CN114180638B - Permanent magnetic ferrite magnetic powder prepared from pickling waste liquid of steel mill and preparation method thereof - Google Patents
Permanent magnetic ferrite magnetic powder prepared from pickling waste liquid of steel mill and preparation method thereof Download PDFInfo
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 100
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 49
- 239000010959 steel Substances 0.000 title claims abstract description 49
- 239000007788 liquid Substances 0.000 title claims abstract description 48
- 239000006247 magnetic powder Substances 0.000 title claims abstract description 46
- 238000005554 pickling Methods 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 91
- 239000011575 calcium Substances 0.000 claims description 31
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 19
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 235000021110 pickles Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/70—Cobaltates containing rare earth, e.g. LaCoO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 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
- C01P2004/62—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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to a permanent magnetic ferrite magnetic powder prepared by using pickling waste liquid of a steel mill, wherein the chemical formula of the permanent magnetic ferrite is (Sr) 1‑x M x ).(Fe 2n‑y Me y )O 19 Wherein x is more than or equal to 0 and less than or equal to 0.7,0, y is more than or equal to 1,5.0 and less than or equal to n is more than or equal to 6.2, M is at least one of Ca, la, ce, pr, and Me is at least one of Al, co and Zn. The preparation method comprises the following steps: (1) carrying out total iron content measurement on pickling waste liquid of a steel plant; (2) According to the measurement result of the total iron content in the pickling waste liquid of the steel mill, determining and selecting powdery raw materials and batching according to the chemical formula of the permanent magnetic ferrite and the values of x, y and n in the chemical formula; (3) Adding the raw materials into the pickling waste liquid of a steel mill under stirring to form a reaction system, adding an alkaline solution to adjust the pH value of the reaction system to 8-10, continuously stirring until the reaction system precipitates and forms a condensate, separating the condensate, and washing the condensate with water, wherein the condensate after washing is a precursor of ferrite; (4) And drying the precursor of ferrite and sintering to obtain the permanent magnet ferrite magnetic powder.
Description
Technical Field
The invention belongs to the field of permanent magnetic ferrite magnetic powder preparation or the field of steel mill pickling waste liquid recycling, and relates to permanent magnetic ferrite magnetic powder prepared by using steel mill pickling waste liquid and a preparation method thereof.
Background
The waste pickling liquid of steel mill is the waste liquid produced by pickling steel, the pickling treatment of steel is widely applied to blank treatment of cold-rolled sheet and surface iron oxide scale removal of hot-rolled sheet (such as surface pretreatment of cold-rolled sheet before electroplating processing, surface treatment of hot-rolled section steel for phosphating or plating, etc.), the produced waste pickling liquid of steel mill contains high-concentration hydrochloric acid and ferrous ions, and the main component is Fe 2+ And a small amount of Fe 3+ And other impurity elements (Si, mn, S, P, etc.).
Regarding the recycling of the pickling waste liquid of the steel mill, the prior art mainly obtains the byproduct iron oxide red while recycling the acid, but the process needs to produce a large amount of waste water and waste gas, which causes serious pollution to the environment.
Regarding the preparation of permanent magnetic ferrite magnetic powder, the prior art is to uniformly mix iron oxide red powder with strontium carbonate, calcium carbonate, lanthanum oxide and other powder, prepare ferrite pre-sintering material by adopting a ceramic solid-phase sintering method, then mix ferrite pre-sintering material with additives by adopting wet ball milling, crushing, mixing and pulping, then filter water content of slurry (controlling the water content to be 35-45%) and then directionally press the slurry into green bodies by adopting a wet pressing magnetic field, and finally sinter the green bodies to obtain the permanent magnetic ferrite magnetic powder. The problems of preparing ferrite pre-sintering material by taking iron oxide red powder and strontium carbonate, calcium carbonate, lanthanum oxide and other powder as raw materials and preparing permanent magnetic ferrite magnetic powder by taking ferrite pre-sintering material and additive as raw materials are as follows: (1) When ferrite pre-sintering material is prepared, the sintering temperature is usually 1300 ℃, so that the grains of the pre-sintering material are obviously grown; (2) When the permanent magnetic ferrite magnetic powder is prepared, the ferrite pre-sintered material is high in hardness and difficult to crush, and magnetic powder particles with single domain grain size are obtained by adopting a long-time ball milling process, so that serious damage of a grain structure, impurity pollution caused by long-time ball milling, adverse effects of widening of particle size distribution of the magnetic powder and the like are brought, and the improvement of the overall magnetic performance, mechanical performance, stability and qualification rate of a product is adverse.
Disclosure of Invention
The invention aims to provide permanent magnetic ferrite magnetic powder prepared from steel mill pickling waste liquid and a preparation method thereof, so as to avoid environmental pollution caused by recycling the steel mill pickling waste liquid in the prior art and obtain the permanent magnetic ferrite magnetic powder with fine and uniform grains and excellent magnetic property.
The invention relates to a permanent magnetic ferrite magnetic powder prepared by using pickling waste liquid of a steel mill, wherein the chemical formula of the permanent magnetic ferrite is (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Wherein x is more than or equal to 0 and less than or equal to 0.7,0, y is more than or equal to 1,5.0 and less than or equal to n is more than or equal to 6.2, M is at least one of Ca, la, ce, pr, and Me is at least one of Al, co and Zn.
The grain size of the permanent magnetic ferrite magnetic powder prepared by using the pickling waste liquid of the steel mill is not more than 1.5 mu m.
The preparation method of the permanent magnetic ferrite magnetic powder prepared by using the pickling waste liquid of the steel mill comprises the following process steps:
(1) Determination of total iron content in pickling waste liquid
Measuring the total iron content of the pickling waste liquid of the steel mill;
(2) Proportioning materials
According to the measurement result of the total iron content in the pickling waste liquid of the steel mill, the chemical formula (Sr) of the permanent magnetic ferrite is adopted 1-x M x ).(Fe 2n-y Me y )O 19 And the values of x, y and n in the chemical formula are determined, powdery raw materials are selected, and the ingredients are prepared;
(3) Precursor preparation of ferrite
Adding the metered raw materials into pickling waste liquid of a steel mill under stirring to form a reaction system, adding alkaline solution to adjust the pH value of the reaction system to 8-10, continuing stirring until the reaction system precipitates and forms a condensate, separating the condensate, cleaning the condensate with water, and stopping cleaning when the pH value of cleaning separation liquid is 7-8, wherein the obtained cleaned condensate is a precursor of ferrite;
(4) Drying and sintering of the precursor
And drying the precursor of ferrite, sintering in air atmosphere at 800-1100 deg.c for 0.5-3 hr, and cooling to room temperature to obtain the permanent magnet ferrite powder.
The preparation method of the permanent magnetic ferrite magnetic powder prepared by using the pickling waste liquid of the steel mill has the chemical formula (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 In (a): the Sr is prepared from strontium carbonate powder; the raw materials of M and Ca are calcium carbonate powder, calcium hydroxide powder or calcium oxide powder, the raw materials of La are lanthanum oxide powder, the raw materials of Ce are cerium oxide powder, and the raw materials of Pr are praseodymium oxide powder; the Me and Al are aluminum oxide powder or aluminum powder, the Co is cobalt oxide powder or cobalt powder, and the Zn is zinc oxide powder or zinc powder.
In the step (3), the alkaline solution is one of sodium hydroxide solution, ammonia water, ammonium oxalate solution and ethylenediamine solution.
In the step (4), the drying temperature of the precursor of ferrite is 250-400 ℃ and the drying time is 1-2 h; the temperature rising rate from room temperature to sintering temperature is 2-10 ℃/min during sintering.
In the step (3), the water for cleaning the condensate is deionized water or distilled water.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a new technical scheme for recycling the pickling waste liquid of the steel mill and preparing the permanent magnetic ferrite magnetic powder.
2. According to the method, the powdery raw materials for generating the ferrite permanent magnetic phase elements are added into the steel mill pickling waste liquid, so that the additive and the precursor of the iron oxide red are mixed at a molecular level through continuous stirring in the process of chemical precipitation and condensation, the activity of subsequent reaction can be improved, the roasting temperature is reduced, and the ferrite precursor directly prepared from the steel mill pickling waste liquid is roasted at a low temperature to obtain the permanent magnetic ferrite powder with the ferrite main phase content of more than 90%, fine and uniform grains and excellent magnetic performance.
3. Example 1 shows that the method of the invention can be used for preparing rare earth-free and noble metal-doped high-performance permanent magnetic ferrite, and can realize the mass production of the international leading level lanthanum-free cobalt ferrite 9 material (Japanese TDK company).
4. The method not only realizes the recycling of the pickling waste liquid of the steel mill, but also can avoid the environmental pollution caused by the recycling of the pickling waste liquid of the steel mill in the prior art.
Drawings
FIG. 1 is an XRD phase analysis spectrum of the permanent magnetic ferrite powder prepared in example 1;
FIG. 2 is a scanning electron microscope image of the permanent magnetic ferrite powder prepared in example 1;
FIG. 3 is an XRD phase analysis spectrum of the permanent magnetic ferrite powder prepared in example 2;
FIG. 4 is a scanning electron microscope image of the permanent magnetic ferrite powder prepared in example 2;
fig. 5 is an XRD phase analysis spectrum of the permanent magnetic ferrite powder prepared in example 3;
fig. 6 is a scanning electron microscope image of the permanent magnetic ferrite powder prepared in example 3.
Detailed Description
The permanent magnetic ferrite magnetic powder prepared by using the pickling waste liquid of the steel mill and the preparation method thereof are further described by the following examples.
In the following examples, the total iron content in the steel mill pickle liquor was measured by a chemical titration method and found to be 75.3g/L, and calculated to be 150.6g, and the total iron content was 2.69mol, with respect to the 2L steel mill pickle liquor.
In each of the examples described below, the starting material powders were analytically pure.
Example 1
The chemical formula of this example is Sr 1 Fe 10.4 O 19 Permanent magnetic ferrite powder of formula (Sr) 1-x M x ).(Fe 2n- y Me y )O 19 Where n=5.2, x=0, y=0. The process comprises the following steps:
(1) Proportioning materials
According to the chemical formula of the permanent magnetic ferrite magnetic powder prepared in the embodiment, the molar ratio of Sr to Fe is 1:10.4, and the total amount of iron elements in 2L of steel mill pickling waste liquid is 2.69mol, so that the amount of Sr is 0.259mol, in the embodiment, the raw material of Sr is strontium carbonate powder, and the strontium carbonate powder corresponding to 0.259mol of Sr is 38.3g.
(2) Precursor preparation of ferrite
Adding 38.3g of measured strontium carbonate powder into 2L of steel mill pickling waste liquid to form a reaction system under stirring, adding sodium hydroxide solution to adjust the pH value of the reaction system to 8, continuously stirring for 1h, separating out precipitate and forming a condensate, filtering to separate the condensate, cleaning the condensate with deionized water, and stopping cleaning when the pH value of the cleaning separation liquid is 7, wherein the obtained cleaned condensate is a precursor of ferrite;
(3) Drying and sintering of the precursor
Drying a precursor of ferrite in an oven at 300 ℃ for 1h, then heating to 870 ℃ in a muffle furnace at a heating rate of 3 ℃/min, sintering for 2h, and cooling to room temperature along with the furnace after sintering is finished, thus obtaining the permanent magnet ferrite magnetic powder.
The obtained permanent magnet ferrite magnetic powder is tested by adopting a VSM (vertical seismic sensor) test, the saturation magnetization intensity is 68emu/g, and the coercivity is 3900Oe; XRD phase analysis is adopted to obtain the ferrite main phase content of the magnetic powder reaching 93 percent (shown in figure 1); the magnetic powder has uniform grain size, complete crystallization, no agglomeration and adhesion phenomenon, and the grain size is about 0.6-0.7 μm (see figure 2) by SEM scanning electron microscope observation.
Example 2
The chemical formula (Sr) is prepared in this example 0.7 Ca 0.3 )·(Fe 11.4 Co 0.2 )O 19 Permanent magnetic ferrite powder of formula (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Where n=5.8, x=0.3, y=0.2, m is Ca and Me is Co. The process comprises the following steps:
(1) Proportioning materials
The formula of the permanent magnetic ferrite magnetic powder prepared according to this example was 0.7:11.4 in mole ratio of Sr to Fe, 0.3:11.4 in mole ratio of Ca to Fe, 0.2:11.4 in mole ratio of Co to Fe, and 2.69mol in total of iron elements in 2L of steel mill pickle liquor, so that the amount of Sr should be 0.165mol, the amount of Ca should be 0.071mol, and the amount of Co should be 0.047mol. In the embodiment, the raw material of Sr is strontium carbonate powder, and the amount of the strontium carbonate powder corresponding to 0.165mol of Sr is 24.42g; the raw material of Ca is calcium carbonate powder, and the content of 0.071mol of calcium carbonate powder corresponding to Ca is 7.1g; the Co material was cobalt monoxide powder, and the cobalt monoxide powder corresponding to 0.047mol Co was 3.54g.
(2) Precursor preparation of ferrite
Adding 24.42g of strontium carbonate powder, 7.1g of calcium carbonate powder and 3.54g of cobalt monoxide powder into 2L of steel mill pickling waste liquid under stirring to form a reaction system, adding ammonia water solution to adjust the pH value of the reaction system to 9, continuously stirring for 2 hours, separating out precipitates and forming agglomerates by the reaction system, filtering to separate the agglomerates, cleaning the agglomerates by using distilled water, and stopping cleaning when the pH value of the cleaning separation liquid is 8, wherein the obtained cleaned agglomerates are precursors of ferrite;
(3) Drying and sintering of the precursor
Drying a precursor of ferrite in an oven at 400 ℃ for 2 hours, then heating to 950 ℃ in a muffle furnace at a heating rate of 6 ℃/min, sintering for 1 hour, and cooling to room temperature along with the furnace after sintering is finished, thus obtaining the permanent magnet ferrite magnetic powder.
The obtained permanent magnet ferrite magnetic powder is tested by adopting a VSM (vertical scanning molecular sieve) test, the saturation magnetization intensity is 71emu/g, and the coercive force is 4100Oe; XRD phase analysis is adopted to obtain the ferrite main phase content of the magnetic powder reaching 92 percent (see figure 3); the magnetic powder has uniform grain size, complete crystallization, no agglomeration and adhesion phenomenon, and the grain size is about 0.8-0.9 μm (see figure 4) by SEM scanning electron microscope observation.
Example 3
The chemical formula (Sr) is prepared in this example 0.6 Ca 0.2 La 0.2 )·(Fe 11.4 Co 0.4 Al 0.2 Zn 0.2 )O 19 Permanent magnetic ferrite powder of formula (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Where n=6.1, x=0.4, y=0.8, m is Ca, la, and the molar ratio Ca: la=1: 1, me is Co, al and Zn, and the molar ratio of Co: al: zn=2: 1:1. the process comprises the following steps:
(1) Proportioning materials
According to the chemical formula of the permanent magnetic ferrite powder prepared in this example, the mole ratio of Sr to Fe is 0.6:11.4, the mole ratio of Ca to Fe is 0.2:11.4, the mole ratio of La to Fe is 0.2:11.4, the mole ratio of Co to Fe is 0.4:11.4, the mole ratio of Al to Fe is 0.2:11.4, the mole ratio of Zn to Fe is 0.2:11.4, and the total amount of iron in 2L of steel mill pickle liquor is 2.69mol, so the amount of Sr should be 0.142mol, the amount of Ca should be 0.047mol, the amount of La should be 0.047mol, the amount of Co should be 0.094mol, the amount of Al should be 0.047mol, and the amount of Zn should be 0.047mol. In the embodiment, the raw material of Sr is strontium carbonate powder, and the 0.142mol of Sr corresponds to 21g of strontium carbonate powder; the raw material of Ca is calcium carbonate powder, and the 0.047mol of Ca corresponds to 4.7g of calcium carbonate powder; la was a lanthanum oxide powder, 0.047mol of La was 7.66g of lanthanum oxide powder, co was a cobalt oxide powder, 0.094mol of Co was 7.8g of cobalt oxide powder, al was an aluminum oxide powder, 0.047mol of Al was 2.4g of aluminum oxide powder, zn was a zinc oxide powder, and 0.047mol of Zn was 3.83g of zinc oxide powder.
(2) Precursor preparation of ferrite
Adding 21g of strontium carbonate powder, 4.7g of calcium carbonate powder, 7.66g of lanthanum oxide powder, 7.8g of cobaltic oxide powder, 2.4g of aluminum oxide powder and 3.83g of zinc oxide powder into 2L of steel mill pickling waste liquid under stirring to form a reaction system, then adding sodium hydroxide solution to adjust the pH value of the reaction system to 10, continuously stirring for 1h, separating out precipitates and forming agglomerates by the reaction system, filtering to separate the agglomerates, cleaning the agglomerates by distilled water, and stopping cleaning when the pH value of a cleaning separation liquid is 7, wherein the obtained cleaned agglomerates are precursors of ferrite;
(3) Drying and sintering of the precursor
Drying a precursor of ferrite in an oven at 350 ℃ for 2 hours, then heating to 1100 ℃ in a muffle furnace at a heating rate of 8 ℃/min, sintering for 0.5 hour, and cooling to room temperature along with the furnace after sintering is finished, thus obtaining the permanent magnet ferrite magnetic powder.
The obtained permanent magnet ferrite magnetic powder is tested by adopting a VSM (vertical scanning microscope), the saturation magnetization intensity is 65.5emu/g, and the coercivity is 4600Oe; XRD phase analysis is adopted to obtain the ferrite main phase content of the magnetic powder reaching 90 percent (see figure 5); the magnetic powder has uniform grain size, complete crystallization, no agglomeration and adhesion phenomenon, and the grain size is about 1.0-1.15 μm (see figure 6) by SEM scanning electron microscope observation.
Example 4
The chemical formula (Sr) is prepared in this example 0.5 Ca 0.2 La 0.2 Pr 0.1 )·(Fe 11.5 Co 0.3 Al 0.1 )O 19 Permanent magnetic ferrite powder of formula (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Where n=5.95, x=0.5, y=0.4, m is Ca, la, pr, and the molar ratio Ca: la: pr=2:2:1, me is Co, al, and molar ratio Co: al=3: 1. the process comprises the following steps:
(1) Proportioning materials
According to the chemical formula of the permanent magnetic ferrite powder prepared in this example, the mole ratio of Sr to Fe is 0.5:11.5, the mole ratio of Ca to Fe is 0.2:11.5, the mole ratio of La to Fe is 0.2:11.5, the mole ratio of Pr to Fe is 0.1:11.5, the mole ratio of Co to Fe is 0.3:11.5, the mole ratio of Al to Fe is 0.1:11.5, and the total amount of iron elements in 2L steel mill pickle liquor is 2.69mol, so the amount of Sr should be 0.117mol, the amount of Ca should be 0.047mol, the amount of La should be 0.047mol, the amount of Pr should be 0.023mol, the amount of Co should be 0.070mol, and the amount of Al should be 0.023mol. In the embodiment, the raw material of Sr is strontium carbonate powder, and the amount of the strontium carbonate powder corresponding to 0.117mol of Sr is 17.32g; the raw material of Ca is calcium oxide powder, and the calcium oxide powder corresponding to 0.047mol of Ca is 2.63g; la is a lanthanum oxide powder, 0.047mol La is 7.66g lanthanum oxide powder, pr is praseodymium oxide powder, 0.023mol Pr is 3.92g praseodymium oxide powder, co is a cobalt monoxide powder, 0.070mol Co is 5.25g cobalt monoxide powder, al is aluminum oxide powder, and 0.023mol Al is 1.17g aluminum oxide powder.
(2) Precursor preparation of ferrite
Adding 17.32g of strontium carbonate powder, 2.63g of calcium oxide powder, 7.66g of lanthanum oxide powder, 3.92g of praseodymium oxide powder, 5.25g of cobalt monoxide powder and 1.17g of alumina powder into 2L of steel mill pickling waste liquid under stirring to form a reaction system, adding ammonium oxalate solution to adjust the pH value of the reaction system to 9, continuously stirring for 1h, separating out precipitates and forming agglomerates by the reaction system, filtering to separate the agglomerates, cleaning the agglomerates by distilled water, and stopping cleaning when the pH value of a cleaning separation liquid is 7, wherein the obtained cleaned agglomerates are precursors of ferrite;
(3) Drying and sintering of the precursor
Drying a precursor of ferrite in an oven at 250 ℃ for 2 hours, then heating to 1000 ℃ in a muffle furnace at a heating rate of 8 ℃/min, sintering for 0.5 hour, and cooling to room temperature along with the furnace after sintering is finished, thus obtaining the permanent magnet ferrite magnetic powder.
The obtained permanent magnet ferrite magnetic powder is tested by adopting a VSM (vertical scanning microscope), the saturation magnetization intensity is 67emu/g, and the coercivity is 4800Oe; XRD phase analysis is adopted to obtain that the ferrite main phase content of the magnetic powder reaches 90%; the magnetic powder has uniform grain size, complete crystallization, no agglomeration and adhesion phenomenon and grain size of about 0.9-1.05 μm by adopting an SEM scanning electron microscope for observation.
Example 5
The chemical formula (Sr) is prepared in this example 0.4 Ca 0.3 La 0.3 )·(Fe 11.3 Co 0.5 Zn 0.1 )O 19 Permanent magnetic ferrite powder of formula (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Where n=5.95, x=0.6, y=0.6, m is Ca, la, and the molar ratio Ca: la=1:1, me is Co, zn, and molar ratio Co: zn=5: 1. the process comprises the following steps:
(1) Proportioning materials
According to the chemical formula of the permanent magnetic ferrite powder prepared in this example, the mole ratio of Sr to Fe is 0.4:11.3, the mole ratio of Ca to Fe is 0.3:11.3, the mole ratio of La to Fe is 0.3:11.3, the mole ratio of Co to Fe is 0.5:11.3, the mole ratio of Zn to Fe is 0.1:11.3, and the total amount of iron elements in 2L steel mill pickle liquor is 2.69mol, so that the amount of Sr should be 0.095mol, the amount of Ca should be 0.071mol, the amount of La should be 0.071mol, the amount of Co should be 0.119mol, and the amount of Zn should be 0.024mol. In the embodiment, the raw material of Sr is strontium carbonate powder, and the content of strontium carbonate powder corresponding to 0.095mol of Sr is 14.06g; the raw material of Ca is calcium hydroxide powder, and the calcium hydroxide powder corresponding to 0.071mol Ca is 5.25g; la was a lanthanum oxide powder, lanthanum oxide powder corresponding to 0.071mol La was 11.57g, co was a cobalt monoxide powder, cobalt monoxide powder corresponding to 0.119mol Co was 8.93g, zn was a zinc oxide powder, and zinc oxide powder corresponding to 0.024mol Zn was 1.95g.
(2) Precursor preparation of ferrite
Adding 14.06g of strontium carbonate powder, 5.25g of calcium hydroxide powder, 11.57g of lanthanum oxide powder, 8.93g of cobalt oxide powder and 1.95g of zinc oxide powder into 2L of steel mill pickling waste liquid under stirring to form a reaction system, adding ethylenediamine solution to adjust the pH value of the reaction system to 8, continuously stirring for 1h, separating out precipitate from the reaction system and forming a condensate, filtering to separate the condensate, washing the condensate with deionized water, and stopping washing when the pH value of a washing separation liquid is 7, wherein the obtained washed condensate is a precursor of ferrite;
(3) Drying and sintering of the precursor
Drying a precursor of ferrite in an oven at 250 ℃ for 2 hours, then heating to 1000 ℃ in a muffle furnace at a heating rate of 5 ℃/min, sintering for 0.5 hours, and cooling to room temperature along with the furnace after sintering is finished, thus obtaining the permanent magnet ferrite magnetic powder.
The obtained permanent magnet ferrite magnetic powder is tested by adopting a VSM (vertical scanning microscope), the saturation magnetization intensity is measured to be 70emu/g, and the coercivity is 4000Oe; XRD phase analysis is adopted to obtain that the ferrite main phase content of the magnetic powder reaches 91%; the magnetic powder has uniform grain size, complete crystallization, no agglomeration and adhesion phenomenon and grain size of about 0.9-1.0 μm by adopting an SEM scanning electron microscope for observation.
Claims (5)
1. Method for preparing permanent magnetic ferrite magnetic powder by using pickling waste liquid of steel mill, wherein the chemical formula of the permanent magnetic ferrite is (Sr) 1-x M x ).(Fe 2n-y Me y )O 19 Wherein x is more than or equal to 0 and less than or equal to 0.7,0, y is more than or equal to 1,5.0 and less than or equal to 6.2, M is at least one of Ca, la, ce, pr, me is at least one of Al, co and Zn, and the method is characterized by comprising the following steps:
(1) Determination of total iron content in pickling waste liquid
Measuring the total iron content of the pickling waste liquid of the steel mill;
(2) Proportioning materials
According to the measurement result of the total iron content in the pickling waste liquid of the steel mill, the chemical formula (Sr) of the permanent magnetic ferrite is adopted 1-x M x ).(Fe 2n- y Me y )O 19 And the values of x, y and n in the chemical formula are determined, powdery raw materials are selected, and the ingredients are prepared;
(3) Precursor preparation of ferrite
Adding the metered raw materials into pickling waste liquid of a steel mill under stirring to form a reaction system, adding alkaline solution to adjust the pH value of the reaction system to 8-10, continuing stirring until the reaction system precipitates and forms a condensate, separating the condensate, cleaning the condensate with water, and stopping cleaning when the pH value of cleaning separation liquid is 7-8, wherein the obtained cleaned condensate is a precursor of ferrite;
(4) Drying and sintering of the precursor
Drying a precursor of ferrite, sintering in an air atmosphere at 800-1100 ℃ for 0.5-3 h, and cooling to room temperature along with a furnace after sintering to obtain permanent magnet ferrite magnetic powder;
chemical formula (Sr) of permanent magnetic ferrite 1-x M x ).(Fe 2n-y Me y )O 19 In (a): the Sr is prepared from strontium carbonate powder; the raw materials of M and Ca are calcium carbonate powder, calcium hydroxide powder or calcium oxide powder, the raw materials of La are lanthanum oxide powder, the raw materials of Ce are cerium oxide powder, and the raw materials of Pr are praseodymium oxide powder; the Me and Al are aluminum oxide powder or aluminum powder, the Co is cobalt oxide powder or cobalt powder, and the Zn is zinc oxide powder or zinc powder.
2. The method for preparing permanent magnetic ferrite magnetic powder by using pickling waste liquid of steel mill as claimed in claim 1, wherein in the step (3), the alkaline solution is one of sodium hydroxide solution, ammonia water, ammonium oxalate solution and ethylenediamine solution.
3. The method for preparing permanent magnetic ferrite magnetic powder by using pickling waste liquid of steel mill according to claim 1 or 2, wherein in the step (4), the drying temperature of the precursor of ferrite is 250-400 ℃ and the drying time is 1-2 h; the temperature rising rate from room temperature to sintering temperature is 2-10 ℃/min during sintering.
4. The method for preparing permanent magnetic ferrite powder from waste pickle liquor of steel mill according to claim 1 or 2, wherein in step (3), water for cleaning the condensate is deionized water or distilled water.
5. A method for producing permanent magnetic ferrite powder from steel mill pickle liquor as claimed in claim 3, wherein in step (3), the water for cleaning the condensate is deionized water or distilled water.
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| FR1311906A (en) * | 1960-10-18 | 1962-12-14 | Magnetic material and its preparation process | |
| CN101157548A (en) * | 2007-09-26 | 2008-04-09 | 中南大学 | Method for preparing high-performance manganese-zinc ferrite material |
| CN107056270A (en) * | 2017-05-31 | 2017-08-18 | 马鞍山市鑫洋永磁有限责任公司 | A kind of hexagonal sintered permanent ferrite magnet and preparation method thereof |
| CN107311635A (en) * | 2017-06-29 | 2017-11-03 | 中国医科大学附属第医院 | A kind of synthetic method of lanthanum zinc doping iron strontium oxide magnetic powder |
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|---|---|---|---|---|
| FR1311906A (en) * | 1960-10-18 | 1962-12-14 | Magnetic material and its preparation process | |
| CN101157548A (en) * | 2007-09-26 | 2008-04-09 | 中南大学 | Method for preparing high-performance manganese-zinc ferrite material |
| CN107056270A (en) * | 2017-05-31 | 2017-08-18 | 马鞍山市鑫洋永磁有限责任公司 | A kind of hexagonal sintered permanent ferrite magnet and preparation method thereof |
| CN107311635A (en) * | 2017-06-29 | 2017-11-03 | 中国医科大学附属第医院 | A kind of synthetic method of lanthanum zinc doping iron strontium oxide magnetic powder |
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