CN109879327A - It is a kind of to prepare Fe using metal oxide oxidation catalyst3O4Method - Google Patents
It is a kind of to prepare Fe using metal oxide oxidation catalyst3O4Method Download PDFInfo
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- CN109879327A CN109879327A CN201910074047.5A CN201910074047A CN109879327A CN 109879327 A CN109879327 A CN 109879327A CN 201910074047 A CN201910074047 A CN 201910074047A CN 109879327 A CN109879327 A CN 109879327A
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Abstract
It is a kind of to prepare Fe using metal oxide catalyst3O4Method, sequentially include the following steps: to Fe2+Metal M oxide powder is added in solution and disperses, aqueous slkali is then added and obtains mixed solution, which carries out hydro-thermal reaction, obtains containing Fe3O4The suspension of particle isolates product Fe3O4；The metal M oxide is CuO, Cu2O, CoO or Co3O4At least one of.Compared to traditional preparation methods, the present invention utilizes CuO, Cu2O, CoO, Co3O4Deng oxidizer again for catalyst, is not needed, from Fe under alkaline condition2+The high-purity micron-sized octahedral Fe of monocrystalline of salting liquid one-step synthesis3O4, the preparation method simple process, efficient quick are at low cost.
Description
Technical field
The present invention relates to a kind of preparation methods of iron compound, and in particular to a kind of to be prepared using metal oxide oxidation catalyst
Fe3O4Method.
Background technique
The iron oxide of Chinese annual pickling millions of tons, causes largely to contain Fe2+Pickle liquor." steel and iron industry water is dirty
Contaminate object discharge standard " (GB 13456.2012) U, the content of the total iron of clear stipulaties is less than 10mg/L.However, general steel acid
It washes in waste liquid, there are the Fe that concentration is greater than 100g/L2+Ion, can not direct emission, need harmless treatment.But it is arranged as waste liquid
It puts, a large amount of Fe2+It is wasted, not only causes huge environmental pressure and a kind of economic loss.Therefore, by the Fe in waste liquid2 +It is converted to the product of economic value, is urgent need.
Fe is prepared by raw material of pickle liquor3O4It is a kind of recycling Fe2+Approach.Since Fe content is higher, Fe3O4It can be with
Ironmaking directly is melted down, in addition, having application in fields such as pigment, magnetic material, medicine bioengineering and catalysis, is worth higher.It is newest
It was found that the octahedral Fe of monocrystalline3O4Play a significant role in fuel cell field.
In conventional hydrothermal method or coprecipitation, pass through Fe2+Ion, which sets out, directly prepares Fe3O4, it usually needs oxidant, or
Add the Fe centainly matched3+Salt.To obtain pure phase Fe3O4, the supply amount and Fe of oxidant2+With Fe3+Ratio need tight adjust
Control.If being unable to control Fe2+The oxidation process of ion, FeOOH, Fe in product2O3Equal impurity contents are higher, and post-processing is difficult,
And greatly increase economic cost.Therefore, conventional method is in practical Fe2+Recycling in terms of difficulty it is larger.
Inventor has found in the research of early period, to Fe2+It is added in solution and contains Cu2+、Ni2+And Co2+Deng salting liquid,
High-purity Fe can efficiently be prepared3O4, as described in patent document CN 108751262A, this method is significantly simple compared with conventional method
Preparation process is changed.Subsequent research further explores Cu2+、Ni2+And Co2+Deng salt preparation Fe3O4Mechanism, in this base
New preparation method is proposed on plinth.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of simple process, high income, product purity high preparation Fe3O4
Method.
Technical solution is as follows:
It is a kind of to prepare Fe using metal oxide oxidation catalyst3O4Method, key is to sequentially include the following steps:
To Fe2+Metal M oxide powder is added in solution and disperses, aqueous slkali is then added and obtains mixed solution, this is mixed
It closes solution and carries out hydro-thermal reaction, obtain containing Fe3O4The suspension of particle isolates product Fe3O4；
The metal M oxide is CuO, Cu2O, CoO or Co3O4At least one of.
As optimal technical scheme, M element and metallic element in the mixed solution in above-mentioned metal M oxide powder
Atomic percent is M/ (M+Fe)=0.1~50at.%.
As optimal technical scheme, M element and metallic element in the mixed solution in above-mentioned metal M oxide powder
Atomic percent is M/ (M+Fe)=1~10at.%.
As optimal technical scheme, the temperature of above-mentioned hydro-thermal reaction is 100~200 DEG C.
As optimal technical scheme, the temperature of above-mentioned hydro-thermal reaction is 120~150 DEG C.
As optimal technical scheme, above-mentioned the hydro-thermal reaction time is 0.5~48h.
As optimal technical scheme, above-mentioned the hydro-thermal reaction time is 4~6h.
As optimal technical scheme, above-mentioned Fe2+Fe in solution2+Concentration be 0.01~5mol/L.
As optimal technical scheme, OH in above-mentioned aqueous slkali-Concentration be 0.2~8mol/L.
Detailed description of the invention
Fig. 1 is sample X-ray diffraction (XRD) map of reference examples preparation；
Fig. 2 is the sample XRD spectrum that section Example method is prepared, in which: (a) embodiment 8；(b) embodiment 9
(on) and embodiment 5 (under)；(c) embodiment 10；(d) embodiment 11；
Fig. 3 is typical scan electron microscope (SEM) picture and energy disperse spectroscopy that sample is made by catalyst of copper oxide
(EDS) result is swept in face.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
(1) Fe3O4Preparation
It is a kind of to prepare Fe using metal oxide catalyst3O4Method, the steps include:
To Fe2+The oxide powder of metal M is added in solution and dispersion, additive amount are, with M in metal M oxide powder
Element and the atomic percentage for mixing metallic element total in suspension, M/ (M+Fe)=0.1~50at.%；
Then stirring is added aqueous slkali and obtains mixed solution, which carries out hydro-thermal reaction, obtains containing Fe3O4?
The suspension of grain, isolates product Fe3O4。
The oxide of metal M is CuO, Cu2O, CoO or Co3O4One or more of combination.Product can by from
The modes such as the heart, membrane filtration, Magnetic filter separate, and when using CuO or CuO as catalyst, since its is nonmagnetic, use Magnetic filter
It more convenient can remove it.
Table 1 gives reactant dosage, concentration and the reaction condition of Examples 1 to 20 and reference examples, wherein each to implement
The oxide powder of metal M is added as catalyst in example, and reference examples do not add the oxide of metal M, remaining step is constant.
Wherein, hydro-thermal reaction carries out in a kettle, and reaction temperature is 100~200 DEG C, and the hydro-thermal reaction time is 0.5~48h.Experiment
It was found that the reaction time can suitably shorten when reaction temperature is higher, the additive amount of the oxide powder of metal M can also be reduced suitably.
Therefore, according to scheduled reaction temperature and time, it can adjust the dosage of the oxide powder catalyst of addition metal M.
The Fe2+Solution can be the inorganic salts such as frerrous chloride, ferrous sulfate and its salt-mixture, it is possible to use citric acid
The organic salts such as salt, acetate and its salt-mixture.Fe2+Fe in solution2+Concentration be 0.01~5mol/L.
NaOH, KOH, LiOH etc. common inorganic base can be used in aqueous slkali, it is possible to use such as ammonium hydroxide and polyethyleneimine
(PEI) organic bases such as；In addition, can also be used in mixed way inorganic base and organic base, when using PEI, dispersing agent both can be used as
It itself is base reagent again to help metal oxide dispersion in the reaction system.OH in aqueous slkali-Concentration or completely ionization
Theoretical concentration be 0.2~8mol/L.All reagents are purchased from Shanghai Aladdin biochemical technology limited liability company.
Specifically, by taking embodiment 5 as an example, Fe is prepared3O4Process are as follows:
Reaction reagent prepares: taking the FeSO of 0.02mol4, it is dissolved in 100ml water, configures the ferrous sulfate solution of 0.2M
It is spare；The NaOH for taking 0.1mol is dissolved in 100ml water, and the NaOH solution for configuring 1M is spare；Take CuO powder spare.
Prepare Fe3O4Process: 20ml FeSO is taken4Hydrothermal reaction kettle is added in solution, and 0.03mmolCuO powder is then added,
It is dispersed with stirring, then 10ml NaOH solution is added dropwise while stirring.Hydrothermal reaction kettle is covered, is put into constant temperature oven, in 120 DEG C
Lower reaction 1h, is down to room temperature, obtains black suspension.
After the reaction was completed, solid particle is filtered to isolate from above-mentioned black suspension using magnetic filter, washing is done
It is dry, obtain product Fe3O4。
The experimentation of reference examples is similar, but does not add CuO powder in ferrous sulfate solution, be added NaOH solution after in
4h is reacted at 150 DEG C, product is green after reaction, and product rapid oxidation is Chinese red during collection.
The reactant and reaction condition of table 1 different embodiments and reference examples
Note: * OH-Concentration refers to existing OH in aqueous slkali-And potential theoretically ionizable OH out-Concentration,
Such as NH in ammonia spirit3·H2The concentration of O.
(2) Characterization of The Products
X-ray diffraction (XRD) analysis, scanning electron microscope (SEM) analysis and energy depressive spectroscopy (EDS) elemental analysis are
Common crystal characterization method, wherein XRD spectrum is capable of the crystal structure of reaction test sample, by scanning electron microscope
(SEM) sample topography can be intuitively observed, content can be formed to sample element using energy depressive spectroscopy (EDS) and detected.
The typical XRD spectrum that sample is prepared using the above method is as depicted in figs. 1 and 2.Fig. 1 is prepared into for reference examples
The sample arrived, product is essentially FeOOH as seen from the figure.Changed according to coloured product in reaction process, thus it is speculated that reaction terminates to generate
Object is the Fe (OH) of green2, rapid oxidation is the FeOOH of Chinese red during collection.
It is respectively the XRD spectrum using the sample of following preparation method preparation: embodiment 8 (a) in Fig. 2；(b) embodiment 9
(on) and embodiment 5 (under)；(c) embodiment 10；(d) embodiment 11.By map it is found that can be prepared under each process conditions
Fe3O4Crystal.With CuO, Cu2O is catalyst, product Fe3O4Purity is higher.With CoO and Co3O4It is isolated for catalyst
Contain micro impurity in product.
The comparison that sample is made with embodiment in reference examples shows that a small amount of CuO, Cu is added2O, CoO or Co3O4Powder enters anti-
Answer system, i.e., Fe under changeable alkaline condition2+The Direction of Reaction, make its towards generate Fe3O4The direction of crystal carries out, and shows
The catalytic action of these types of oxidate powder.Compared to traditional preparation methods, this method preparation process is simple, and reaction system is without tight
Lattice control is oxidation or reducing atmosphere, to the adaptable of reaction condition.
Be made sample typical SEM pictures (a) and EDS map (b, c, d, e) as shown in figure 3, the sample by embodiment 5
Method is made.(b) in Fig. 3, (c), (d) are respectively that figure is swept in the face of element O, Fe, Cu, and light represents respective element in figure
Distributed areas.It can be seen that Fe obtained3O4Particle is regular octahedron monocrystalline, and particle size is in several hundred nanometers to several microns of models
It encloses.Constituent content analysis is the results show that Cu constituent content is very low in product, Cu/ (Cu+Fe)=0.63at.%.
The utility model has the advantages that the present invention utilizes CuO, Cu compared to traditional preparation methods2O、CoO、Co3O4Deng for catalyst, no
Oxidizer again is needed, from Fe under alkaline condition2+The high-purity micron-sized octahedral Fe of monocrystalline of salting liquid one-step synthesis3O4,
The preparation method simple process, efficient quick, it is at low cost.In addition, CuO, Cu2O etc. does not have magnetism, and Fe3O4It is a kind of paramagnetic
Property material can pass through the isolated Fe of magnetic recovery in scale application3O4, thus with before good industrial application
Scape is a kind of innoxious, recycling processing method for industrial iron and steel pickling waste liquid.
Finally, it should be noted that foregoing description is only the preferred embodiment of the present invention, the ordinary skill people of this field
Member under the inspiration of the present invention, without prejudice to the purpose of the present invention and the claims, can make multiple similar tables
Show, such transformation is fallen within the scope of protection of the present invention.
Claims (9)
1. a kind of prepare Fe using metal oxide oxidation catalyst3O4Method, it is characterised in that sequentially include the following steps:
To Fe2+Metal M oxide powder is added in solution and disperses, aqueous slkali is then added and obtains mixed solution, the mixing is molten
Liquid carries out hydro-thermal reaction, obtains containing Fe3O4The suspension of particle isolates product Fe3O4；
The metal M oxide is CuO, Cu2O, CoO or Co3O4At least one of.
2. a kind of utilization metal oxide oxidation catalyst according to claim 1 prepares Fe3O4Method, it is characterised in that: it is described
In metal M oxide powder in M element and the mixed solution atomic percent of metallic element be M/ (M+Fe)=0.1~
50at.%.
3. a kind of utilization metal oxide oxidation catalyst according to claim 2 prepares Fe3O4Method, it is characterised in that: it is described
In metal M oxide powder in M element and the mixed solution atomic percent of metallic element be M/ (M+Fe)=1~
10at.%.
4. a kind of utilization metal oxide oxidation catalyst according to any one of claims 1 to 3 prepares Fe3O4Method, it is special
Sign is: the temperature of the hydro-thermal reaction is 80~300 DEG C.
5. a kind of utilization metal oxide oxidation catalyst according to claim 4 prepares Fe3O4Method, it is characterised in that: it is described
The temperature of hydro-thermal reaction is 120~150 DEG C.
6. a kind of utilization metal oxide oxidation catalyst according to claim 4 prepares Fe3O4Method, it is characterised in that: it is described
The hydro-thermal reaction time is 0.5~48h.
7. a kind of utilization metal oxide oxidation catalyst according to claim 6 prepares Fe3O4Method, it is characterised in that: it is described
The hydro-thermal reaction time is 4~6h.
8. a kind of utilization metal oxide oxidation catalyst according to any one of claims 1 to 3 prepares Fe3O4Method, it is special
Sign is: the Fe2+Fe in solution2+Concentration be 0.01~5mol/L.
9. a kind of utilization metal oxide oxidation catalyst according to any one of claims 1 to 3 prepares Fe3O4Method, it is special
Sign is: OH in the aqueous slkali-Concentration be 0.2~8mol/L.
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| CN101445277A (en) * | 2008-11-14 | 2009-06-03 | 东北大学 | Nano-crystalline Fe*O* particles with high absorption capacity and preparation method thereof |
| CN102516822A (en) * | 2011-11-04 | 2012-06-27 | 昆明理工大学 | Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof |
| CN103030169A (en) * | 2012-12-26 | 2013-04-10 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
| CN103241776A (en) * | 2012-02-11 | 2013-08-14 | 中国科学院合肥物质科学研究院 | Ferroferric oxide nano-composite particle and preparation method and applications thereof |
| CN108375574A (en) * | 2018-02-01 | 2018-08-07 | 上海工程技术大学 | Ferroso-ferric oxide supports negative nickel carburization zone nanotube and its preparation method and application |
| CN108751262A (en) * | 2018-06-14 | 2018-11-06 | 重庆科技学院 | It is a kind of to prepare Fe3O4Method |
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- 2019-01-25 CN CN201910074047.5A patent/CN109879327B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003090927A1 (en) * | 2002-04-24 | 2003-11-06 | Beijing University Of Chemical Technology | Magnetic superfine solid acid catalyst with double shell structure and process for preparing |
| CN101445277A (en) * | 2008-11-14 | 2009-06-03 | 东北大学 | Nano-crystalline Fe*O* particles with high absorption capacity and preparation method thereof |
| CN102516822A (en) * | 2011-11-04 | 2012-06-27 | 昆明理工大学 | Surface-functionalized Fe3O4 nanoparticles as well as preparation method and application thereof |
| CN103241776A (en) * | 2012-02-11 | 2013-08-14 | 中国科学院合肥物质科学研究院 | Ferroferric oxide nano-composite particle and preparation method and applications thereof |
| CN103030169A (en) * | 2012-12-26 | 2013-04-10 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
| CN108375574A (en) * | 2018-02-01 | 2018-08-07 | 上海工程技术大学 | Ferroso-ferric oxide supports negative nickel carburization zone nanotube and its preparation method and application |
| CN108751262A (en) * | 2018-06-14 | 2018-11-06 | 重庆科技学院 | It is a kind of to prepare Fe3O4Method |
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