CN115595495A - Fe-Hf-rare earth intermediate alloy and preparation method thereof - Google Patents
Fe-Hf-rare earth intermediate alloy and preparation method thereof Download PDFInfo
- Publication number
- CN115595495A CN115595495A CN202211299372.XA CN202211299372A CN115595495A CN 115595495 A CN115595495 A CN 115595495A CN 202211299372 A CN202211299372 A CN 202211299372A CN 115595495 A CN115595495 A CN 115595495A
- Authority
- CN
- China
- Prior art keywords
- slag
- parts
- hafnium
- rare earth
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 112
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000003723 Smelting Methods 0.000 claims abstract description 41
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000000638 solvent extraction Methods 0.000 claims abstract description 12
- 238000009628 steelmaking Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 230000006698 induction Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000007670 refining Methods 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- 239000000779 smoke Substances 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910007926 ZrCl Inorganic materials 0.000 claims description 5
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052845 zircon Inorganic materials 0.000 abstract description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract description 4
- GVNLTKPENATPJA-UHFFFAOYSA-N 4-methylpentan-2-one;hydrochloride Chemical compound Cl.CC(C)CC(C)=O GVNLTKPENATPJA-UHFFFAOYSA-N 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 2
- 235000019738 Limestone Nutrition 0.000 abstract description 2
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000010436 fluorite Substances 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 abstract description 2
- 239000004571 lime Substances 0.000 abstract description 2
- 239000006028 limestone Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 abstract description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 abstract description 2
- 230000009471 action Effects 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- LAKFTXSXDDJHPQ-UHFFFAOYSA-N [Fe].[Hf] Chemical compound [Fe].[Hf] LAKFTXSXDDJHPQ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- USPBSVTXIGCMKY-UHFFFAOYSA-N hafnium Chemical compound [Hf].[Hf] USPBSVTXIGCMKY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2200/00—Recycling of waste material
-
- 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
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of rare earth alloy preparation, in particular to an iron-hafnium-rare earth intermediate alloy and a preparation method thereof, wherein the intermediate alloy comprises the following material components: 14-16.5 parts of Fe, 1.5-1.7 parts of Hf1.5 and 0.75-1.05 parts of rare earth elements; the invention utilizes the waste generated by steel making to stir and mix, adds in limestone, iron ore, fluorite and slag containing Si or silicon alloy to make pre-slag, then adds in aluminum wire or aluminum particle to deoxidize, and adds in lime and pre-slag to make white slag to desulfurize, and makes secondary slag to produce pure iron, at the same time makes alkali fusion of zircon by zircon chlorine, and uses the solvent extraction separation method of hydrochloric acid methyl isobutyl ketone system and tributyl phosphate system to separate hafnium chloride and zirconium chloride to make coarse hafnium sponge, and makes distillation on the coarse hafnium sponge to make high-purity hafnium, then uses high-purity iron and hafnium to add rare earth metal raw material to make smelting, and makes high-quality intermediate alloy after forming, and improves processing efficiency.
Description
Technical Field
The invention relates to the technical field of rare earth alloy preparation, in particular to an iron-hafnium-rare earth intermediate alloy and a preparation method thereof.
Background
The rare earth metal is one of the main components of the rare earth permanent magnet material, the addition amount can reach 30wt%, the magnetic property of the permanent magnet material can be improved after the rare earth metal is added, but the rare earth metal does not have the improvement effect on the high-temperature magnetism of the permanent magnet material, so that the rare earth permanent magnet material has defects. The metal hafnium can greatly improve the high-temperature demagnetization resistance of the permanent magnet material, but the hafnium has high chemical activity and melting point, is easy to burn at high temperature, causes difficulty in addition and can only be added in the form of intermediate alloy. Meanwhile, hafnium and rare earth metal are difficult to form alloy, so in order to improve the magnetic property of rare earth permanent magnet materials, rare earth elements are usually added in the form of iron-rare earth intermediate alloy, hafnium metal is added in the form of iron-hafnium intermediate alloy, the iron-rare earth intermediate alloy is mainly produced by an electrolytic method and a vacuum melting method, and the production technology is mature, but if the purity of iron or hafnium raw materials is not high in the production process, the impurities are more, and the produced intermediate alloy contains a large amount of impurities easily, so that the quality of products is affected.
Disclosure of Invention
The present invention is directed to provide an iron-hafnium-rare earth intermediate alloy and a method for preparing the same, which solve the problems set forth in the background art described above.
In order to achieve the purpose, the invention provides the following technical scheme: the iron-hafnium-rare earth intermediate alloy comprises the following material components: 14-16.5 parts of Fe, 1.5-1.7 parts of Hf1.5 and 0.75-1.05 parts of rare earth elements.
The preparation method of the iron-hafnium-rare earth intermediate alloy comprises the following steps:
s1, preparing pure iron, namely putting a mixture of converter steelmaking smoke dust and scrap steel and 98-105 parts of a converter steelmaking smoke dust mixture into an induction heating furnace for stirring, stirring the mixed materials at 1200-1480 ℃ for 0.5-1h until the mixed materials are completely melted and mixed together, and then sequentially adding 10-20 parts of CaO and CaMg (CO) 3 ) 2 5-10 parts of coarse smelting slag is produced by converter blowing at 1500-1610 ℃;
s2, in the slag discharging process in the step (S1), adding 8-12 parts of Al for carrying out deoxidation reaction, then adding 7.6-10.4 parts of CaO7 and 5.8-7.6 parts of premelting slag for carrying out slag washing, transferring the coarse smelting slag after the slag washing into a refining furnace, carrying out diffusion deoxidation by using 8.5-9.6 parts of carbon powder and 4.3-7.9 parts of ferrosilicon powder as reducing agents, taking the formed slag as white slag, carrying out desulfurization reaction on the coarse smelting slag in the refining furnace for 13-16min, carrying out slag fishing operation to reduce the thickness of a slag layer to be below 25mm, then adding the premelting slag into the refining furnace again for carrying out secondary slagging, carrying out iron content detection after slag discharging, injecting molten iron into a steel ladle after reaching a pure iron standard, adding 6.7-7.8 parts of Al for carrying out deoxidation, finally injecting into a mold for casting, and obtaining pure iron after solidification, namely Fe;
s3, preparing pure Hf, taking ZrSiO 4 4.6-7.3 parts of sodium hydroxide and 2.6-4.8 parts of NaHO are melted at 580-620 ℃, then KSiF2.1-3.3 parts of sodium hydroxide are used for sintering, KF solution containing Zr and Hf is obtained after water immersion, hfCl and ZrCl in the KF solution are separated by a solvent extraction separation method of a hydrochloric acid-MIBK system and an HNO-TBP system, mg2.2-5.2 parts of sodium hydroxide are added into the HfCl for reduction at 500-700 ℃, crude hafnium sponge is prepared, the crude hafnium sponge is distilled to remove MgCl and recover redundant metal magnesium, and the obtained finished product is hafnium sponge, namely the Hf metal with the purity of 99.999%;
s4, putting the raw materials of Fe, hf and the rare earth metal into a crucible, putting the crucible into a vacuum smelting furnace, heating to 1400-1500 ℃ to smelt for 15-32min, finally pouring the alloy melt in the crucible into a mould to cool and form, and demoulding to obtain the Fe-Hf-rare earth intermediate alloy.
Preferably, in the step S1, the induction heating furnace is a power frequency induction furnace, a medium frequency induction furnace or a high frequency induction furnace.
Preferably, in the step S1, the blowing temperature is controlled to be 1470-1630 ℃, the alkalinity of the crude slag is controlled to be 2.8-3.7, and the FeO content of the crude slag is 18-25%.
Preferably, in the step S2, the sulfur content of S in the slag-washed crude slag is less than 16ppm and 0 2 Is less than 9ppm.
Preferably, in the step S2, before the desulfurization reaction of the coarse smelting slag, caO and Al in the slag are controlled 2 O 3 The ratio of (A) to (B) is 0.8: 1-1.5: 1.
Preferably, in the step S2, after the reconstruction slag is finished and before slag is discharged, calcium treatment is performed, the soft blowing time is kept within 5-10min, and the temperature of the molten steel is controlled at 1700-1800 ℃.
Preferably, in step S3, the solvent extraction separation process is performed under an environment of 20 atmospheric pressures.
Preferably, in the step S3, the distillation of the hafnium sponge is performed in a vacuum environment.
Preferably, in the step S4, the vacuum degree in the vacuum smelting furnace is less than or equal to-0.1 MPa, and then nitrogen is filled as protective gas to keep the vacuum degree at-0.08 to-0.06 MPa.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the waste generated by steel making to stir and mix, adds in limestone, iron ore, fluorite and slag containing Si or silicon alloy to make pre-slag, then adds in aluminum wire or aluminum particle to deoxidize, and adds in lime and pre-slag to make white slag to desulfurize, and makes secondary slag to produce pure iron, at the same time makes alkali fusion of zircon by zircon chlorine, and uses the solvent extraction separation method of hydrochloric acid methyl isobutyl ketone system and tributyl phosphate system to separate hafnium chloride and zirconium chloride to make coarse hafnium sponge, and makes distillation on the coarse hafnium sponge to make high-purity hafnium, then uses high-purity iron and hafnium to add rare earth metal raw material to make smelting, and makes high-quality intermediate alloy after forming, and improves processing efficiency.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The first embodiment is as follows:
the preparation method of the iron-hafnium-rare earth intermediate alloy comprises the following steps:
s1, preparing pure iron, namely putting 98 parts of converter steelmaking smoke dust, waste steel mixture and converter steelmaking smoke dust mixture into an induction heating furnace for stirring, wherein the used induction heating furnace is a power frequency induction furnace, a medium frequency induction furnace or a high frequency induction furnace, the mixed materials are stirred for 0.5 hour at 1200 ℃ until the mixed materials are completely melted and mixed together, and then 10 parts of CaO and CaMg (CO) are sequentially added 3 ) 2 5 parts of the crude slag are blown in a converter at 1500 ℃ to produce crude slag;
s2, in the slag discharging process in the step (S1), 8 parts of Al are added for deoxidation reaction, 7.6 parts of CaO7 and 5.8 parts of premelted slag are added for slag washing, and the sulfur content of S in the coarse smelting slag after the slag washing is less than 16ppm and 0 2 The content of the pre-melted slag is less than 9ppm, the coarse smelting slag after slag washing is transferred to a refining furnace, 8.5 parts of carbon powder and 4.3 parts of ferrosilicon powder are used as reducing agents for diffusion deoxidation, the formed slag is used as white slag, after desulfurization reaction is carried out on the coarse smelting slag in the refining furnace for 13min, slag fishing operation is carried out, the thickness of a slag layer is reduced to be below 25mm, then the pre-melted slag is added into the refining furnace again for secondary slagging, after slag tapping, iron content detection is carried out, when the standard of pure iron is achieved, molten iron is injected into a steel ladle, 6.7 parts of AlO is added for deoxidation, finally, the molten iron is injected into a mold for casting, and pure iron is obtained after solidification, namely Fe;
s3, preparing pure Hf, taking ZrSiO 4 4.6 parts of the raw materials and 2.6 parts of NaOH2 are melted at 580 ℃, then KSiF2.1 parts of the raw materials are sintered, KF solution containing Zr and Hf is obtained after water immersion, and a solvent extraction separation method of a hydrochloric acid-MIBK system and an HNO-TBP system is adoptedSeparating HfCl and ZrCl in a KF solution, wherein a solvent extraction separation method is carried out under the environment of 20 atmospheric pressures, mg2.2 parts is added into HfCl to carry out reduction at 500 ℃ to prepare crude sponge hafnium, the crude sponge hafnium is distilled to remove MgCl and recover redundant metal magnesium, and the obtained finished product is sponge metal hafnium, namely Hf metal with the purity of 99.999%;
s4, putting raw materials of Fe, hf and rare earth metal into a crucible, putting the crucible into a vacuum smelting furnace, heating to 1400 ℃, smelting for 15min, finally pouring the alloy melt in the crucible into a mold, cooling and molding, and demolding to obtain the iron-hafnium-rare earth intermediate alloy.
The second embodiment:
the preparation method of the iron-hafnium-rare earth intermediate alloy comprises the following steps:
s1, preparing pure iron, namely putting 100 parts of converter steelmaking smoke dust, waste steel mixture and converter steelmaking smoke dust mixture into an induction heating furnace for stirring, wherein the used induction heating furnace is a power frequency induction furnace, a medium frequency induction furnace or a high frequency induction furnace, the mixed materials are stirred for 0.7h at 1300 ℃ until being completely melted and mixed together, and then, 15 parts of CaO and CaMg (CO) are sequentially added 3 ) 2 7, carrying out converter blowing at 1550 ℃ to produce crude smelting slag, wherein the blowing temperature is controlled at 1550 ℃, the alkalinity of the crude smelting slag is controlled at 3.5, and the FeO content of the crude smelting slag is 18%;
s2, in the slag discharging process in the step (S1), 10 parts of Al is added for deoxidation reaction, then 8.5 parts of CaO8 and 6.6 parts of premelted slag are added for slag washing, and the sulfur content of S in the slag-washed crude smelting slag is less than 16ppm and 0 2 The content of the slag is less than 9ppm, the coarse smelting slag after the slag washing is transferred to a refining furnace, 9.0 parts of carbon powder and 5.5 parts of ferrosilicon powder are used as reducing agents for diffusion deoxidation, the formed slag is used as white slag, and before the coarse smelting slag is subjected to desulfurization reaction, caO and Al in the slag are controlled 2 O 3 The ratio of (1) is 0.8: 1, carrying out desulfurization reaction on the crude slag in the refining furnace for 14min, carrying out slag fishing operation to reduce the thickness of a slag layer to be below 25mm, then adding the premelting slag into the refining furnace again for secondary slagging, carrying out iron content detection after slagging, and when the pure iron standard is reached, carrying out molten iron desulphurization reaction on the molten ironPouring into a steel ladle, adding 7.0 parts of AlO for deoxidation, finally pouring into a mould for pouring, and solidifying to obtain pure iron, namely Fe;
s3, preparing pure Hf, taking ZrSiO 4 5.8 parts of the hafnium sponge and 3.5 parts of NaHOH are melted at 600 ℃, then KSiF3.0 parts of the hafnium sponge are sintered, a KF solution containing Zr and Hf is obtained after water immersion, hfCl and ZrCl in the KF solution are separated by a solvent extraction separation method of a hydrochloric acid-MIBK system and a HNO-TBP system, the solvent extraction separation method is carried out under the environment of 20 atmospheric pressures, mg4.5 parts of the hafnium sponge are added into the HfCl and reduced at 600 ℃ to prepare crude hafnium sponge, the crude hafnium sponge is subjected to vacuum distillation to remove MgCl and recover redundant magnesium metal, and the obtained finished product is hafnium sponge, namely the Hf metal with the purity of 99.999%;
s4, putting raw materials of Fe, hf and rare earth metal into a crucible, putting the crucible into a vacuum smelting furnace, heating to 1450 ℃, smelting for 28min, finally pouring the alloy melt in the crucible into a mold, cooling and molding, and demolding to obtain the iron-hafnium-rare earth intermediate alloy.
Example three:
the preparation method of the iron-hafnium-rare earth intermediate alloy comprises the following steps:
s1, preparing pure iron, namely putting 105 parts of converter steelmaking smoke dust, waste steel mixture and converter steelmaking smoke dust mixture into an induction heating furnace for stirring, wherein the used induction heating furnace is a power frequency induction furnace, a medium frequency induction furnace or a high frequency induction furnace, the mixed materials are stirred for 1 hour at 1480 ℃ until the mixed materials are completely melted and mixed together, and then 20 parts of CaO and CaMg (CO) are sequentially added 3 ) 2 10 parts of the coarse smelting slag is blown in a converter at 1610 ℃ to produce coarse smelting slag, the blowing temperature is controlled at 1630 ℃, the alkalinity of the coarse smelting slag is controlled at 3.7, and the FeO content of the coarse smelting slag is 25%;
s2, in the slag discharging process in the step (S1), 12 parts of Al are added for deoxidation reaction, 10.4 parts of CaO10 and 7.6 parts of premelted slag are added for slag washing, and the sulfur content of S in the coarse smelting slag after the slag washing is less than 16ppm and 0 2 The content of the iron-silicon-containing slag is less than 9ppm, the crude smelting slag after the slag washing is transferred to a refining furnace, 9.6 parts of carbon powder and 7.9 parts of ferrosilicon powder are used as reducing agents for diffusion deoxidation, and the formed productThe slag is used as white slag, caO and Al in the slag are controlled before the coarse smelting slag is subjected to desulfurization reaction 2 O 3 The ratio of the coarse slag to the coarse slag is 1.5: 1, after 16min of desulfurization reaction is carried out on the coarse slag in the refining furnace, slag salvaging is carried out, the thickness of a slag layer is reduced to be below 25mm, then the premelting slag is added into the refining furnace again for secondary slag making, after the slag reconstruction is finished, calcium treatment is carried out before slag tapping, the soft blowing time is kept within 10min, the temperature of molten steel is controlled to be 1800 ℃, after slag tapping, iron content detection is carried out, after the standard of pure iron is achieved, molten iron is injected into a steel ladle, 7.8 parts of AlO is added for deoxidation, finally, the molten iron is injected into a mold for pouring, and pure iron is obtained after solidification, namely Fe;
s3, preparing pure Hf, taking ZrSiO 4 7.3 parts of the hafnium sponge and 4.8 parts of NaHOH are melted at 620 ℃, then KSiF3.3 parts of the hafnium sponge are sintered, KF solution containing Zr and Hf is obtained after water immersion, hfCl and ZrCl in the KF solution are separated by a solvent extraction separation method of a hydrochloric acid-MIBK system and a HNO-TBP system, the solvent extraction separation method is carried out under the environment of 20 atmospheric pressures, mg5.2 parts of the hafnium sponge are added into the HfCl and reduced at 700 ℃ to obtain crude hafnium sponge, the crude hafnium sponge is subjected to vacuum distillation to remove MgCl and recover redundant metal magnesium, and the obtained finished product is the hafnium sponge, namely the Hf metal with the purity of 99.999%;
s4, putting the raw materials of Fe, hf and rare earth metal into a crucible, putting the crucible into a vacuum smelting furnace, heating to 1500 ℃ for smelting for 32min, wherein the vacuum degree in the vacuum smelting furnace is less than or equal to-0.1 MPa, then filling nitrogen as protective gas, keeping the vacuum degree at-0.08 to-0.06 MPa, finally pouring the alloy solution in the crucible into a mold for cooling and molding, and demolding to obtain the Fe-Hf-rare earth intermediate alloy.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. An iron-hafnium-rare earth master alloy characterized by: the material comprises the following components: 14-16.5 parts of Fe, 1.5-1.7 parts of Hf1.5 and 0.75-1.05 parts of rare earth elements.
2. The preparation method of the iron-hafnium-rare earth intermediate alloy is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, preparing pure iron, namely putting a mixture of converter steelmaking smoke dust and scrap steel and 98-105 parts of a converter steelmaking smoke dust mixture into an induction heating furnace for stirring, stirring the mixed materials at 1200-1480 ℃ for 0.5-1h until the mixed materials are completely melted and mixed together, and then sequentially adding 10-20 parts of CaO and CaMg (CO) 3 ) 2 5-10 parts of coarse smelting slag is produced by converter blowing at 1500-1610 ℃;
s2, in the slag discharging process in the step (S1), adding 8-12 parts of Al for carrying out deoxidation reaction, then adding 7.6-10.4 parts of CaO7 and 5.8-7.6 parts of premelting slag for carrying out slag washing, transferring the coarse smelting slag after the slag washing into a refining furnace, carrying out diffusion deoxidation by using 8.5-9.6 parts of carbon powder and 4.3-7.9 parts of ferrosilicon powder as reducing agents, taking the formed slag as white slag, carrying out desulfurization reaction on the coarse smelting slag in the refining furnace for 13-16min, carrying out slag fishing operation to reduce the thickness of a slag layer to be below 25mm, then adding the premelting slag into the refining furnace again for carrying out secondary slagging, carrying out iron content detection after slag discharging, injecting molten iron into a steel ladle after reaching a pure iron standard, adding 6.7-7.8 parts of Al for carrying out deoxidation, finally injecting into a mold for casting, and obtaining pure iron after solidification, namely Fe;
s3, preparing pure Hf, taking ZrSiO 4 4.6-7.3 parts of sodium hydroxide and 2.6-4.8 parts of NaHO are melted at 580-620 ℃, then KSiF2.1-3.3 parts of sodium hydroxide are used for sintering, KF solution containing Zr and Hf is obtained after water immersion, hfCl and ZrCl in the KF solution are separated by a solvent extraction separation method of a hydrochloric acid-MIBK system and an HNO-TBP system, mg2.2-5.2 parts of sodium hydroxide are added into the HfCl for reduction at 500-700 ℃, crude hafnium sponge is prepared, the crude hafnium sponge is distilled to remove MgCl and recover redundant metal magnesium, and the obtained finished product is hafnium sponge, namely the Hf metal with the purity of 99.999%;
s4, putting raw materials of Fe, hf and rare earth metal into a crucible, putting the crucible into a vacuum smelting furnace, heating to 1400-1500 ℃, smelting for 15-32min, finally pouring the alloy melt in the crucible into a mold, cooling and molding, and demolding to obtain the Fe-Hf-rare earth intermediate alloy.
3. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S1, the induction heating furnace is a power frequency induction furnace, a medium frequency induction furnace or a high frequency induction furnace.
4. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S1, the blowing temperature is controlled to be 1470-1630 ℃, the alkalinity of the crude smelting slag is controlled to be 2.8-3.7, and simultaneously the FeO content of the crude smelting slag is 18-25%.
5. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S2, the sulfur content of S in the coarse smelting slag after slag washing is less than 16ppm and 0 2 Is less than 9ppm.
6. The method of preparing an iron-hafnium-rare earth master alloy of claim 2, wherein: in the step S2, before the desulfurization reaction of the coarse smelting slag, the control is carried outCaO and Al in slag 2 O 3 The ratio of (A) to (B) is 0.8: 1-1.5: 1.
7. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S2, after the reconstruction slag is finished, calcium treatment is carried out before slag discharging, the soft blowing time is kept within 5-10min, and the temperature of molten steel is controlled to be 1700-1800 ℃.
8. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S3, the solvent extraction and separation method is performed under an environment of 20 atmospheres.
9. The method of preparing an iron-hafnium-rare earth master alloy according to claim 2, wherein: in the step S3, the distillation of the hafnium sponge is performed in a vacuum environment.
10. The method of preparing an iron-hafnium-rare earth master alloy of claim 2, wherein: in the step S4, the vacuum degree in the vacuum smelting furnace is less than or equal to minus 0.1MPa, and then nitrogen is filled as protective gas to keep the vacuum degree at minus 0.08 to minus 0.06MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211299372.XA CN115595495A (en) | 2022-10-24 | 2022-10-24 | Fe-Hf-rare earth intermediate alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211299372.XA CN115595495A (en) | 2022-10-24 | 2022-10-24 | Fe-Hf-rare earth intermediate alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115595495A true CN115595495A (en) | 2023-01-13 |
Family
ID=84849372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211299372.XA Pending CN115595495A (en) | 2022-10-24 | 2022-10-24 | Fe-Hf-rare earth intermediate alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115595495A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008115063A (en) * | 2006-11-06 | 2008-05-22 | Mitsuhide Kawasaki | High purity hafnium material and method of manufacturing the material by using solvent extraction method |
| CN108517458A (en) * | 2018-05-18 | 2018-09-11 | 全南晶环科技有限责任公司 | iron-hafnium-rare earth intermediate alloy and preparation method thereof |
| CN108998683A (en) * | 2017-06-06 | 2018-12-14 | 叶安祺 | The method for separating zirconium oxide and hafnium oxide mixture |
| CN110129588A (en) * | 2019-06-03 | 2019-08-16 | 南通晶朋新材料科技有限公司 | A kind of preparation method of high purity metal hafnium |
| CN113512619A (en) * | 2021-06-30 | 2021-10-19 | 湖南华菱湘潭钢铁有限公司 | Production method of industrial pure iron |
-
2022
- 2022-10-24 CN CN202211299372.XA patent/CN115595495A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008115063A (en) * | 2006-11-06 | 2008-05-22 | Mitsuhide Kawasaki | High purity hafnium material and method of manufacturing the material by using solvent extraction method |
| CN108998683A (en) * | 2017-06-06 | 2018-12-14 | 叶安祺 | The method for separating zirconium oxide and hafnium oxide mixture |
| CN108517458A (en) * | 2018-05-18 | 2018-09-11 | 全南晶环科技有限责任公司 | iron-hafnium-rare earth intermediate alloy and preparation method thereof |
| CN110129588A (en) * | 2019-06-03 | 2019-08-16 | 南通晶朋新材料科技有限公司 | A kind of preparation method of high purity metal hafnium |
| CN113512619A (en) * | 2021-06-30 | 2021-10-19 | 湖南华菱湘潭钢铁有限公司 | Production method of industrial pure iron |
Non-Patent Citations (1)
| Title |
|---|
| 中国大百科全书总编辑委员会《矿冶》编辑委员会: "《中国大百科全书 矿冶》", 中国大百科全书出版社, pages: 236 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103060513B (en) | Method for smelting tire cord steel and method for continuously casting tire cord steel | |
| CA3017325C (en) | Gray cast iron inoculant | |
| CN101333579B (en) | Method for producing tube blank steel for nuclear electricity | |
| CN108330245A (en) | A kind of high-purity smelting process of stainless steel | |
| CN102071287A (en) | Method for melting high-temperature-resistance and high-pressure-resistance alloy steel | |
| CN111910045A (en) | Smelting method of high-purity austenitic stainless steel | |
| CN113774277B (en) | Ultra-low carbon and ultra-low manganese industrial pure iron and preparation method thereof | |
| TWI300444B (en) | Method for reducing cr from cr-containing metallurgical slags | |
| CN115595495A (en) | Fe-Hf-rare earth intermediate alloy and preparation method thereof | |
| CN111349803A (en) | Method for preparing yttrium intermediate alloy | |
| KR20140037831A (en) | Method for manufacturing stainless steel | |
| CN1011981B (en) | Process for continuously melting of steel | |
| CN102766729A (en) | Low phosphor control method for high-speed axle steel | |
| CN110373599B (en) | Refining method of high-toughness alloy steel | |
| CN111041240B (en) | Method for preparing ferrotitanium alloy by using perovskite concentrate as raw material | |
| CN102220452B (en) | Method for duplex dephosphorization of intermediate frequency furnace and vacuum induction furnace | |
| CN111057877A (en) | Ingredient for refining vanadium from low-grade vanadium waste residue | |
| CN109536839A (en) | A kind of midium-carbon steel ingot and production method | |
| CN1363698A (en) | Process for preparing Mn-Si alloy from slags generated by smelting low-carbon ferromanganese | |
| CN101260454A (en) | Preparation of calcium-iron alloy for smelting steel by using calcium carbide as raw material and calcium-containing composite desoxidant | |
| CN112458237B (en) | Steelmaking method for reducing slag quantity and modifying slag components on line | |
| CN116970872A (en) | Aluminum-silicon-calcium-iron alloy and preparation method and application thereof | |
| CN111910046A (en) | Strong-deoxidation high-purity aluminum-iron alloy and preparation method thereof | |
| CN106555025A (en) | A kind of low field trash production method for cord steel | |
| CN117187563A (en) | Micro-carbon ferromanganese alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230113 |