CN113173604A - Method for preparing nano iron and oxide thereof by taking sintering ash as raw material - Google Patents
Method for preparing nano iron and oxide thereof by taking sintering ash as raw material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 54
- 238000005245 sintering Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000005406 washing Methods 0.000 claims abstract description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000007885 magnetic separation Methods 0.000 claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 16
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 70
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 23
- 238000001914 filtration Methods 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C01G49/04—Ferrous oxide [FeO]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to the technical field of nano material preparation, in particular to a method for preparing nano iron and oxide thereof by taking sintered ash as a raw material. The method extracts the nano ferric oxide from the sintering ash of the steel rabbet, has the advantages of easily obtained reaction raw materials, lower cost, simple and easily controlled reaction equipment, shorter reaction time and no pollution to the environment; the purity of the extracted nano iron oxide is improved by creatively adopting a mode of combining water washing, magnetic separation and alkali washing; in the step of extracting the nano ferric oxide, most soluble impurities and nonmagnetic substances are firstly washed away by water to save NaOH, and the washing after alkaline washing selects a leaching mode to save water resources.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a method for preparing nano iron and oxide thereof by taking sintered ash as a raw material.
Background
Iron is one of the most abundant metal elements in the earth's crust, and in general, mobile dislocations exist between metal iron atoms, but when the size of metal iron is reduced to the nano-scale, the grain size is too small to generate dislocations, and stress generated upon compression is greater, so that the metal iron becomes rather hard. The nano iron not only has high strength and hardness, but also has good plasticity and toughness, because the nano iron has a large interface, the atomic arrangement of the interface is quite disordered, and atoms are easy to migrate under the condition of external force deformation, so that the nano iron material shows some novel mechanical properties.
The nano iron particles are generally black, have strong infrared ray absorption capacity and have a large ratio of absorption rate to heat capacity. The thermal property difference between the nano iron and the bulk material comes from the surface effect or quantum effect, and the melting point, initial sintering temperature and crystallization temperature of the nano iron are usually much lower than those of the conventional powder because the close neighbor coordination of the surface atoms of the nano iron particles is incomplete, not only has more than surface atoms, but also has higher surface energy and activity, and the volume of the nano iron particles is much smaller than that of the bulk material, so that the internal energy required to be increased when the nano iron is melted is much smaller than that of the conventional powder, and therefore, the melting point is sharply reduced. Therefore, the property of the nano iron powder has practical application value.
The nano iron and the oxide thereof are in the nano scale level, have small size, large specific surface area, strong reducing capability and high reaction activity, and the particles have the basic effects of nano materials such as surface effect, small size effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the nano iron and the oxide thereof show some brand new physical and chemical properties and have wide application prospect. The nano-structured iron and the oxide thereof have a nano effect, show a plurality of exotic characteristics, have larger development potential and wide application space, and are good functional materials. However, most of the existing preparation methods of nano iron and its oxides have the problems of complex process, high cost, low yield and the like.
The iron ore sintering is used as an important process for preparing iron and steel production furnace burden, flue gas generated by sintering is collected by an electric precipitator to form sintering ash, the iron, potassium, lead and carbon contents of the sintering ash are high, and the main chemical component is Fe2O3、Fe3O4、CaO、C、SiO2、KCl、NaCl、PbCl2And PbOHCl and the like, the sintering ash yield accounts for about 2-4% of the sintering ore yield, and according to data, the sintering ash generated by China every year is about thousands of tons. And because the sintering ash contains a large amount of harmful elements such as potassium, sodium, copper, zinc, lead and the like which are harmful to steel smelting, the conventional treatment method is adopted, so that the harmful elements cannot be removed, and the elements are enriched in the blast furnace, thereby seriously influencing the normal production of the blast furnace. The accumulation treatment and the landfill treatment of the dust can cause the waste of resources and the environmental pollution. Therefore, the sintered ash is used as a raw material to prepare the nano iron and the oxide thereof, and the method is economical and practical and has wide sources.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the method for preparing the nano iron and the oxide thereof by taking the sintering ash as the raw material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing nano iron and its oxide by using sintered ash as raw material includes preparing nano iron oxide firstly, its preparation method includes the following operation steps:
1) taking a certain amount of sintering ash, washing with water, and separating out primary solid matters through magnetic separation;
2) washing the magnetically separated primary solid matters with water again, performing magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and keeping secondary magnetically separated solid matters;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable to obtain a primary purified solid matter;
4) sequentially carrying out alkaline washing, suction filtration and water leaching on the primary purified solid substance prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkaline washing, suction filtration and water leaching for multiple times until the conductivity is stable to obtain a purified solid substance;
5) drying the purified solid substance prepared in the step 4) to obtain the nano ferric oxide.
In order to obtain the nano-iron, some embodiments of the invention further include an operation step of reducing the nano-iron oxide, including subjecting the nano-iron oxide prepared in the step 5) to a reduction treatment in a mixed gas environment of a reducing gas and a stabilizing gas.
In order to further improve the purity of the prepared nano iron and the oxide thereof, the water adopted in the preparation method is preferably deionized water. Further preferably, the ratio of the sintering ash to the deionized water in the step 1) is 1: 0.6-8 times of cleaning, and 1-10 times of cleaning.
Optionally, in some embodiments of the present invention, step 4) is performed with an alkaline wash with NaOH solution; further preferably, the concentration of the NaOH solution is 0.1-0.6 mol/L.
In order to control the reduction effect on the nano iron oxide and the composition, the uniformity of the particle size distribution and the dispersibility of the obtained nano iron and the oxide thereof, in some embodiments of the present invention, the compositions of the reducing gas and the stabilizing gas are optimally selected, and the temperature of the reduction process is controlled in a programmed manner, specifically, optionally, the reducing gas in the mixed gas is: h2CO and/or NH3The volume content is 1-45%; the stabilizing gas being N2Ar and/or He. Optionally, heating to 280-480 ℃ at a heating rate of 1-20 ℃/min, and reducing the nano iron oxide into nano ferroferric oxide; heating to 400-700 ℃, and reducing the nano ferric oxide into nano ferrous oxide; heating to 500-1100 ℃, and reducing the nano iron into nano iron; the reaction time is 1-300 min.
The invention extracts the nanometer ferric oxide from the sintering ash of the steel rabbet, and has the advantages of easily obtained reaction raw materials and lower cost. The reaction equipment is simple and easy to control, the reaction time is short, and no pollution is caused to the environment; the purity of the extracted nano iron oxide is improved by creatively adopting a mode of combining water washing, magnetic separation and alkali washing; in the step of extracting the nano ferric oxide, most soluble impurities and nonmagnetic substances are firstly washed away by water to save NaOH, and the washing after alkaline washing selects a leaching mode to save water resources.
In addition, the invention reduces the nano iron oxide by a temperature programming reduction method, and then changes experimental conditions such as used reducing gas and content thereof, temperature, heating rate, reaction time and the like, so that various nano oxides or nano iron with better dispersity can be obtained.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the present invention is not limited to the examples in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, the reagents and materials used in the following examples are commercially available and the source of the sintering ash used is the dust particles collected by the sintering machine head flue gas electric dust collector during the iron ore sintering process in the steel plant.
Example 1
A method for preparing nano ferroferric oxide by taking sintered ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture 8 times in a proportion of 1, extracting iron oxide by electromagnetic separation in each washing, and mixing the solid matters magnetically separated in each time to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.1 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5), putting the nano iron oxide into an adsorption tube, and filling reductive mixed gas into the adsorption tube, wherein the mixed gas consists of H2And He, H2The content is 1-45%, the temperature is raised to 380 ℃ under the condition of the temperature rise rate of 4 ℃/min, and the reaction is carried out for 30 min.
The nano ferroferric oxide obtained in the embodiment 1 of the invention has the average particle size of 98.62nm, good dispersibility and average particle size.
Example 2
A method for preparing nano ferrous oxide by taking sintered ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture for 6 times at a ratio of 2.5, wherein iron oxide is obtained by electromagnetic separation in each washing, and the solid matters obtained by each magnetic separation are mixed to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.2 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5), putting the nano iron oxide into an adsorption tube, and filling reductive mixed gas into the adsorption tube, wherein the mixed gas consists of CO and N2，H2The content is 15 percent, the temperature is increased to 550 ℃ under the condition of the temperature increase rate of 8 ℃/min, and the reaction is carried out for 100 min.
The average particle size of the nano ferrous oxide sample obtained in the embodiment 2 of the invention is 129.48nm, the product has good dispersibility and the average particle size.
Example 3
A method for preparing nano iron by taking sintering ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture for 6 times in a ratio of 3, wherein iron oxide is obtained by electromagnetic separation in each washing, and the solid matters magnetically separated in each time are mixed to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.3 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5), putting the nano iron oxide into an adsorption tube, and filling reductive mixed gas into the adsorption tube, wherein the mixed gas consists of H2And He, H2The content is 35 percent, the temperature is increased to 850 ℃ under the condition of the temperature increase rate of 15 ℃/min, and the reaction is carried out for 100 min.
The average particle size of the nano-iron sample obtained in the embodiment 3 of the invention is 223.51nm, the product has good dispersibility and the average particle size.
Example 4
A method for preparing nano ferrous oxide by taking sintered ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture for 5 times in a proportion of 5, wherein iron oxide is obtained by electromagnetic separation in each washing, and the solid matters magnetically separated in each time are mixed to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.4 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5), putting the nano iron oxide into an adsorption tube, and filling reductive mixed gas into the adsorption tube, wherein the mixed gas consists of CO, Ar and H2The content is 15 percent, the temperature is increased to 550 ℃ under the condition of the temperature increase rate of 15 ℃/min, and the reaction is carried out for 100 min.
The average particle size of the nano ferrous oxide sample obtained in the embodiment 4 of the invention is 457.26nm, the product dispersibility is lower than that of the embodiment 2, and the particle size is average.
Example 5
A method for preparing nano iron by taking sintering ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture for 4 times at a ratio of 5.5, wherein iron oxide is obtained by electromagnetic separation in each washing, and the solid matters obtained by each magnetic separation are mixed to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.5 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5)Loading into an adsorption tube, and introducing reductive gas mixture into the adsorption tube, wherein the gas mixture comprises NH3And He, H2The content is 35 percent, the temperature is increased to 850 ℃ under the condition of the temperature increase rate of 15 ℃/min, and the reaction is carried out for 250 min.
The average particle size of the nano-iron sample obtained in the embodiment 5 of the invention is 673.25nm, the product has good dispersibility, and the particle size is very average.
Comparative example 1
A method for preparing nano ferroferric oxide by taking sintered ash as a raw material comprises the following specific operation steps:
1) 80g of the sintering ash was taken and mixed with deionized water according to a ratio of 1: washing the mixture for 6 times in a ratio of 3, wherein iron oxide is obtained by electromagnetic separation in each washing, and the solid matters magnetically separated in each time are mixed to obtain primary solid matters;
2) washing the primary solid matter prepared in the step 1) with deionized water again, carrying out magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and reserving the secondary magnetic separation solid matter;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a primary purified solid matter;
4) sequentially performing alkali washing (performing alkali washing on a NaOH solution with the concentration of 0.6 mol/L), suction filtering and deionized water leaching on the primary purified solid matter prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkali washing, suction filtering and deionized water leaching for multiple times until the conductivity is stable (the conductivity is the same as or close to that of the used deionized water), so as to obtain a purified solid matter;
5) drying the purified solid substance prepared in the step 4) to prepare nano iron oxide;
6) weighing 50mg of the nano iron oxide prepared in the step 5), putting the nano iron oxide into an adsorption tube, and filling reductive mixed gas into the adsorption tube, wherein the mixed gas consists of H2And He, H2The content is 55 percent, the temperature is increased to 380 ℃ under the condition of the temperature increase rate of 4 ℃/min, and the reaction is carried out for 30 min.
The nano ferroferric oxide obtained in the embodiment 1 of the invention has the average particle size of 1561.84nm, poor dispersibility and large particle difference.
Test example 1
The results of the settings of the process conditions for preparing nano-iron and oxidizing the nano-iron in comparative examples 1 to 5 and comparative example 1, and the dispersibility and particle size data of the finally prepared nano-iron or oxide thereof are shown in the following table 1:
TABLE 1
From the results in table 1, it can be seen that:
as can be seen from comparison of example 1 and comparative example 1, the content of the reducing gas has a large influence on the size of the particles;
as is clear from comparison between examples 2 and 4, the kind of the stabilizing gas and the temperature increase rate have little influence on the size of the particles;
the comparison of examples 3 and 5 shows that the kind of the reducing gas and the reaction time have a certain influence on the particle size, but are not particularly large.
Through verification, the preparation method of the invention is characterized in that the alkali cleaning agent is prepared by the following steps of 1: 0.6-8 solid-to-liquid ratio, washing for 1-10 times with H2CO and/or NH3The reducing gas is 1-45% by volume; with N2Ar and/or He is a stable gas; heating to 280-480 ℃, or 400-700 ℃, or 500-1100 ℃ at a heating rate of 1-20 ℃/min, and preparing the nano iron with nano distribution or the corresponding nano iron oxide with the particle size in a certain range.
Test example 2
The nanometer iron oxide before alkaline washing and after alkaline washing and water washing is measured by an atomic absorption spectrometer, and the iron content data obtained according to the obtained data is shown in the following table 2:
TABLE 2
| Iron content (%) | Example 1 | Comparative example 1 | Example 2 | Example 4 | Example 3 | Example 5 |
| Before alkaline washing | 99.24 | 97.87 | 98.63 | 98.55 | 96.97 | 99.38 |
| After alkali washing and water washing | 99.85 | 99.79 | 99.84 | 99.93 | 99.68 | 99.96 |
From the results in table 2, it can be seen that: the invention creatively adds the steps of alkali washing and water leaching after water washing, and improves the purity of the prepared nano iron oxide.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for preparing nano iron and its oxide by using sintered ash as raw material is characterized by that firstly, the nano iron oxide is prepared, and its preparation method includes the following operation steps:
1) taking a certain amount of sintering ash, washing with water, and separating out primary solid matters through magnetic separation;
2) washing the magnetically separated primary solid matters with water again, performing magnetic separation again after washing, measuring the conductivity of the residual water after magnetic separation, and keeping secondary magnetically separated solid matters;
3) repeating the step 2) for multiple times on the secondary magnetic separation solid matter until the conductivity is stable to obtain a primary purified solid matter;
4) sequentially carrying out alkaline washing, suction filtration and water leaching on the primary purified solid substance prepared in the step 3), measuring the conductivity of water after leaching, and repeating the alkaline washing, suction filtration and water leaching for multiple times until the conductivity is stable to obtain a purified solid substance;
5) drying the purified solid substance prepared in the step 4) to obtain the nano ferric oxide.
2. The method for preparing nano-iron and its oxides using sintering ash as raw material according to claim 1, characterized by further comprising an operation step of reducing nano-iron oxide, comprising subjecting the nano-iron oxide prepared in step 5) to a reduction treatment in a mixed gas environment of reducing gas and stabilizing gas.
3. The method for preparing nano iron and oxides thereof using sintering ash as raw material according to claim 1 or 2, wherein the water is deionized water.
4. The method for preparing nano iron and oxides thereof by using sintering ash as a raw material according to claim 3, wherein the ratio of sintering ash to deionized water in the step 1) is 1: 0.6 to 8.
5. The method for preparing nano iron and oxides thereof using sintering ash as raw material according to claim 4, wherein the number of washing in step 1) is 1-10.
6. The method for preparing nano iron and oxides thereof by using sintering ash as a raw material according to claim 4 or 5, wherein step 4) is carried out with alkali washing by using NaOH solution.
7. The method for preparing nano-iron and the oxide thereof by using sintering ash as a raw material according to claim 6, wherein the concentration of the NaOH solution is 0.1-0.6 mol/L.
8. The method for preparing nano-iron and its oxides using sintering ash as raw material according to claim 2, characterized in that the reducing gas in the mixed gas is H2CO and/or NH3The volume content is 1-45%; the stabilizing gas being N2Ar and/or He.
9. The method for preparing nano iron and oxides thereof by using sintering ash as a raw material according to claim 2 or 8, wherein the reduction treatment is to heat the temperature to 280-480 ℃ to reduce nano iron oxide into nano ferroferric oxide;
or heating to 400-700 ℃, and reducing the nano ferric oxide into nano ferrous oxide;
or heating to 500-1100 deg.c to reduce the nanometer iron into nanometer iron;
wherein the temperature rise rate is 1-20 ℃/min, and the reaction time is 1-300 min.
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