CN102838172A - Method for preparing nanometer alpha-Fe2O3 material - Google Patents
Method for preparing nanometer alpha-Fe2O3 material Download PDFInfo
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- CN102838172A CN102838172A CN2012103580847A CN201210358084A CN102838172A CN 102838172 A CN102838172 A CN 102838172A CN 2012103580847 A CN2012103580847 A CN 2012103580847A CN 201210358084 A CN201210358084 A CN 201210358084A CN 102838172 A CN102838172 A CN 102838172A
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- Prior art keywords
- alpha
- feooh
- quality
- nanometer
- addition
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Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 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 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000000084 colloidal system Substances 0.000 claims abstract description 21
- 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 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 14
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 13
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 13
- 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 13
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 230000004913 activation Effects 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 229910006540 α-FeOOH Inorganic materials 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 5
- 239000003513 alkali 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
- 239000006185 dispersion Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 160
- 239000000243 solution Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000007701 flash-distillation Methods 0.000 description 8
- 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
- 230000000694 effects Effects 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
- 230000007062 hydrolysis 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012467 final product Substances 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic 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
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- -1 transmitter Substances 0.000 description 1
Images
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 a kind of preparation nanometer α-Fe
2O
3The method of material.
Background technology
Nano material is owing to its small-size effect that has, quantum effect, macro quanta tunnel effect, surface and interface effect etc.; With the macroscopic particle material highly significant ground difference is arranged on physics, chemistry, mechanical property; And have 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; Absorb well and shielding effect because of having well weathering resistance, photostabilization, magnetic and ultraviolet ray being had; Can be widely used in main field such as luster coating, transmitter, plastics, leather, automobile finish, electronics, high magnetic recording material and catalyzer, nanometer α-Fe
2O
3Dispersion-s has obtained widespread use, and the home market begins to take shape, and the market requirement progressively enlarges.
Existing in the world at present German BASF and U.S. LOOKWOOD are at production nanometer α-Fe
2O
3, domestic also have some units to study nanometer α-Fe
2O
3Preparation, for example, publication number is that the Chinese invention patent application of CN1310206A discloses a kind of nanometer level iron oxide red powder and its major technique characteristics of preparation method are Fe
3+Solution adds alkali and forms the ironic hydroxide gel, and then low temperature is converted into α-Fe fast in the presence of micro-phase reforming catalyst
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, this method is carried out as follows: a. adds the solubility strong base-weak acid salt in being dissolved with ferrous soluble salt solution, be stirred to the generation yellow mercury oxide; B. inserts reaction kettle then, and reaction finishes postcooling to room temperature under heating; C. gets the one dimension alpha-FeOOH nano material through washing and dry again.The one dimension alpha-FeOOH nano material was calcined 1.5-2.5 hour down at 240-360 ℃, obtained one dimension α-Fe
2O
3Nano material.
Notification number is that the Chinese invention patent of CN 101423257B discloses a kind of nanoscale iron oxide red preparation method, comprising: with the water-soluble basic soln of processing of alkaline matter, mix with the crystal formation control agent; Get in the ferrum sulfuricum oxydatum solutum that a certain amount of above-mentioned mixing solutions adds to 30～50 ℃,, be warming up to 65～75 ℃ of reactions again to pH value 8～10; Generate colloid, the preparation crystal seed is regulated pH value to 2～5; Add a certain amount of copperas solution, be warming up to 85～110 ℃, aging reaction 3～9 hours; After the filtration filter cake is used water rinse, dry, pulverizing promptly gets the transparent ferric oxide bloom, makes the nano transparent red iron oxide through 280～400 ℃ of calcinings, drying, pulverizing.
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 of its dispersed index can not be resolved, be difficult to carry out real suitability for industrialized production, and on using, be very limited.BASF and LOOKWOOD have adopted lyophilize on drying.Lyophilize, because of it requires height to equipment and technology, fund input amount is big, 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 that adopts because of dispersed index.
Summary of the invention
The invention provides a kind of preparation nanometer α-Fe
2O
3The method of material, the α-Fe for preparing
2O
3Particle diameter is little, and is scattered, narrowly distributing and evenly.
A kind of preparation nanometer α-Fe
2O
3The method of material comprises:
(1) to Fe
2+Add strong oxidizer in the solution, with Fe
2+Be oxidized to Fe
3+, Fe
3+Strong base solution is added to pH value 6.0-11.0 in activated back, generates Fe (OH)
3The crystal seed colloid;
(2) with said Fe (OH)
3The crystal seed colloid is warming up to 80-90 ℃, adds Fe successively
2+, Fe
3+And Fe
0, reaction is 8-12 hour under the 80-90 ℃ of condition, makes Fe (OH)
3Seeded growth becomes the nanometer alpha-feooh, and the reaction end pH value is 3.5-6.0;
(3) with said nanometer alpha-feooh filter, wash alpha-feooh filter cake, said alpha-feooh filtration cakes torrefaction, pulverizing after 300-400 ℃ of calcining promptly gets nanometer α-Fe
2O
3Material.
Said Fe
2+Solution is preferably the refining green vitriol (FeSO that purifies
47H
2O) the aqueous solution, said strong base solution are preferably the NaOH aqueous solution or the KOH aqueous solution, and said strong oxidizer is preferably NaClO
3Or KClO
3, said oxidizing reaction is carried out under acidic conditions; The Fe that adds in the 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 following:
(1) the 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 for preparing
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) nanometer alpha-feooh dehydration reaction
2α-FeOOH→2α-Fe
2O
3
Among the present invention at Fe
2+Be oxidized to Fe
3+The back is to Fe
3+Carry out activation, control crystal seed colloidal is stablized the growth with crystal seed, especially can control the ratio of the major and minor axis of crystal seed, and the crystal after the growth becomes acicular structure, has better dispersiveness.
Preferably, the activatory method is described in the step (1):
Under 50-60 ℃ of condition, add mixed additive, reacted 5～10 hours, said mixed additive is at least a in Vinylpyrrolidone polymer (PVP), X 2073, sodium oleate, sodium naphthalene sulfonate and the alkyl polyoxyethylene ether.
More preferably, said mixed additive is the mixture of Vinylpyrrolidone polymer, X 2073, sodium oleate and sodium naphthalene sulfonate, and the addition of said Vinylpyrrolidone polymer is Fe in the step (1)
2+0.1～0.3% of quality, the addition of X 2073 are Fe in the step (1)
2+1～3% of quality, the addition of sodium naphthalene sulfonate are Fe in the step (1)
2+0.1～0.3% of quality, the addition of sodium oleate are Fe in the step (1)
2+0.1～0.3% of quality.
Most preferably, the addition of said Vinylpyrrolidone polymer is Fe in the step (1)
2+0.1% of quality, the addition of X 2073 are Fe in the step (1)
2+1% of quality, the addition of sodium naphthalene sulfonate are Fe in the step (1)
2+0.1% of quality, the addition of sodium oleate are Fe in the step (1)
2+0.1% of quality.
Add strong base solution in the step (1) to pH value 8.5-9.5, generate Fe (OH)
3The crystal seed colloid.At Fe (OH)
3In the crystal seed colloid generative process, the pH value is high, and the crystal seed of generation is bigger, helps the growth of crystal seed, and crystal seed is big more, and growth is just fast more, and last product dispersiveness is good more, and therefore, this pH value selects 6～11 among the present invention, is preferably 8.5-9.5.
The present invention is at Fe (OH)
3The crystal 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)
3The crystal seed colloid surface generates alpha-feooh, because Fe
3+Be activated before generating crystal seed, effectively the speed of inhibited oxidation reduction reaction, FeSO simultaneously
4Adding make the Zeta electric potential of system further become big, make Fe (OH) on the one hand
3The crystal seed colloid is more stable; Can effectively control Fe on the other hand
2(SO
4)
3Take place to produce H after the hydrolysis
2SO
4And Fe
0Speed of reaction, and finally reduce Fe
0Consumption.
Preferably, Fe described in the step (2)
2+And Fe
3+Addition to amount to into FeSO
47H
2The O meter is respectively Fe (OH)
3The 5-10% of crystal seed quality and 20-30%; Said Fe
0Addition be Fe (OH)
3The 10-20% of crystal seed quality.
Fe (OH) described in the step (2)
3It is 85 ℃ that seeded growth becomes the terminal temperature of nanometer alpha-feooh, and reaction end pH value is 3.5-4.0.
Fe (OH) described in the 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-feoohs+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 prolongs 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 accelerate the Fe that produces in the system simultaneously
2+Concentration rises, and this moment, reaction formula was: 2FeSO
4+ 1/2O
2+ 3H
2O → 2 alpha-feoohs+2H
2O (this reaction equation is made as X2), though the X2 product also is finally to produce alpha-feooh, the product specific surface of X2 and X1 is accomplished different, 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 descend, and therefore most preferably terminal temperature is 85 ℃.
Reaction end is suppressed at pH3.5-4.0 in the step (2), makes H in the system
2SO
4And Fe
0Do not react final Fe
2(SO
4)
3The hydrolysis stopped reaction.So the reaction end pH of this patent is 3.5-4.0.
Dry described in the step (3) is 5～10% for adopting microwave drying to alpha-feooh water cut earlier, is 2.5～3% through expansion drying to alpha-feooh water ratio again.
The thickness of alpha-feooh filter cake is no more than 3cm during said microwave drying.
Electric power is 80～100kw/mg during microwave drying.
The drying means that utilizes microwave and flash distillation to combine has thoroughly solved nanometer α-Fe
2O
3Agglomeration traits in drying process, dispersiveness are further guaranteed, it can be scattered in all kinds of media in practical application at an easy rate, have solved nano material and have been difficult for the dispersive key issue.
The said per-cent of the present invention all refers to mass percent except that specified otherwise.
Beneficial effect of the present invention:
Preparing method of the present invention passes through mixed additive to Fe
3+Activation, control crystal seed colloid-stabilised growth, crystal seed generates the back by Fe
2(SO
4)
3Hydrolysis generates alpha-feooh at seed surface, through microwave and flash distillation bonded drying means system is generated alpha-feooh at last and carries out drying, thoroughly solves nanometer α-Fe
2O
3Agglomeration traits in drying process, dispersiveness are further guaranteed, by the nanometer α-Fe of the inventive method preparation
2O
3Through electromicroscopic photograph, be fusiform, acicular structure.Major axis 60-80nm, minor axis 10-20nm, the nanometer α of preparation-Fe
2O
3The brilliant narrowly distributing of grain, uniform particles, shape intact, not having reunites is prone to disperse.
Description of drawings
Fig. 1 is the α-Fe of embodiment 1 preparation
2O
3Powder thank to Electronic Speculum figure thoroughly.
Fig. 2 is the α-Fe of embodiment 1 preparation
2O
3The XRD diffractogram of powder.
Fig. 3 is NaOH and Fe
3+PH value during reaction is to the figure that influences of the specific surface of product alpha-feooh, and ordinate zou s is the specific surface area of product among the figure, and X-coordinate is pH.
Embodiment
Used product is the commercially available prod in following examples.
Get the refining green vitriol (FeSO that purifies
47H
2O), use deionized water to be configured to concentration and (amount to into FeSO as 75g/l
47H
2O) contain Fe
2+Under the solution, 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%), add a certain amount of again (for containing Fe
2+Fe in the solution
2+Quality 7.0%) NaClO
3Reaction makes Fe
2+(FeSO
47H
2O) thoroughly become Fe
3+(Fe
2(SO
4)
3), with Fe
2(SO
4)
3Add H
2O is diluted to the solution that concentration is 35g/l (amounting to into FeSO47H2O), and the mixture that adds PVP, X 2073, sodium oleate and sodium naphthalene sulfonate under 200 rev/mins, 50 ℃ conditions carries out activation, and the addition of PVP is for containing Fe
2+Fe in the solution
2+0.1% of quality, the addition of X 2073 is for containing Fe
2+Fe in the solution
2+1% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+Fe in the solution
2+0.1% of quality, the addition of sodium oleate is for containing Fe
2+Fe in the solution
2+0.1% of quality.
Fe (OH)
3The crystal seed colloid is warming up to 85 ℃, adds FeSO successively
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
2The O meter is respectively Fe (OH)
38% and 25% of crystal seed quality; The addition of iron sheet is Fe (OH)
3The crystal seed quality 15%), 85 ℃ the reaction 10 hours, make Fe (OH)
3Seeded growth and generate alpha-feooh, reaction end pH is 4.0.
After reaction finishes, the nanometer alpha-feooh is carried out drying after filtering and washing, drying is earlier through microwave drying; In the microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg; In the microwave drying; The employing Teflon tap transports, and gait of march is 30 meters/hour, and final water cut is controlled at 5-10%.Through flash distillation 5-10% water is dried to less than 3% at last, final water cut 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, promptly gets nanometer α-Fe
2O
3Powder is red powder.
Shown in Figure 1 is the α-Fe of present embodiment preparation
2O
3The TEM figure of powder can be known by Fig. 1, by the nanometer α-Fe of the inventive method preparation
2O
3Through electromicroscopic photograph, be fusiform, acicular structure, major axis 60-80nm, minor axis 10-20nm, the nanometer α of preparation-Fe
2O
3The brilliant narrowly distributing of grain, uniform particles, shape intact, not having reunites is prone to disperse.
α-Fe with the present embodiment preparation
2O
3Powder carries out qualitative analysis of phase with X-pert PRO X-ray diffractometer, and its XRD diffractogram collection of illustrative plates is as shown in Figure 2, and through the X-ray diffraction analysis, the sample of present embodiment preparation is α-Fe
2O
3, do not find other thing phases.
On the basis of this embodiment, research NaOH and Fe
3+PH value during reaction is to the influence of the specific surface of product alpha-feooh, and the result is as shown in Figure 3, and the pH value mainly influences Fe (OH)
3Colloidal size, and Fe (OH)
3Colloidal concentration is the minor effect factor.Can know that like figure when pH value 6 increased to 8, size of particles sharply increased, cause specific surface from 400m
2/ g sharply drops to 100m
2/ g.The crystal seed that generates is big more, and growth is just fast more, and last product dispersiveness is good more.The seed ratio surface is big more, and the product alpha-feooh particle of generation is just more little, can cause the dispersed decline of final product, and therefore, pH is preferably 8.5-9.5.
Get the refining green vitriol (FeSO that purifies
47H
2O), use deionized water to be configured to concentration and (amount to into FeSO as 100g/l
47H
2O) contain Fe
2+Under the solution, 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 the solution
2+Quality 0.015%), add a certain amount of again (for containing Fe
2+Fe in the solution
2+Quality 7.0%) NaClO
3Reaction 8 makes Fe
2+(FeSO
47H
2O) thoroughly become Fe
3+(Fe
2(SO
4)
3), with Fe
2(SO
4)
3Add H
2O is diluted to the solution that concentration is 50g/l (amounting to into FeSO47H2O), and the mixture that adds PVP, X 2073, sodium oleate and sodium naphthalene sulfonate under 200 rev/mins, 60 ℃ conditions carries out activation, and the addition of PVP is for containing Fe
2+Fe in the solution
2+0.3% of quality, the addition of X 2073 is for containing Fe
2+Fe in the solution
2+3% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+Fe in the solution
2+0.3% of quality, the addition of sodium oleate is for containing Fe
2+Fe in the solution
2+0.3% of quality.
Fe (OH)
3The crystal seed colloid is warming up to 85 ℃, adds FeSO successively
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
2The O meter is respectively Fe (OH)
310% and 30% of crystal seed quality; The addition of iron sheet is Fe (OH)
3The crystal seed quality 20%), 85 ℃ the reaction 10 hours, make Fe (OH)
3Seeded growth and generate alpha-feooh, reaction end pH is 4.0.
After reaction finishes, the nanometer alpha-feooh is carried out microwave drying earlier after filtering and washing, drying is earlier through microwave drying; In the microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg; In the microwave drying; The employing Teflon tap transports, and gait of march is 30 meters/hour, and final water cut is controlled at 5-10%.Through flash distillation 5-10% water is dried to less than 3% at last, final water cut 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, promptly gets nanometer α-Fe
2O
3Red powder body material.
Get the refining green vitriol (FeSO that purifies
47H
2O), use deionized water to be configured to concentration and (amount to into FeSO as 30g/l
47H
2O) contain Fe
2+Under the solution, 55 ℃, 150r/min stirring velocity, add a certain amount of (for containing Fe
2+Fe in the solution
2+Quality 0.015%) 98% industrial sulphuric acid adds a certain amount of (for containing Fe again
2+Fe in the solution
2+Quality 7.0%) NaClO
3Reaction makes Fe
2+(FeSO
47H
2O) thoroughly become Fe
3+(Fe
2(SO
4)
3), with Fe
2(SO
4)
3Add H
2O is diluted to the solution that concentration is 50g/l (amounting to into FeSO47H2O), and the mixture that adds PVP, X 2073, sodium oleate and sodium naphthalene sulfonate under 200 rev/mins, 50 ℃ conditions carries out activation, and the addition of PVP is for containing Fe
2+Fe in the solution
2+0.2% of quality, the addition of X 2073 is for containing Fe
2+Fe in the solution
2+2% of quality, the addition of sodium naphthalene sulfonate is for containing Fe
2+Fe in the solution
2+0.2% of quality, the addition of sodium oleate is for containing Fe
2+Fe in the solution
2+0.2% of quality.
Fe (OH)
3The crystal seed colloid is warming up to 85 ℃, adds FeSO successively
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
2The O meter is respectively Fe (OH)
35% and 20% of crystal seed quality; The addition of iron sheet is Fe (OH)
3The crystal seed quality 10%), 90 ℃ the reaction 8 hours, make Fe (OH)
3Seeded growth and generate alpha-feooh, reaction end pH is 3.0.
After reaction finishes, the nanometer alpha-feooh is carried out microwave drying earlier after filtering and washing, drying is earlier through microwave drying; In the microwave drying, it is thick that the thickness of filter cake should be no more than 3cm, and electric power is 80kw/mg; In the microwave drying; The employing Teflon tap transports, and gait of march is 30 meters/hour, and final water cut is controlled at 5-10%.Through flash distillation 5-10% water is dried to less than 3% at last, final water cut 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, promptly gets nanometer α-Fe
2O
3Red powder body material.
Claims (8)
1. one kind prepares nanometer α-Fe
2O
3The method of material is characterized in that, comprising:
(1) to Fe
2+Add strong oxidizer in the solution, with Fe
2+Be oxidized to Fe
3+, Fe
3+Strong base solution is added to pH value 6.0-11.0 in activated back, generates Fe (OH)
3The crystal seed colloid;
(2) with said Fe (OH)
3The crystal seed colloid is warming up to 80-90 ℃, adds Fe
2+, Fe
3+And Fe
0, reaction is 8-12 hour under the 80-90 ℃ of condition, makes Fe (OH)
3Seeded growth becomes the nanometer alpha-feooh, and reaction end pH value is 3.5-6.0;
(3) with said nanometer alpha-feooh filter, wash alpha-feooh filter cake, said alpha-feooh filtration cakes torrefaction, pulverizing after 300-400 ℃ of calcining promptly gets nanometer α-Fe
2O
3Material.
2. method according to claim 1 is characterized in that, the activatory method is described in the step (1):
Under 50-60 ℃ of condition, add mixed additive, reacted 5～10 hours, said mixed additive is at least a in Vinylpyrrolidone polymer, X 2073, sodium oleate, sodium naphthalene sulfonate and the alkyl polyoxyethylene ether.
3. method according to claim 2 is characterized in that, said mixed additive is the mixture of Vinylpyrrolidone polymer, X 2073, sodium oleate and sodium naphthalene sulfonate, and the addition of said Vinylpyrrolidone polymer is Fe in the step (1)
2+0.1～0.3% of quality, the addition of X 2073 are Fe in the step (1)
2+1～3% of quality, the addition of sodium naphthalene sulfonate are Fe in the step (1)
2+0.1～0.3% of quality, the addition of sodium oleate are Fe in the step (1)
2+0.1～0.3% of quality.
4. method according to claim 1 is characterized in that, adds strong base solution in the step (1) to pH value 8.5-9.5, generates Fe (OH)
3The crystal seed colloid.
5. method according to claim 1 is characterized in that, Fe described in the step (2)
2+And Fe
3+Addition to amount to into FeSO
47H
2The O meter is respectively Fe (OH)
3The 5-10% of crystal seed quality and 20-30%; Said Fe
0Addition be Fe (OH)
3The 10-20% of crystal seed quality.
6. method according to claim 1 is characterized in that, Fe (OH) described in the step (2)
3It is 85 ℃ that seeded growth becomes the terminal temperature of nanometer alpha-feooh, and reaction end pH value is 3.5-4.0.
7. method according to claim 1 is characterized in that, dry described in the step (3) is 5～10% for adopting microwave drying to alpha-feooh water cut earlier, is 2.5～3% through expansion drying to alpha-feooh water ratio again.
8. method according to claim 7 is characterized in that, the thickness of alpha-feooh filter cake is no more than 3cm during said microwave drying.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928689A (en) * | 2014-04-21 | 2014-07-16 | 合肥工业大学 | Method for preparing heterogeneous electric Fenton cathode material |
| CN104150541A (en) * | 2014-09-03 | 2014-11-19 | 安徽工业大学 | Preparation method for rice grain-shaped alpha-Fe2O3 (alpha-ferric oxide) nanometer powder |
| CN105731548A (en) * | 2016-03-07 | 2016-07-06 | 北京天下兴科技有限公司 | Catalytic oxidation method for converting ferrous iron into ferric iron at normal temperature and normal pressure |
| CN110026195A (en) * | 2019-05-05 | 2019-07-19 | 河北师范大学 | A kind of high activity α-Fe2O3Nanometer sheet and its preparation method and application |
| CN110255625A (en) * | 2019-07-02 | 2019-09-20 | 浙江华源颜料股份有限公司 | A kind of preparation method and applications of high activated catalyst iron oxide red |
| CN112047384A (en) * | 2020-08-13 | 2020-12-08 | 桂林理工大学 | Method for preparing nano iron oxide negative electrode material for lithium ion battery by using tin ore tailing sulfuric acid leaching solution |
| CN114134567A (en) * | 2021-12-07 | 2022-03-04 | 贵州民族大学 | Method for synthesizing FeOOH crystal of iron oxyhydroxide at high temperature and high pressure |
| CN114570412A (en) * | 2022-02-18 | 2022-06-03 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
| CN114854278A (en) * | 2022-04-25 | 2022-08-05 | 铜陵同达兴实业有限责任公司 | Preparation process of nano iron oxide coating dispersion system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289746A (en) * | 1979-05-22 | 1981-09-15 | Central Glass Company, Limited | Process for preparation of micaceous iron oxide |
| CN101423257A (en) * | 2008-11-07 | 2009-05-06 | 浙江正奇化工有限公司 | Method for preparing nano grade iron oxide red |
| CN102092794A (en) * | 2010-12-08 | 2011-06-15 | 浙江大学 | Preparation method of nano iron oxide yellow or nano iron oxide red |
-
2012
- 2012-09-24 CN CN201210358084.7A patent/CN102838172B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289746A (en) * | 1979-05-22 | 1981-09-15 | Central Glass Company, Limited | Process for preparation of micaceous iron oxide |
| CN101423257A (en) * | 2008-11-07 | 2009-05-06 | 浙江正奇化工有限公司 | Method for preparing nano grade iron oxide red |
| CN102092794A (en) * | 2010-12-08 | 2011-06-15 | 浙江大学 | Preparation method of nano iron oxide yellow or nano iron oxide red |
Non-Patent Citations (1)
| Title |
|---|
| 黄坚等: "氯酸钠氧化法制备超细氧化铁黄的研究", 《广州化学》 * |
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| 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 |
| CN110026195A (en) * | 2019-05-05 | 2019-07-19 | 河北师范大学 | A kind of high activity α-Fe2O3Nanometer sheet and its preparation method and application |
| 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 | Preparation method and application of high-activity catalyst iron oxide red |
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| CN114570412A (en) * | 2022-02-18 | 2022-06-03 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
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