CN113684335B - Metal iron and preparation method thereof - Google Patents
Metal iron and preparation method thereof Download PDFInfo
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- CN113684335B CN113684335B CN202111045268.3A CN202111045268A CN113684335B CN 113684335 B CN113684335 B CN 113684335B CN 202111045268 A CN202111045268 A CN 202111045268A CN 113684335 B CN113684335 B CN 113684335B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a metallic iron and a preparation method thereof, wherein the preparation method of the metallic iron adopts gamma-Fe 2 O 3 And carbon as main raw materials, and the preparation method specifically comprises the following steps of adding gamma-Fe with preset molar ratio 2 O 3 And carbon (C)gamma-Fe 2 O 3 Mixing with carbon, fully and uniformly mixing, and fully and uniformly mixing gamma-Fe 2 O 3 And placing the carbon into a high-temperature vacuum furnace for heat preservation and solid phase reaction, and cooling in inert gas after the reaction is completed to obtain metallic iron. The temperature condition required by the preparation method is far lower than 1200 ℃ in the prior art, the lower the temperature requirement of the reaction is, the less energy is required to be consumed, so that the energy consumption is greatly reduced, the discharge amount of dangerous gas is reduced by the reaction, and the pollution to the environment is reduced.
Description
Technical Field
The invention relates to the technical field of ferroalloy, in particular to metallic iron and a preparation method thereof.
Background
Iron making technology is a key technology for maintaining the iron and steel industry, wherein blast furnace iron making by using a blast furnace as equipment is an important link of iron and steel production. Blast furnace iron smelting is a method for continuously producing liquid pig iron in a vertical reactor-blast furnace by using coke, iron-containing ore and flux, the operation temperature of the method needs to reach 1200 ℃, a large amount of energy sources are required to be consumed, the energy efficiency is low, a large amount of dangerous gas is generated in the production process, and the discharge amount of the dangerous gas is high. Therefore, how to prepare metallic iron at low temperature is a technical problem to be solved.
Disclosure of Invention
Based on this, it is necessary to provide a metal iron and a preparation method thereof, so as to solve the technical problem that a large amount of energy is required to be consumed when the metal iron is prepared at a high temperature in the prior art.
The invention provides a preparation method of metallic iron, which uses gamma-Fe 2 O 3 And carbon is used as a main raw material, and the metal iron is prepared and obtained, and the preparation method specifically comprises the following steps:
step 1: is added with the gamma-Fe with a preset molar ratio 2 O 3 And the carbon;
step 2: subjecting the gamma-Fe to 2 O 3 Mixing with the carbon, and fully and uniformly mixing;
step 3: mixing the gamma-Fe fully and uniformly 2 O 3 And placing the carbon into a high-temperature vacuum furnace for heat preservation and solid phase reaction;
step 4: cooling in inert gas after the reaction is completed to obtain metallic iron.
Further, the gamma-Fe in step 1 2 O 3 And the preset molar ratio of the carbon is 1:50-1:3.
Further, the mixing mode in the step 2 comprises grinding, stirring and ball milling.
Further, the heat preservation and reaction conditions in the step 3 are as follows: preserving heat for 18-80h at 430-700 ℃.
Further, the heat preservation and reaction conditions in the step 3 are as follows: the temperature was kept at 430℃for 80h.
Further, the cooling conditions in step 4 are: cooling to 20-50 ℃ in inert gas.
Further, the inert gas in step 4 includes nitrogen and/or nitrogen.
Further, the cooling in inert gas after the reaction in the step 4 comprises:
purging the reacted material with an inert gas.
In another embodiment, the invention further provides a preparation method of metallic iron, wherein Fe-MOF-74 is used as a raw material to prepare and obtain the metallic iron, and the preparation method specifically comprises the following steps:
step 1: placing the Fe-MOF-74 into a high-temperature vacuum furnace for heat treatment for 18-80 hours, wherein the temperature of the heat treatment is 430-700 ℃;
step 2: cooling in inert gas after the reaction is completed to obtain metallic iron.
In another embodiment, the invention also provides the metal iron prepared by the method, wherein the content of Fe in the prepared metal iron is 90-95%, the content of Fe2O3 is 3-7%, and the content of carbon is 3-7%.
The invention provides a preparation method of metallic iron, which comprises the steps of mixing gamma-Fe with a preset molar ratio 2 O 3 Mixing with carbon, fully and uniformly mixing, placing into a high-temperature vacuum furnace for heat preservation and solid-phase reaction, and cooling in inert gas after the reaction is completed to obtain metallic iron.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing XRPD patterns after heat treatment at 430℃for various times in an embodiment of the invention;
FIG. 2 is an XRPD pattern obtained by finishing after heat treatment at 430℃for 80 hours in the example of the present invention;
FIG. 3 is an XRPD pattern for a heat treatment of 200℃at 300℃at 400℃for 36h in an example of the invention;
FIG. 4 is a TEM image of a heat treatment at 200deg.C, 300deg.C, 400deg.C for 36h in an embodiment of the invention;
FIG. 5 is an XRPD pattern for a heat treatment at 700℃for 24h in an embodiment of the invention;
fig. 6 is a TEM image of a heat treatment at 700 ℃ for 24h in the example of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement, etc. between the components in a particular posture (as shown in the drawings), and if the particular posture is changed, the directional indicator is changed accordingly.
Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The method for preparing metallic iron according to the invention uses gamma-Fe 2 O 3 And carbon is used as a main raw material, the raw materials are uniformly mixed according to a preset proportion, a fully and uniformly mixed sample is put into a high-temperature furnace for heat preservation and solid phase reaction, and the mixture is cooled in inert gas after the reaction is finished, so that the metallic iron is finally prepared. The method can make gamma-Fe at low temperature 2 O 3 The iron is reduced, and compared with the blast furnace iron smelting technology in the prior art, the method greatly reduces the operating temperature and reduces the energy consumption. Since the reaction is performed in a milder environment, the harmful gas generated by the reaction is less than that generated by the blast furnace in the prior art, and the harmful gas is easy to collect and treat, so that the pollution to the environment can be reduced. The method can improve ferric oxide conversion rate and reduce goldBelongs to the production cost of iron, has higher commercial value and is suitable for large-scale industrial production.
The method comprises the following steps:
step 1: is added with the gamma-Fe with a preset molar ratio 2 O 3 And the carbon;
step 2: subjecting the gamma-Fe to 2 O 3 Mixing with the carbon, and fully and uniformly mixing;
step 3: mixing the gamma-Fe fully and uniformly 2 O 3 And placing the carbon into a high-temperature vacuum furnace for heat preservation and solid phase reaction;
step 4: cooling in inert gas after the reaction is completed to obtain metallic iron.
Specifically, in step 1, the gamma-Fe 2 O 3 And the molar ratio of the carbon is 1:50-1:3. The mixing mode in the step 2 comprises grinding, stirring and ball milling.
More specifically, the incubation and reaction conditions in step 3 are: preserving heat for 18-80h at 430-700 ℃. The heat preservation and reaction conditions in the step 3 are as follows: the temperature was kept at 430℃for 80h.
Further, the cooling conditions in step 4 are: cooling to 20-50 ℃ in inert gas. The inert gas in step 4 comprises nitrogen and/or nitrogen. Cooling in inert gas after the reaction in the step 4 comprises the following steps:
purging the reacted material with an inert gas. For example, the material after the completion of the reaction is purged with high purity nitrogen.
Further, a method for preparing metallic iron by using Fe-MOF-74 as a raw material comprises the following steps:
step 1: placing the Fe-MOF-74 into a high-temperature vacuum furnace for heat treatment for 18-80h, wherein the temperature of the heat treatment is 430-700 ℃;
step 2: cooling in inert gas after the reaction is completed to obtain metallic iron.
Specifically, the gamma-Fe 2 O 3 And precursors of said carbon (including metal organic frameworks MOF-74, MIL-101, MIL-100, MIL-88B, MIL-53, MOF-101, MOF-199, MOF-235, MOF-525, MOF-535, MOF-545, etc. and others possibly converted to said gamma-Fe by various conditions) 2 O 3 And said carbon), taking MOF-74 as an example: anhydrous FeCl2 (2.20 g) and 1, 4-dihydroxyterephthalic acid (1.42 g) were dissolved in 500ml of deoxyN, N-Dimethylformamide (DMF). The solution was reacted at 120℃for 5 days under the protection of argon. The product was washed 3 times with deoxygenated DMF, soaked in deoxygenated methanol for 3 days, and the sample was dried in vacuo at 60 ℃ to obtain the gamma-Fe 2O3 and the carbon precursor.
The content of Fe in the metallic iron prepared by the method is 90-95%, fe 2 O 3 The content is 3-7%, the carbon content is 3-7%, and other trace elements can be ignored.
As shown in FIG. 1, fe-MOF-74 was heat treated at 430℃under vacuum for 18-80h to give the corresponding XRPD patterns.
Can be analyzed by diffraction peak, and after 18h, the sample contains gamma-Fe 2 O 3 And Fe (Fe) 3 And C. After 36h, fe 3 C disappears and alpha-Fe (body centered cubic lattice) appears. From this, it was found that gamma-Fe was produced by thermal decomposition of Fe-MOF-74 2 O 3 Is Fe 3 C mediated process, after 80 hours of heat treatment, most of the gamma-Fe 2 O 3 Has been reduced to alpha-Fe.
As shown in FIG. 2, the XPRD spectrum obtained at 80h was refined to obtain α -Fe and γ -Fe 2 O 3 The weight ratio of (2) is 86.9:13.1, thereby calculating Fe 2 O 3 The conversion to Fe was 91.2%.
Example 1
The Fe-MOF-74 was heat treated at 200deg.C and 300deg.C under vacuum for 36 hours, respectively, to obtain its XRPD pattern (as shown in FIG. 3) and transmission electron microscope pattern (as shown in FIGS. 4a, b), respectively. Analysis of the XRPD pattern shows that under both conditions the crystal structure of the Fe-MOF-74 sample is substantially lost (only a weak diffraction peak at the individual position). From the TEM image, no obvious particles are found at 200 ℃, and only a small amount of tiny particles are found at 300 ℃, which is consistent with the analysis result of the spectrogram.
Example 2
The Fe-MOF-74 was heat treated at 400℃under vacuum for 36 hours to obtain its XRPD pattern (as shown in FIG. 3) and transmission electron microscopy image (as shown in FIG. 4 c). Analysis of XRPD patterns revealed gamma-Fe at 400 ℃ 2 O 3 Exists. From TEM images, it can be seen that gamma-Fe 2 O 3 The aggregates of NPs coexist with the carbon remaining after decomposition of Fe-MOF-74, consistent with the results of the spectrogram analysis, but no alpha-Fe was found to be present.
Example 3
The Fe-MOF-74 was heat treated at 700℃under vacuum for 24 hours, the XRPD pattern of the product (as shown in FIG. 5) had significant alpha-Fe presence, and the transmission electron microscopy image showed (as shown in FIG. 6) that the alpha-Fe particle size was greater than 200nm.
Example 4
The XRPD pattern of the product obtained by heat treating Fe-MOF-74 at 600℃for 36 hours under vacuum shows the presence of significant alpha-Fe.
Example 5
Fe-MOF-74 was heat treated at 500℃under vacuum for 48 hours, as was the presence of significant alpha-Fe found in the XRPD pattern of the product.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the description of the present invention and the accompanying drawings or direct/indirect application in other related technical fields are included in the scope of the invention.
Claims (7)
1. A method for preparing metallic iron is characterized in that gamma-Fe is adopted in the preparation method 2 O 3 And carbon is used as a main raw material, and the metal iron is prepared and obtained, and the preparation method specifically comprises the following steps:
step 1: is added with the gamma-Fe with a preset molar ratio 2 O 3 And the carbon;
step 2: subjecting the gamma to-Fe 2 O 3 Mixing with the carbon, and fully and uniformly mixing, wherein the mixing mode comprises grinding, stirring and ball milling;
step 3: mixing the gamma-Fe fully and uniformly 2 O 3 And placing the carbon into a high-temperature vacuum furnace for heat preservation and solid phase reaction;
step 4: cooling in inert gas after the reaction is completed to obtain metallic iron;
wherein, the heat preservation and reaction conditions in the step 3 are as follows: preserving heat for 18-80h at 430-700 ℃;
wherein the preset molar ratio of the gamma-Fe 2O3 to the carbon in the step 1 is 1:50-1:3.
2. The method for preparing metallic iron as set forth in claim 1, wherein the heat preservation and reaction conditions in step 3 are: the temperature was kept at 430℃for 80h.
3. The method for producing metallic iron as set forth in claim 1, wherein the cooling conditions in step 4 are: cooling to 20-50 ℃ in inert gas.
4. The method for producing metallic iron as set forth in claim 1, wherein the inert gas in step 4 includes nitrogen.
5. The method for producing metallic iron as set forth in claim 1, wherein the cooling in an inert gas after the completion of the reaction in step 4 comprises:
purging the reacted material with an inert gas.
6. The method for producing metallic iron as set forth in any one of claims 1 to 5, wherein the Fe content in the metallic iron produced is 90% to 95%, fe 2 O 3 3-7% of carbon and 3-7% of carbon.
7. The preparation method of the metal iron is characterized by taking Fe-MOF-74 as a raw material, and preparing and obtaining the metal iron, and specifically comprises the following steps:
step 1: placing the Fe-MOF-74 into a high-temperature vacuum furnace for heat treatment, wherein after 18 hours, the sample contains gamma-Fe 2 O 3 And Fe (Fe) 3 C mixture, after 36h, fe 3 C disappears, alpha-Fe appears, and gamma-Fe is generated by thermal decomposition of Fe-MOF-74 2 O 3 Is Fe 3 C mediated process, after 80 hours of heat treatment, most of the gamma-Fe 2 O 3 Has been reduced to α -Fe, wherein the temperature of the heat treatment is in the temperature range of 430 ℃ to 700 ℃;
step 2: cooling in inert gas after the reaction is completed to obtain metallic iron.
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| DE3231192A1 (en) * | 1982-08-21 | 1984-02-23 | Basf Ag, 6700 Ludwigshafen | MOLDED IRON CATALYST, THEIR PRODUCTION AND USE |
| JP2011252226A (en) * | 2010-05-06 | 2011-12-15 | Kobe Steel Ltd | Manufacturing method of metal iron |
| CN103255357B (en) * | 2013-05-17 | 2016-01-20 | 荥经华盛冶金科技有限公司 | A kind of method utilizing stainless steel oxidation iron sheet to produce Ni-Cr-Mn iron alloy |
| CN109913743B (en) * | 2019-04-28 | 2021-02-05 | 北京科技大学 | Method for preparing ferromolybdenum from molybdenum carbide and iron oxide |
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