe (OH)
3crystal seed colloid is more stable; Can effectively control on the other hand Fe
2(SO
4)
3occur to produce H after hydrolysis
2sO
4and Fe
0speed of reaction, and finally reduce Fe
0consumption.
Preferably, Fe described in step (2)
2+and Fe
3+addition to amount to into FeSO
47H
2o meter is respectively Fe (OH)
3the 5-10% of crystal seed quality and 20-30%; Described Fe
0addition be Fe (OH)
3the 10-20% of crystal seed quality.
Fe (OH) described in step (2)
3it is 85 ℃ that seeded growth becomes the terminal temperature of nano α-FeOOH, and reaction end pH value is 3.5-4.0.
Fe (OH) described in step (2)
3seeded growth, most critical is Fe
2(SO
4)
3the control of final hydrolysising reacting temperature.
Fe
2(SO
4)
3+ 4H
2o → 2 alpha-feooh+3H
2sO
4(this reaction equation is made as X1)
Temperature is lower than 85 ℃, Fe
2(SO
4)
3hydrolysis reaction slow, seeded growth speed is slow, finally extends the reaction times; Temperature is higher than 85 ℃, Fe
2(SO
4)
3hydrolysis reaction obviously accelerate, cause H
2sO
4and Fe
0speed of response also simultaneously accelerate, the Fe producing in system
2+concentration rises, and now reaction formula is: 2FeSO
4+ 1/2O
2+ 3H
2o → 2 alpha-feooh+2H
2o (this reaction equation is made as X2), although X2 product is also finally to produce alpha-feooh, the product specific surface of X2 and X1 completes difference, the specific surface area of X2 product is 81-100m
2/ g, and the specific surface area of X1 product is 130-160m
2/ g, finally also makes the dispersiveness of product decline, and therefore most preferably terminal temperature is 85 ℃.
In step (2), reaction end is suppressed at pH3.5-4.0, makes H in system
2sO
4and Fe
0do not react, final Fe
2(SO
4)
3hydrolysis stopped reaction.Therefore the reaction end pH of this patent is 3.5-4.0.
Described in step (3), being dried as first adopting microwave drying to alpha-feooh water content is 5～10%, then is 2.5～3% by expansion drying to alpha-feooh water ratio.
When described microwave drying, the thickness of alpha-feooh filter cake is no more than 3cm.
When microwave drying, electric power is 80～100kw/mg.
The drying means that utilizes microwave and flash distillation to combine, has thoroughly solved nanometer α-Fe
2o
3agglomeration traits in drying process, dispersiveness is further guaranteed, it can be scattered in all kinds of media in actual applications easily, has solved nano material and has been difficult for the key issue of disperseing.
The said per-cent of the present invention all refers to mass percent except specified otherwise.
Beneficial effect of the present invention:
Preparation method of the present invention by mixed additive to Fe
3+activation, control crystal seed colloid-stabilised growth, after crystal seed generates by Fe
2(SO
4)
3hydrolysis generates alpha-feooh at seed surface, finally by the drying means of microwave and flash distillation combination, system is generated to alpha-feooh and is dried, and thoroughly solves nanometer α-Fe
2o
3agglomeration traits in drying process, dispersiveness is further guaranteed, the nanometer α-Fe being prepared by the inventive method
2o
3by electromicroscopic photograph, be fusiform, acicular structure.Major axis 60-80nm, minor axis 10-20nm, the nanometer α-Fe of preparation
2o
3the brilliant narrowly distributing of grain, uniform particles, shape is complete, easily disperses without reuniting.
Accompanying drawing explanation
Fig. 1 is α-Fe prepared by embodiment 1
2o
3powder thoroughly thank to Electronic Speculum figure.
Fig. 2 is α-Fe prepared by embodiment 1
2o
3the XRD diffractogram of powder.
Fig. 3 is NaOH and Fe
3+the specific surface of pH value when reaction on product alpha-feooh affect figure, the specific surface area that in figure, ordinate zou s is product, X-coordinate is pH.
Embodiment
In following examples, product used is commercially available prod.
Embodiment 1
Get the refining green vitriol (FeSO that purifies
47H
2o), being configured to concentration with deionized water is that 75g/l (amounts to into FeSO
47H
2o) containing Fe
2+solution, under 60 ℃, 150r/min stirring velocity, (the interpolation quality of 98% industrial sulphuric acid is for containing Fe to add a certain amount of 98% industrial sulphuric acid
2+solution Fe
2+quality 0.015%), then add a certain amount of (for containing Fe
2+fe in solution
2+quality 7.0%) NaClO
3reaction, makes Fe
2+(FeSO
47H
2o) thoroughly become Fe
3+(Fe
2(SO
4)
3), by Fe
2(SO
4)
3add H
2o is diluted to the solution that concentration is 35g/l (amounting to into FeSO47H2O), under 200 revs/min, 50 ℃ conditions, adds the mixture of PVP, Sodium dodecylbenzene sulfonate, sodium oleate and sodium naphthalene sulfonate to activate, and the addition of PVP is for containing Fe
2+fe in solution
2+0.1% of quality, the addition of Sodium dodecylbenzene sulfonate is for containing Fe
2+fe in solution
2+1% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+fe in solution
2+0.1% of quality, the addition of sodium oleate is for containing Fe
2+fe in solution
2+0.1% of quality.
Activate 8 hours, stirring velocity when activation is 250r/min, and activation temperature is controlled at 55 ℃, and NaOH solution to the pH value that has activated rear interpolation 15% is 9, and the control of interpolation time is 2 hours, and temperature is controlled at 30 ℃, generates Fe (OH)
3crystal seed colloid.
Fe (OH)
3crystal seed colloid is warming up to 85 ℃, adds successively FeSO
47H
2o, Fe
2(SO
4)
3, and iron sheet (FeSO
47H
2o and Fe
2(SO
4)
3addition is to amount to into FeSO
47H
2o meter is respectively Fe (OH)
38% and 25% of crystal seed quality; The addition of iron sheet is Fe (OH)
3crystal seed quality 15%), 85 ℃ reaction 10 hours, make Fe (OH)
3seeded growth and generate alpha-feooh, reaction end pH is 4.0.
After reaction finishes, nano α-FeOOH is dried after filtration with after washing, dry is first by microwave drying, in microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg, in microwave drying, employing Teflon tap transports, and gait of march is 30 ms/h, and final water content is controlled at 5-10%.Finally by flash distillation, 5-10% water is dried to and is less than 3%, final water content is controlled at 2.5-3.0%, and flash distillation power is 40HZ, and flash-off time is 8 hours.
Dried alpha-feooh is in silica tube electric heating roasting case, and maturing temperature is controlled at 350 ℃, and roasting time is 0.5 hour, obtains nanometer α-Fe
2o
3powder is red powder.
Shown in Fig. 1, be α-Fe prepared by the present embodiment
2o
3the TEM figure of powder, as shown in Figure 1, the nanometer α-Fe being prepared by the inventive method
2o
3by electromicroscopic photograph, be fusiform, acicular structure, major axis 60-80nm, minor axis 10-20nm, the nanometer α-Fe of preparation
2o
3the brilliant narrowly distributing of grain, uniform particles, shape is complete, easily disperses without reuniting.
α-Fe prepared by the present embodiment
2o
3powder carries out qualitative analysis of phase with X-pert PRO X-ray diffractometer, and as shown in Figure 2, through X-ray diffraction analysis, sample prepared by the present embodiment is α-Fe to its XRD diffractogram collection of illustrative plates
2o
3, do not find other thing phases.
On the basis of this embodiment, research NaOH and Fe
3+the impact of the specific surface of pH value when reaction on product alpha-feooh, result as shown in Figure 3, pH value major effect Fe (OH)
3the size of colloid, and Fe (OH)
3the concentration of colloid is minor effect factor.As figure shows, in the time that pH value 6 increases to 8, size of particles sharply increases, and causes specific surface from 400m
2/ g sharply drops to 100m
2/ g.The crystal seed generating is larger, and growth is just faster, and last product dispersiveness is better.Seed ratio surface is larger, and the product alpha-feooh particle of generation is just less, can cause the dispersed decline of final product, and therefore, pH is preferably 8.5-9.5.
Embodiment 2
Get the refining green vitriol (FeSO that purifies
47H
2o), being configured to concentration with deionized water is that 100g/l (amounts to into FeSO
47H
2o) containing Fe
2+solution, under 65 ℃, 150r/min stirring velocity, (the interpolation quality of 98% industrial sulphuric acid is for containing Fe to add a certain amount of 98% industrial sulphuric acid
2+fe in solution
2+quality 0.015%), then add a certain amount of (for containing Fe
2+fe in solution
2+quality 7.0%) NaClO
3reaction 8, makes Fe
2+(FeSO
47H
2o) thoroughly become Fe
3+(Fe
2(SO
4)
3), by Fe
2(SO
4)
3add H
2o is diluted to the solution that concentration is 50g/l (amounting to into FeSO47H2O), under 200 revs/min, 60 ℃ conditions, adds the mixture of PVP, Sodium dodecylbenzene sulfonate, sodium oleate and sodium naphthalene sulfonate to activate, and the addition of PVP is for containing Fe
2+fe in solution
2+0.3% of quality, the addition of Sodium dodecylbenzene sulfonate is for containing Fe
2+fe in solution
2+3% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+fe in solution
2+0.3% of quality, the addition of sodium oleate is for containing Fe
2+fe in solution
2+0.3% of quality.
Activate 10 hours, stirring velocity when activation is 250r/min, and activation temperature is controlled at 60 ℃, and NaOH solution to the pH value that has activated rear interpolation 15% is 9.5, and the control of interpolation time is 3 hours, and temperature is controlled at 40 ℃, generates Fe (OH)
3crystal seed colloid.
Fe (OH)
3crystal seed colloid is warming up to 85 ℃, adds successively FeSO
47H
2o, Fe
2(SO
4)
3, and iron sheet (FeSO
47H
2o and Fe
2(SO
4)
3addition is to amount to into FeSO
47H
2o meter is respectively Fe (OH)
310% and 30% of crystal seed quality; The addition of iron sheet is Fe (OH)
3 crystal seed quality 20%), 85 ℃ reaction 10 hours, make Fe (OH)
3seeded growth and generate alpha-feooh, reaction end pH is 4.0.
After reaction finishes, nano α-FeOOH is first carried out to microwave drying after filtration with after washing, dry is first by microwave drying, in microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg, in microwave drying, employing Teflon tap transports, and gait of march is 30 ms/h, and final water content is controlled at 5-10%.Finally by flash distillation, 5-10% water is dried to and is less than 3%, final water content is controlled at 2.5-3.0%, and flash distillation power is 40HZ, and flash-off time is 8 hours.
Dried alpha-feooh is in silica tube electric heating roasting case, and maturing temperature is controlled at 400 ℃, and roasting time is 0.5 hour, obtains nanometer α-Fe
2o
3red powder body material.
Embodiment 3
Get the refining green vitriol (FeSO that purifies
47H
2o), being configured to concentration with deionized water is that 30g/l (amounts to into FeSO
47H
2o) containing Fe
2+solution, under 55 ℃, 150r/min stirring velocity, adds a certain amount of (for containing Fe
2+fe in solution
2+quality 0.015%) 98% industrial sulphuric acid, then add a certain amount of (for containing Fe
2+fe in solution
2+quality 7.0%) NaClO
3reaction, makes Fe
2+(FeSO
47H
2o) thoroughly become Fe
3+(Fe
2(SO
4)
3), by Fe
2(SO
4)
3add H
2o is diluted to the solution that concentration is 50g/l (amounting to into FeSO47H2O), under 200 revs/min, 50 ℃ conditions, adds the mixture of PVP, Sodium dodecylbenzene sulfonate, sodium oleate and sodium naphthalene sulfonate to activate, and the addition of PVP is for containing Fe
2+fe in solution
2+0.2% of quality, the addition of Sodium dodecylbenzene sulfonate is for containing Fe
2+fe in solution
2+2% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+fe in solution
2+0.2% of quality, the addition of sodium oleate is for containing Fe
2+fe in solution
2+0.2% of quality.
Activate 8 hours, stirring velocity when activation is 250r/min, and activation temperature is controlled at 55 ℃, and NaOH solution to the pH value that has activated rear interpolation 15% is 8.5, and the control of interpolation time is 3 hours, and temperature is controlled at 30 ℃, generates Fe (OH)
3crystal seed colloid.
Fe (OH)
3crystal seed colloid is warming up to 85 ℃, adds successively FeSO
47H
2o, Fe
2(SO
4)
3, and iron sheet (FeSO
47H
2o and Fe
2(SO
4)
3addition is to amount to into FeSO
47H
2o meter is respectively Fe (OH)
35% and 20% of crystal seed quality; The addition of iron sheet is Fe (OH)
3 crystal seed quality 10%), 90 ℃ reaction 8 hours, make Fe (OH)
3seeded growth and generate alpha-feooh, reaction end pH is 3.0.
After reaction finishes, nano α-FeOOH is first carried out to microwave drying after filtration with after washing, dry is first by microwave drying, in microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg, in microwave drying, employing Teflon tap transports, and gait of march is 30 ms/h, and final water content is controlled at 5-10%.Finally by flash distillation, 5-10% water is dried to and is less than 3%, final water content is controlled at 2.5-3.0%, and flash distillation power is 40HZ, and flash-off time is 8 hours.
Dried alpha-feooh is in silica tube electric heating roasting case, and maturing temperature is controlled at 300 ℃, and roasting time is 0.5 hour, obtains nanometer α-Fe
2o
3red powder body material.
Claims (5)
1. prepare nanometer α-Fe for one kind
2o
3the method of material, is characterized in that, comprising:
(1) to Fe
2+in solution, add strong oxidizer, by Fe
2+be oxidized to Fe
3+, Fe
3+activated rear interpolation strong base solution, to pH value 6.0-11.0, generates Fe (OH)
3crystal seed colloid;
The method of described activation is:
Under 50-60 ℃ of condition, add mixed additive, react 5～10 hours;
Described mixed additive is the mixture of polyvinylpyrrolidone, Sodium dodecylbenzene sulfonate, sodium oleate and sodium naphthalene sulfonate, and the addition of described polyvinylpyrrolidone is Fe in step (1)
2+0.1～0.3% of quality, the addition of Sodium dodecylbenzene sulfonate is Fe in step (1)
2+1～3% of quality, the addition of sodium naphthalene sulfonate is Fe in step (1)
2+0.1～0.3% of quality, the addition of sodium oleate is Fe in step (1)
2+0.1～0.3% of quality;
(2) by described Fe (OH)
3crystal seed colloid is warming up to 80-90 ℃, adds Fe
2+, Fe
3+and Fe
0, under 80-90 ℃ of condition, react 8-12 hour, make Fe (OH)
3seeded growth becomes nano α-FeOOH, and reaction end pH value is 3.5-6.0;
(3) described nano α-FeOOH is filtered, is washed alpha-feooh filter cake, described alpha-feooh filtration cakes torrefaction, obtain nanometer α-Fe through 300-400 ℃ of calcining after pulverizing
2o
3material;
Described to be dried as first adopting microwave drying to alpha-feooh water content be 5～10%, then be 2.5～3% by expansion drying to alpha-feooh water ratio.
2. method according to claim 1, is characterized in that, adds strong base solution to pH value 8.5-9.5 in step (1), generates Fe (OH)
3crystal seed colloid.
3. method according to claim 1, is characterized in that, Fe described in step (2)
2+and Fe
3+addition to amount to into FeSO
47H
2o meter is respectively Fe (OH)
3the 5-10% of crystal seed quality and 20-30%; Described Fe
0addition be Fe (OH)
3the 10-20% of crystal seed quality.
4. method according to claim 1, is characterized in that, Fe (OH) described in step (2)
3it is 85 ℃ that seeded growth becomes the terminal temperature of nano α-FeOOH, and reaction end pH value is 3.5-4.0.
5. method according to claim 1, is characterized in that, when described microwave drying, the thickness of alpha-feooh filter cake is no more than 3cm.
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| CN103928689B (en) * | 2014-04-21 | 2016-08-24 | 合肥工业大学 | A kind of preparation method of heterogeneous Fenton cathode material |
| CN104150541B (en) * | 2014-09-03 | 2015-08-12 | 安徽工业大学 | A kind of grain of rice shape α-Fe 2o 3the preparation method of nanometer powder |
| CN105731548B (en) * | 2016-03-07 | 2017-11-28 | 北京天下兴科技有限公司 | Ferrous iron is converted into ferric catalysed oxidation processes under a kind of normal temperature and pressure |
| CN110026195B (en) * | 2019-05-05 | 2021-09-03 | 河北师范大学 | High-activity alpha-Fe2O3Nanosheet and preparation method and application thereof |
| CN110255625B (en) * | 2019-07-02 | 2021-10-22 | 浙江华源颜料股份有限公司 | A kind of preparation method of high activity catalyst iron oxide red and its application |
| CN112047384B (en) * | 2020-08-13 | 2022-11-11 | 桂林理工大学 | Method for preparing nano iron oxide anode material for lithium ion battery by using sulfuric acid leaching solution of tin ore tailings |
| CN114134567B (en) * | 2021-12-07 | 2024-02-06 | 贵州民族大学 | Method for preparing FeOOH crystal by high-temperature high-pressure synthesis |
| CN114570412B (en) * | 2022-02-18 | 2024-03-08 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
| CN114854278B (en) * | 2022-04-25 | 2023-03-31 | 铜陵同达兴实业有限责任公司 | Preparation process of nano iron oxide coating dispersion system |
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