CN110255627A - Nano ferriferrous oxide and preparation method thereof and system - Google Patents
Nano ferriferrous oxide and preparation method thereof and system Download PDFInfo
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- CN110255627A CN110255627A CN201910631781.7A CN201910631781A CN110255627A CN 110255627 A CN110255627 A CN 110255627A CN 201910631781 A CN201910631781 A CN 201910631781A CN 110255627 A CN110255627 A CN 110255627A
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- ferriferrous oxide
- nano ferriferrous
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000004094 surface-active agent Substances 0.000 claims abstract description 57
- 238000000975 co-precipitation Methods 0.000 claims abstract description 50
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000012266 salt solution Substances 0.000 claims abstract description 46
- 150000002505 iron Chemical class 0.000 claims abstract description 45
- 239000012065 filter cake Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 34
- 230000001376 precipitating effect Effects 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 229910001447 ferric ion Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000009777 vacuum freeze-drying Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229940056319 ferrosoferric oxide Drugs 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- -1 iron salt ferric chloride Chemical class 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- NQYSLAZBHMLYIA-UHFFFAOYSA-N [Fe+2].[N+](=O)([O-])[O-].[Fe+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [Fe+2].[N+](=O)([O-])[O-].[Fe+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] NQYSLAZBHMLYIA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000032696 parturition Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of nano ferriferrous oxide and preparation method thereof and systems, this method comprises: (1) mixes ferric salt solution with divalent iron salt solution；(2) the resulting mixed molysite solution of step (1) and precipitating reagent, surfactant are mixed under inert gas protection and carry out coprecipitation reaction；(3) step (2) resulting reaction solution dispersed, filtered and carrying out washing treatment, obtain filtrate and filter cake；(4) frozen drying processing will be carried out after the filter cake pulp, to obtain nano ferriferrous oxide.This method introduces surfactant in coprecipitation process, while being handled by the way of frozen drying pulp filter cake, can significantly reduce the generation of agglomeration, obtains the uniform nano ferriferrous oxide of grain diameter size distribution.
Description
Technical field
The invention belongs to magnetic Nano material fields, specifically, the present invention relates to nano ferriferrous oxide and its preparations
Method and system.
Background technique
The large specific surface area of magnetic Nano material, surface functional group is abundant, has skin effect, bulk effect, quantum ruler
The features such as very little effect and macro quanta tunnel effect, application is very extensive.Nano magnetic material Fe3O4Contain Fe simultaneously2+With
Fe3+, chemical property is stable, and for partial size minimum up to several nanometers, catalytic activity is high, can be used for coating, water process, plastics, leather etc.
A variety of industries.
Prepare nanometer Fe both at home and abroad at present3O4The method of material mainly has the precipitation method, mechanical attrition method, thermal decomposition method, electrification
Learn sedimentation, microemulsion method, hydro-thermal method and sol-gel method etc..These preparation methods principle is different, and mode of operation is different, obtains
To product pattern and performance be very different.
Mechanical attrition method is by physical grinding and squeezes preparation nanometer Fe3O4, this method is easily operated, but prepared
Particle purity is low and particle size is not uniform enough；Hydro-thermal method is that the oxide of iron in solvent occurs under high temperature and pressure effect
Chemical reaction generates nanometer Fe3O4, it can be achieved that the control to product morphology, but equipment operation is more demanding.Coprecipitation preparation
Period is short, mild condition, at low cost and process equipment manipulation are simple, is to prepare nanometer Fe3O4Main stream approach, but traditional be total to
The precipitation method prepare nanometer Fe3O4Magnetic material, fuzzy to the control of nucleation and crystallization process, crystal growing process is usually associated with
The aggregation of nucleus causes product agglomeration obvious, and grain diameter size distribution is uneven.It is existing to use coprecipitation and bimodulus
Dispersion method prepares the Fe that average grain diameter is 10-20nm3O4, higher cost, and the operating condition of membrane module is more harsh, can grasp
The property made is poor.
Therefore, the existing technique for preparing nano ferriferrous oxide is further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of nano ferriferrous oxide and preparation method thereof and system.This method introduces in coprecipitation process
Surfactant, while pulp filter cake is handled by the way of frozen drying, agglomeration can be significantly reduced
Occur, obtains the uniform nano ferriferrous oxide of grain diameter size distribution.
In one aspect of the invention, the invention proposes a kind of methods for preparing nano ferriferrous oxide, according to this hair
Bright embodiment, this method comprises:
(1) ferric salt solution is mixed with divalent iron salt solution；
(2) the resulting mixed molysite solution of step (1) is mixed under inert gas protection with precipitating reagent, surfactant
Stirring carries out coprecipitation reaction；
(3) step (2) resulting reaction solution dispersed, filtered and carrying out washing treatment, obtain filtrate and filter cake；
(4) frozen drying processing will be carried out after the filter cake pulp, to obtain nano ferriferrous oxide.
The method according to an embodiment of the present invention for preparing nano ferriferrous oxide, by the way that ferric iron and ferrous will be contained
Mixed molysite and precipitating reagent, surfactant are mixed under inert gas protection carries out coprecipitation reaction, surfactant
The surface state of changeable crystal grain, avoids the aggregation of nucleus, so that being able to achieve during entire coprecipitation reaction to nucleus
The control of growth, and strengthen the formation of nucleus.Meanwhile surfactant can weaken combination work of the surface tension to particle of water
With further, by the way that the reunion between nano particle can be significantly reduced to filter cake progress frozen drying processing after pulp
Degree, to obtain the uniform nano ferriferrous oxide of grain diameter size distribution.As a result, using four oxidation three of this method preparation
The speed of iron is high, is suitble to industrialized production, and can prepare stable four oxygen of nanometer of uniform granular size, good sphericity, property
Change three-iron.
In addition, the method according to the above embodiment of the present invention for preparing nano ferriferrous oxide can also have following add
Technical characteristic:
In some embodiments of the invention, in step (1), the trivalent iron salt is selected from ferric nitrate, iron chloride, sulphur
At least one of sour iron.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, in step (1), the divalent iron salt is selected from ferrous nitrate, protochloride
At least one of iron, ferrous sulfate.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, in step (1), in the ferric salt solution ferric ion with it is described
The molar ratio of ferrous ion is 0.5-0.8:1 in divalent iron salt solution.It can further improve nano ferriferrous oxide as a result,
Quality.
In some embodiments of the invention, in step (2), in the mixed molysite solution ferric iron and ferrous iron from
Total concentration of son is 50-200g/L.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, the precipitating reagent is sodium hydroxide solution, 5- selected from 50-150g/L
At least one of ammonium hydroxide of 25wt%.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, the surfactant be in sodium citrate or enuatrol at least it
One.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, in step (2), the concentration of the surfactant is 0.001-
0.002mol/L.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, the mixed molysite solution and the precipitating reagent, described in step (2)
The mass ratio of surfactant is 1:1.5-2.0:0.05-0.1.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, in step (2), the temperature of the coprecipitation reaction is 20-30 DEG C, stirring
Speed is 800-1500r/min, pH 10.5-11.5, reaction time 1-4h.It can further improve the oxidation of nanometer four as a result,
The quality of three-iron.
In some embodiments of the invention, in step (3), the carrying out washing treatment is washing 3-5 times.It as a result, can be into
The quality of one step raising nano ferriferrous oxide.
In some embodiments of the invention, in step (4), the temperature of the frozen drying processing is -40--
30 DEG C, the time is 15-20 hours.It can further improve the quality of nano ferriferrous oxide as a result,.
In another aspect of the invention, the invention proposes a kind of suitable for the above-mentioned side for preparing nano ferriferrous oxide
The system of method, according to an embodiment of the invention, the system includes:
Mixing arrangement, the mixing arrangement have ferric salt solution entrance, divalent iron salt solution inlet and mixed molysite
Taphole；
There is mixed molysite solution inlet, precipitant inlet, surfactant to enter for codepostion device, the codepostion device
Mouth and reaction solution outlet, the mixed molysite solution inlet are connected with the mixed molysite taphole；
There is reaction solution entrance and dispersion liquid to export for dispersal device, the dispersal device, the reaction solution entrance with it is described
Reaction solution outlet is connected；
Filtration wash unit, the filtration wash unit have dispersion liquid entrance, cleaning solution entrance, filtrate (liquid and filter cake
Outlet, the dispersion liquid entrance are connected with dispersion liquid outlet；
Low temperature freeze-drying equipment, the low temperature freeze-drying equipment have filter cake entrance and the oxidation of nanometer four three after pulp
Iron outlet, filter cake entrance is connected with the filtered solid outlet after the pulp.
The system according to an embodiment of the present invention for preparing nano ferriferrous oxide, by the way that ferric iron and ferrous will be contained
Mixed molysite and precipitating reagent, surfactant are mixed under inert gas protection carries out coprecipitation reaction, surfactant
The surface state of changeable crystal grain, avoids the aggregation of nucleus, so that being able to achieve during entire coprecipitation reaction to nucleus
The control of growth, and strengthen the formation of nucleus.Meanwhile surfactant can weaken combination work of the surface tension to particle of water
With further, by the way that the reunion between nano particle can be significantly reduced to filter cake progress frozen drying processing after pulp
Degree, to obtain the uniform nano ferriferrous oxide of grain diameter size distribution.As a result, using four oxidation three of system preparation
The speed of iron is high, is suitble to industrialized production, and can prepare stable four oxygen of nanometer of uniform granular size, good sphericity, property
Change three-iron.
In addition, the system according to the above embodiment of the present invention for preparing nano ferriferrous oxide can also have following add
Technical characteristic:
In some embodiments of the invention, the codepostion device is closed heating reaction kettle.It as a result, can be further
Improve the quality of nano ferriferrous oxide.
In some embodiments of the invention, the filtration wash unit be in centrifuge or filter press at least it
One.It can further improve the quality of nano ferriferrous oxide as a result,.
In some embodiments of the invention, the low temperature freeze-drying equipment is vacuum freeze drier.It as a result, can be into
The quality of one step raising nano ferriferrous oxide.
In an additional aspect of the present invention, the invention proposes a kind of nano ferriferrous oxide, implementation according to the present invention
Example, the nano ferriferrous oxide are using the above-mentioned method for preparing nano ferriferrous oxide or to prepare nano ferriferrous oxide
What system was prepared.The nano ferriferrous oxide granule particle size distribution is uniform, average grain diameter 20-50nm.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing nano ferriferrous oxide；
Fig. 2 is the system structure diagram according to an embodiment of the invention for preparing nano ferriferrous oxide；
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 gained nano ferriferrous oxide of the embodiment of the present invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of 2 gained nano ferriferrous oxide of the embodiment of the present invention；
Fig. 5 is the scanning electron microscope (SEM) photograph of 3 gained nano ferriferrous oxide of the embodiment of the present invention；
Fig. 6 is the scanning electron microscope (SEM) photograph of 1 gained ferroso-ferric oxide of comparative example of the present invention；
Fig. 7 is the scanning electron microscope (SEM) photograph of 2 gained ferroso-ferric oxide of comparative example of the present invention；
Fig. 8 is the scanning electron microscope (SEM) photograph of 3 gained ferroso-ferric oxide of comparative example of the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements, unless otherwise restricted clearly.For those of ordinary skill in the art
For, the specific meanings of the above terms in the present invention can be understood according to specific conditions.
In one aspect of the invention, the invention proposes a kind of methods for preparing nano ferriferrous oxide, according to this hair
Bright embodiment, with reference to Fig. 1, this method comprises:
S100: ferric salt solution is mixed with divalent iron salt solution
In the step, ferric salt solution is mixed with divalent iron salt solution.Further, ferric salt solution and divalent
Specific trivalent iron salt and divalent iron salt type are not particularly restricted in iron salt solutions, and those skilled in the art can be according to reality
Border is selected, such as trivalent iron salt can be for selected from least one of ferric nitrate, iron chloride, ferric sulfate, ferrous iron
Salt can be for selected from least one of ferrous nitrate, frerrous chloride, ferrous sulfate.Inventors have found that the dissolution of above-mentioned molysite
Du Genggao is easier to participate in subsequent coprecipitation process.Further, ferric ion and divalent iron salt solution in ferric salt solution
The molar ratio of middle ferrous ion is not particularly restricted, and those skilled in the art can select according to actual needs, example
It can be such as 0.5-0.8:1, such as can be 0.5/0.6/0.7/0.8:1.Inventors have found that whether in ferric salt solution
The too high levels of ferrous ion, can all cause the waste of raw material in ferric ion or divalent iron salt solution.
S200: the resulting mixed molysite solution of S100 is mixed under inert gas protection with precipitating reagent, surfactant
Stirring carries out coprecipitation reaction
In the step, under inert gas protection with precipitating reagent, surfactant by the resulting mixed molysite solution of S100
It is mixed and carries out coprecipitation reaction.Inventors have found that by will containing ferric iron and ferrous mixed molysite and precipitating reagent,
Surfactant is mixed under inert gas protection carries out coprecipitation reaction, and the table of crystal grain can be changed in surfactant
Surface state avoids the aggregation of nucleus, so that being able to achieve the control to nucleus growth during entire coprecipitation reaction, and strengthens crystalline substance
The formation of core.Meanwhile surfactant can weaken combination of the surface tension to particle of water, change the surface electricity of particle
Position, so that the degree of scatter of particle is higher.Specifically, above-mentioned mixed molysite solution and precipitating reagent can be added with certain flow rate
In codepostion device, and a certain amount of surfactant is added during the reaction and is modified with the surface state to nucleus,
Filled with argon gas or nitrogen protection in codepostion device, coprecipitation reaction is carried out at certain reaction temperature, mixing speed and pH,
Obtain satisfactory reaction solution.
According to one embodiment of present invention, total concentration of ferric iron and ferrous ion is not in mixed molysite solution
It being particularly limited, those skilled in the art can select according to actual needs, such as can be 50-200g/L, specifically,
It such as can be 50g/L, 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L.Inventor
It was found that if in mixed molysite solution ferric iron and ferrous ion total excessive concentration, it is uneven to will lead to precipitating, if mixed
Total concentration of ferric iron and ferrous ion is too low in conjunction iron salt solutions, then can make final products low output, be not suitable for giving birth to
It produces.Further, the concrete type of precipitating reagent is not particularly restricted, and those skilled in the art can carry out according to actual needs
Selection, such as can be sodium hydroxide solution, at least one of the ammonium hydroxide of 5-25wt% selected from 50-150g/L, specifically,
The concentration of sodium hydroxide solution can be 50g/L, 70g/L, 90g/L, 110g/L, 130g/L, 150g/L, and the concentration of ammonium hydroxide can be with
For 5wt%, 10wt%, 15wt%, 20wt%, 25wt%.Inventors have found that sodium hydroxide activity is strong, it is miscellaneous that other will not be brought into
Matter is introduced into sediment, the speed of growth and uniformity coefficient of the adjustable particle of ammonium hydroxide.Further, surfactant can be
Selected from least one of sodium citrate or enuatrol, the concentration of surfactant can be 0.001-0.002mol/L, such as
It can be 0.001mol/L, 0.0012mol/L, 0.0014mol/L, 0.0016mol/L, 0.0018mol/L, 0.002mol/L.
Inventors have found that sodium citrate or enuatrol will not introduce other indissolubility impurity, if the concentration of surfactant is too low, point
It is bad to dissipate effect, if the excessive concentration of surfactant, will cause the waste of reagent, while can bring not to subsequent solution processing
Benefit influences.
Still another embodiment in accordance with the present invention, mixed molysite solution and precipitating reagent, surfactant mass ratio not
It is particularly limited, those skilled in the art can select according to actual needs, such as can be 1:1.5-2.0:0.05-
0.1, such as can be 1:1.5/1.6/1.7/1.8/1.9/2.0:0.05/0.06/0.07/0.08/0.09/0.1.Invention human hair
Existing, if mixed molysite solution quality is excessively high, the quality relative deficiency of precipitating reagent and surfactant can not precipitate completely, and
If mixed molysite solution quality is too low, the waste of precipitating reagent and surfactant will lead to.Further, above-mentioned co-precipitation is anti-
The actual conditions answered are not particularly restricted, and those skilled in the art can select according to actual needs, such as be co-precipitated
The temperature of reaction can be 20-30 DEG C, such as can be 20 DEG C, 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C, 30 DEG C, and mixing speed can be with
It for 800-1500r/min, such as can be 800r/min, 1000r/min, 1200r/min, 1400r/min, 1500r/min, pH
It can be 10.5-11.5, such as can be 10.5,10.7,10.9,11.1,11.3,11.5, the reaction time can be 1-4h, example
It such as can be 1h, 2h, 3h, 4h.Inventors have found that the temperature of coprecipitation reaction, mixing speed and pH value will affect final production
Pattern, reaction rate and the yield of object.
S300: the resulting reaction solution of S200 is dispersed, is filtered and carrying out washing treatment
In the step, the resulting reaction solution of S200 is dispersed, is filtered and carrying out washing treatment, filtrate and filter cake are obtained.It needs
It is noted that the concrete form that the resulting reaction solution of S200 is dispersed, filtered and washed is not particularly restricted, ability
Field technique personnel can select according to actual needs, such as can be dispersed using ultrasonic wave, can using centrifugation or
The form of filters pressing is filtered and washed.Further, the specific number of carrying out washing treatment is not particularly restricted, art technology
Personnel can select according to actual needs, such as can be determined according to the pH value of liquid after washing, the pH value of liquid after washing
When to 8 or so, washing terminates, specifically, in the actual operation process, can wash 3-5 times.
S400: frozen drying processing will be carried out after filter cake pulp
In the step, frozen drying processing will be carried out after filter cake pulp, to obtain nano ferriferrous oxide.Invention
People's discovery can use the sublimation of aqueous solution by using frozen drying, eliminate because surface tension to particle it
Between combination.By carrying out frozen drying processing to filter cake after pulp, the group between nano particle can be significantly reduced
Poly- degree, to obtain the uniform nano ferriferrous oxide of grain diameter size distribution.Further, frozen drying is handled
Actual conditions be not particularly restricted, those skilled in the art can select according to actual needs, such as cryogenic freezing
The temperature of drying process can be -40--30 DEG C, such as can be -40 DEG C, -38 DEG C, -36 DEG C, -34 DEG C, -32 DEG C, -30 DEG C,
Time can be 15-20 hours, such as can be 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours.Invention
People's discovery, if the temperature of frozen drying processing is excessively high, freezing efficiency is low, and if the temperature mistake of frozen drying processing
Low, then energy consumption increases；If the time of frozen drying processing is short, complete freezing cannot achieve, and if frozen drying
The time of processing is long, and energy consumption is high.
The method according to an embodiment of the present invention for preparing nano ferriferrous oxide, by the way that ferric iron and ferrous will be contained
Mixed molysite and precipitating reagent, surfactant are mixed under inert gas protection carries out coprecipitation reaction, surfactant
The surface state of changeable crystal grain, avoids the aggregation of nucleus, so that being able to achieve during entire coprecipitation reaction to nucleus
The control of growth, and strengthen the formation of nucleus.Meanwhile surfactant can weaken combination work of the surface tension to particle of water
With further, by the way that the reunion between nano particle can be significantly reduced to filter cake progress frozen drying processing after pulp
Degree, to obtain the uniform nano ferriferrous oxide of grain diameter size distribution.As a result, using four oxidation three of this method preparation
The speed of iron is high, is suitble to industrialized production, and can prepare stable four oxygen of nanometer of uniform granular size, good sphericity, property
Change three-iron.
In another aspect of the invention, the invention proposes a kind of suitable for the above-mentioned side for preparing nano ferriferrous oxide
The system of method, according to an embodiment of the invention, the system includes: mixing arrangement 100, codepostion device 200, dispersion with reference to Fig. 2
Device 300, filtration wash unit 400 and low temperature freeze-drying equipment 500.
According to an embodiment of the invention, there is mixing arrangement 100 ferric salt solution entrance 101, divalent iron salt solution to enter
Mouth 102 and mixed molysite taphole 103, and be suitable for mixing ferric salt solution with divalent iron salt solution, to be mixed
Close iron salt solutions.It is mixed specifically, ferric salt solution is carried out configuration according to certain molar ratio with divalent iron salt solution.Into
One step, specific trivalent iron salt and divalent iron salt type are not limited especially in ferric salt solution and divalent iron salt solution
System, those skilled in the art can select according to actual needs, such as trivalent iron salt can be for selected from ferric nitrate, chlorination
At least one of iron, ferric sulfate, divalent iron salt can in ferrous nitrate, frerrous chloride, ferrous sulfate at least it
One.Inventors have found that the solubility of above-mentioned molysite is higher, it is easier to participate in subsequent coprecipitation process.Further, trivalent iron salt is molten
The molar ratio of ferric ion and ferrous ion in divalent iron salt solution is not particularly restricted in liquid, those skilled in the art
It can be selected according to actual needs, such as can be 0.5-0.8:1, specifically, for example can be 0.5/0.6/0.7/
0.8:1.Inventors have found that whether ferrous ion in ferric ion or divalent iron salt solution in ferric salt solution
Too high levels can all cause the waste of raw material.
According to an embodiment of the invention, codepostion device 200 has mixed molysite solution inlet 201, precipitant inlet
202, surfactant entrance 203 and reaction solution outlet 204, mixed molysite solution inlet 201 and mixed molysite taphole 103
It is connected, and is suitable for mixing mixed molysite solution with precipitating reagent, surfactant and carries out coprecipitation reaction, to be reacted
Liquid.It should be noted that the concrete type of codepostion device is not particularly restricted, those skilled in the art can be according to reality
It is selected, such as can be closed heating reaction kettle.Inventors have found that by will be containing ferric iron and ferrous
Mixed molysite and precipitating reagent, surfactant are mixed under inert gas protection carries out coprecipitation reaction, surfactant
The surface state of changeable crystal grain, avoids the aggregation of nucleus, so that being able to achieve during entire coprecipitation reaction to nucleus
The control of growth, and strengthen the formation of nucleus.Meanwhile surfactant can weaken combination work of the surface tension to particle of water
With changing the surface potential of particle, so that the degree of scatter of particle is higher.Specifically, can be with certain flow rate by above-mentioned mixing
Iron salt solutions and precipitating reagent are added in codepostion device, and a certain amount of surfactant is added during the reaction to nucleus
Surface state modified, filled with argon gas or nitrogen protection in codepostion device, certain reaction temperature, mixing speed and
Coprecipitation reaction is carried out under pH, obtains satisfactory reaction solution.
According to one embodiment of present invention, total concentration of ferric iron and ferrous ion is not in mixed molysite solution
It being particularly limited, those skilled in the art can select according to actual needs, such as can be 50-200g/L, specifically,
It such as can be 50g/L, 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L.Inventor
It was found that if in mixed molysite solution ferric iron and ferrous ion total excessive concentration, it is uneven to will lead to precipitating, if mixed
Total concentration of ferric iron and ferrous ion is too low in conjunction iron salt solutions, then can make final products low output, be not suitable for giving birth to
It produces.Further, the concrete type of precipitating reagent is not particularly restricted, and those skilled in the art can carry out according to actual needs
Selection, such as can be sodium hydroxide solution, at least one of the ammonium hydroxide of 5-25wt% selected from 50-150g/L, specifically,
The concentration of sodium hydroxide solution can be 50g/L, 70g/L, 90g/L, 110g/L, 130g/L, 150g/L, and the concentration of ammonium hydroxide can be with
For 5wt%, 10wt%, 15wt%, 20wt%, 25wt%.Inventors have found that sodium hydroxide activity is strong, it is miscellaneous that other will not be brought into
Matter is introduced into sediment, the speed of growth and uniformity coefficient of the adjustable particle of ammonium hydroxide.Further, surfactant can be
Selected from least one of sodium citrate or enuatrol, the concentration of surfactant can be 0.001-0.002mol/L, such as
It can be 0.001mol/L, 0.0012mol/L, 0.0014mol/L, 0.0016mol/L, 0.0018mol/L, 0.002mol/L.
Inventors have found that sodium citrate or enuatrol will not introduce other indissolubility impurity, if the concentration of surfactant is too low, point
It is bad to dissipate effect, if the excessive concentration of surfactant, will cause the waste of reagent, while can bring not to subsequent solution processing
Benefit influences.
Still another embodiment in accordance with the present invention, mixed molysite solution and precipitating reagent, surfactant mass ratio not
It is particularly limited, those skilled in the art can select according to actual needs, such as can be 1:1.5-2.0:0.05-
0.1, such as can be 1:1.5/1.6/1.7/1.8/1.9/2.0:0.05/0.06/0.07/0.08/0.09/0.1.Invention human hair
Existing, if mixed molysite solution quality is excessively high, the quality relative deficiency of precipitating reagent and surfactant can not precipitate completely, and
If mixed molysite solution quality is too low, the waste of precipitating reagent and surfactant will lead to.Further, above-mentioned co-precipitation is anti-
The actual conditions answered are not particularly restricted, and those skilled in the art can select according to actual needs, such as be co-precipitated
The temperature of reaction can be 20-30 DEG C, such as can be 20 DEG C, 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C, 30 DEG C, and mixing speed can be with
It for 800-1500r/min, such as can be 800r/min, 1000r/min, 1200r/min, 1400r/min, 1500r/min, pH
It can be 10.5-11.5, such as can be 10.5,10.7,10.9,11.1,11.3,11.5, the reaction time can be 1-4h, example
It such as can be 1h, 2h, 3h, 4h.Inventors have found that the temperature of coprecipitation reaction, mixing speed and pH value will affect final production
Pattern, reaction rate and the yield of object.
According to an embodiment of the invention, dispersal device 300 has reaction solution entrance 301 and dispersion liquid outlet 302, reaction solution
Entrance 301 is connected with reaction solution outlet 204, and is suitable for reaction solution carrying out decentralized processing, to obtain dispersion liquid.It needs to illustrate
, the concrete type of dispersal device is not particularly restricted, and those skilled in the art can select according to actual needs.
According to an embodiment of the invention, filtration wash unit 400 has dispersion liquid entrance 401, cleaning solution entrance 402, filter
Liquid outlet 403 and filtered solid outlet 404, dispersion liquid entrance 401 are connected with dispersion liquid outlet 302, and are suitable for carrying out dispersion liquid
Filter, and washed using cleaning solution, to obtain filtrate and filter cake.It should be noted that the concrete kind of filtration wash unit
Type is not particularly restricted, and those skilled in the art can select according to actual needs, for example, can selected from centrifuge or
At least one of filter press.Further, the specific number of carrying out washing treatment is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, such as it can determine that the pH value of liquid is to 8 or so after washing according to the pH value of liquid after washing
When, washing terminates, specifically, in the actual operation process, can wash 3-5 times.
According to an embodiment of the invention, low temperature freeze-drying equipment 500 has four oxygen of filter cake entrance 501 and nanometer after pulp
Change three-iron outlet 502, filter cake entrance 501 is connected with filtered solid outlet 404 after pulp, and is suitable for filter cake after pulp carrying out low temperature cold
Be lyophilized it is dry, to obtain nano ferriferrous oxide.Inventors have found that can use aqueous solution by using frozen drying
Sublimation, eliminate because surface tension to the combination between particle.By carrying out cryogenic freezing to filter cake after pulp
It is dried, the reunion degree between nano particle can be significantly reduced, to obtain the uniform nanometer of grain diameter size distribution
Ferroso-ferric oxide.Further, the actual conditions of frozen drying processing are not particularly restricted, and those skilled in the art can
To be selected according to actual needs, such as the temperature of frozen drying processing can be -40--30 DEG C, such as can be -
40 DEG C, -38 DEG C, -36 DEG C, -34 DEG C, -32 DEG C, -30 DEG C, time can be 15-20 hour, such as can be 15 hours, 16 small
When, 17 hours, 18 hours, 19 hours, 20 hours.Inventors have found that being freezed if the temperature of frozen drying processing is excessively high
Low efficiency, and if the temperature of frozen drying processing is too low, energy consumption increase；If the time of frozen drying processing is short,
Then cannot achieve complete freezing, and if the time of frozen drying processing it is long, energy consumption is high.It should be noted that cryogenic freezing
The concrete type of drying device is not particularly restricted, and those skilled in the art can select according to actual needs, such as
It can be vacuum freeze drier.
The system according to an embodiment of the present invention for preparing nano ferriferrous oxide, by the way that ferric iron and ferrous will be contained
Mixed molysite and precipitating reagent, surfactant are mixed under inert gas protection carries out coprecipitation reaction, surfactant
The surface state of changeable crystal grain, avoids the aggregation of nucleus, so that being able to achieve during entire coprecipitation reaction to nucleus
The control of growth, and strengthen the formation of nucleus.Meanwhile surfactant can weaken combination work of the surface tension to particle of water
With further, by the way that the reunion between nano particle can be significantly reduced to filter cake progress frozen drying processing after pulp
Degree, to obtain the uniform nano ferriferrous oxide of grain diameter size distribution.As a result, using four oxidation three of system preparation
The speed of iron is high, is suitble to industrialized production, and can prepare stable four oxygen of nanometer of uniform granular size, good sphericity, property
Change three-iron.
In an additional aspect of the present invention, the invention proposes a kind of nano ferriferrous oxide, implementation according to the present invention
Example, the nano ferriferrous oxide are using the above-mentioned method for preparing nano ferriferrous oxide or to prepare nano ferriferrous oxide
What system was prepared.The nano ferriferrous oxide granule particle size distribution is uniform, average grain diameter 20-50nm.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
By trivalent iron salt iron nitrate solution and divalent iron salt ferrous nitrate solution according to ferric ion and ferrous iron from
The molar ratio of son is 0.5:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 50g/L；
By the sodium hydroxide solution precipitating reagent of mixed molysite solution and 50g/L, the surfactant citric acid that concentration is 0.001mol/L
Sodium is mixed under inert gas argon gas shielded according to mass ratio 1:1.5:0.05 carries out coprecipitation reaction, coprecipitation reaction
Temperature is 20 DEG C, mixing speed 800r/min, pH 10.5, reaction time 4h；By the resulting reaction solution of coprecipitation reaction
Dispersed using ultrasonic wave, be filtered and washed processing using centrifuge, washed 3 times, obtain filtrate and filter cake；By filter cake
Frozen drying processing is carried out after pulp, the temperature of frozen drying processing is -35 DEG C, time 18h, obtains average grain
Degree is the nano ferriferrous oxide of 30nm, and scanning electron microscope (SEM) photograph is as shown in Figure 3.
Embodiment 2
By trivalent iron salt ferric chloride solution and divalent iron salt solution of ferrous chloride according to ferric ion and ferrous ion
Molar ratio is 0.6:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 100g/L；It will mix
Close the sodium hydroxide solution of iron salt solutions and precipitating reagent 100g/L, the surfactant enuatrol that concentration is 0.0015mol/L is pressed
It is mixed under inert nitrogen gas protection according to mass ratio 1:1.8:0.07 and carries out coprecipitation reaction, the temperature of coprecipitation reaction
It is 25 DEG C, mixing speed 1100r/min, pH 11.0, reaction time 2h；The resulting reaction solution of coprecipitation reaction is used
Ultrasonic wave is dispersed, is filtered and washed processing using centrifuge, is washed 4 times, is obtained filtrate and filter cake；By filter cake pulp
Frozen drying processing is carried out afterwards, and the temperature of frozen drying processing is -30 DEG C, time 20h, and obtaining average particle size is
The nano ferriferrous oxide of 25nm, scanning electron microscope (SEM) photograph are as shown in Figure 4.
Embodiment 3
By trivalent iron salt ferrum sulfuricum oxydatum solutum and divalent iron salt ferrous sulfate solution according to ferric ion and ferrous ion
Molar ratio is 0.8:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 200g/L；It will mix
Close the sodium hydroxide solution of iron salt solutions and precipitating reagent 150g/L, the surfactant sodium citrate that concentration is 0.002mol/L is pressed
It is mixed under inert nitrogen gas protection according to mass ratio 1:2.0:0.1 and carries out coprecipitation reaction, the temperature of coprecipitation reaction
It is 30 DEG C, mixing speed 1500r/min, pH 11.5, reaction time 1h；The resulting reaction solution of coprecipitation reaction is used
Ultrasonic wave is dispersed, is filtered and washed processing using filter press, is washed 5 times, is obtained filtrate and filter cake；By filter cake pulp
Frozen drying processing is carried out afterwards, and the temperature of frozen drying processing is -40 DEG C, time 15h, and obtaining average particle size is
The nano ferriferrous oxide of 20nm, scanning electron microscope (SEM) photograph are as shown in Figure 5.
Comparative example 1 is dried at room temperature
By trivalent iron salt iron nitrate solution and divalent iron salt ferrous nitrate solution according to ferric ion and ferrous ion
Molar ratio is 0.5:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 50g/L；It will mix
Close the sodium hydroxide solution precipitating reagent of iron salt solutions and 50g/L, the surfactant sodium citrate that concentration is 0.001mol/L is pressed
It is mixed under inert gas argon gas shielded according to mass ratio 1:1.5:0.05 and carries out coprecipitation reaction, the temperature of coprecipitation reaction
It is 20 DEG C, mixing speed 800r/min, pH 10.5, reaction time 4h；The resulting reaction solution of coprecipitation reaction is used
Ultrasonic wave is dispersed, is filtered and washed processing using centrifuge, is washed 3 times, is obtained filtrate and filter cake；By filter cake pulp
Be dried at room temperature afterwards, obtain average particle size be 50nm ferroso-ferric oxide, scanning electron microscope (SEM) photograph as shown in fig. 6,
As seen from the figure, resulting ferroso-ferric oxide has apparent agglomeration, and particle degree of scatter is poor.
Surfactant is not added in comparative example 2
By trivalent iron salt ferric chloride solution and divalent iron salt solution of ferrous chloride according to ferric ion and ferrous ion
Molar ratio is 0.6:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 100g/L；It will mix
It closes iron salt solutions and is mixed under inert nitrogen gas protection with the sodium hydroxide solution of precipitating reagent 100g/L according to mass ratio 1:1.8
Stirring carries out coprecipitation reaction, and the temperature of coprecipitation reaction is 25 DEG C, mixing speed 1100r/min, pH 11.0, when reaction
Between be 2h；The resulting reaction solution of coprecipitation reaction is dispersed using ultrasonic wave, place is filtered and washed using centrifuge
Reason washes 4 times, obtains filtrate and filter cake；Frozen drying processing will be carried out after filter cake pulp, frozen drying processing
Temperature be -30 DEG C, time 20h, obtain average particle size be 35nm ferroso-ferric oxide, scanning electron microscope (SEM) photograph as shown in fig. 7, by
Figure is it is found that the degree of scatter of particle is bad.
Comparative example 3 is dry at room temperature, surfactant is not added
By trivalent iron salt ferrum sulfuricum oxydatum solutum and divalent iron salt ferrous sulfate solution according to ferric ion and ferrous ion
Molar ratio is 0.8:1 mixing, and the total concentration for obtaining ferric iron and ferrous ion is the mixed molysite solution of 200g/L；It will mix
It closes iron salt solutions and is mixed under inert nitrogen gas protection with the sodium hydroxide solution of precipitating reagent 150g/L according to mass ratio 1:2.0
Stirring carries out coprecipitation reaction, and the temperature of coprecipitation reaction is 30 DEG C, mixing speed 1500r/min, pH 11.5, when reaction
Between be 1h；The resulting reaction solution of coprecipitation reaction is dispersed using ultrasonic wave, place is filtered and washed using filter press
Reason washes 5 times, obtains filtrate and filter cake；It will be dried at room temperature after filter cake pulp, obtaining average particle size is 40nm
Ferroso-ferric oxide, scanning electron microscope (SEM) photograph is as shown in figure 8, as seen from the figure, the degree of scatter of particle is bad.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing nano ferriferrous oxide characterized by comprising
(1) ferric salt solution is mixed with divalent iron salt solution；
(2) the resulting mixed molysite solution of step (1) is mixed under inert gas protection with precipitating reagent, surfactant
Carry out coprecipitation reaction；
(3) step (2) resulting reaction solution dispersed, filtered and carrying out washing treatment, obtain filtrate and filter cake；
(4) frozen drying processing will be carried out after the filter cake pulp, to obtain nano ferriferrous oxide.
2. the method according to claim 1, wherein the trivalent iron salt is selected from nitric acid in step (1)
At least one of iron, iron chloride, ferric sulfate；
It is optional, in step (1), the divalent iron salt be in ferrous nitrate, frerrous chloride, ferrous sulfate at least it
One；
Optional, in step (1), ferric ion and ferrous iron in the divalent iron salt solution in the ferric salt solution
The molar ratio of ion is 0.5-0.8:1.
3. method according to claim 1 or 2, which is characterized in that in step (2), three in the mixed molysite solution
Total concentration of valence iron and ferrous ion is 50-200g/L；
Optional, in step (2), the precipitating reagent is the ammonium hydroxide of sodium hydroxide solution selected from 50-150g/L, 5-25wt%
At least one of；
Optional, in step (2), the surfactant is selected from least one of sodium citrate or enuatrol；
Optional, in step (2), the concentration of the surfactant is 0.001-0.002mol/L；
Optional, in step (2), the mass ratio of the mixed molysite solution and the precipitating reagent, the surfactant is
1:1.5-2.0:0.05-0.1；
Optional, in step (2), the temperature of the coprecipitation reaction is 20-30 DEG C, mixing speed 800-1500r/min,
PH is 10.5-11.5, reaction time 1-4h.
4. the method according to claim 1, wherein the carrying out washing treatment is washing 3-5 times in step (3).
5. the method according to claim 1, wherein in step (4), the temperature of the frozen drying processing
Degree is -40--30 DEG C, and the time is 15-20 hours.
6. a kind of system suitable for the method for any of claims 1-5 for preparing nano ferriferrous oxide, special
Sign is, comprising:
Mixing arrangement, the mixing arrangement have ferric salt solution entrance, divalent iron salt solution inlet and mixed molysite solution
Outlet；
Codepostion device, the codepostion device have mixed molysite solution inlet, precipitant inlet, surfactant entrance and
Reaction solution outlet, the mixed molysite solution inlet are connected with the mixed molysite taphole；
There is reaction solution entrance and dispersion liquid to export for dispersal device, the dispersal device, and the reaction solution entrance is reacted with described
Liquid outlet is connected；
There is dispersion liquid entrance, cleaning solution entrance, filtrate (liquid and filter cake to go out for filtration wash unit, the filtration wash unit
Mouthful, the dispersion liquid entrance is connected with dispersion liquid outlet；
Low temperature freeze-drying equipment, the low temperature freeze-drying equipment go out with filter cake entrance after pulp and nano ferriferrous oxide
Mouthful, filter cake entrance is connected with the filtered solid outlet after the pulp.
7. system according to claim 6, which is characterized in that the codepostion device is closed heating reaction kettle.
8. system according to claim 6 or 7, which is characterized in that the filtration wash unit is selected from centrifuge or pressure
At least one of filter.
9. system according to claim 6, which is characterized in that the low temperature freeze-drying equipment is vacuum freeze drying
Machine.
10. a kind of nano ferriferrous oxide, which is characterized in that the nano ferriferrous oxide is appointed using in claim 1-5
The oxidation of preparation nanometer four described in any one of method or claim 6-9 of nano ferriferrous oxide three is prepared described in one
What the system of iron was prepared.
Priority Applications (1)
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