CN113481545A - Lanthanum-iron alloy - Google Patents

Lanthanum-iron alloy Download PDF

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CN113481545A
CN113481545A CN202110377619.4A CN202110377619A CN113481545A CN 113481545 A CN113481545 A CN 113481545A CN 202110377619 A CN202110377619 A CN 202110377619A CN 113481545 A CN113481545 A CN 113481545A
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lanthanum
iron
alloy
content
iron alloy
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CN113481545B (en
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刘玉宝
赵二雄
张志宏
陈国华
高日增
吕卫东
于雅樵
于兵
陈宇昕
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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
    • 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
    • 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

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Abstract

The invention discloses a lanthanum-iron alloy, wherein the content of lanthanum is 10.04-50.05 wt% and 59.97-95.06 wt%, the balance is iron and inevitable impurities with the total amount less than 0.5 wt%, wherein the content of oxygen is less than or equal to 0.01 wt%, the content of carbon is less than or equal to 0.01 wt%, the content of phosphorus is less than or equal to 0.01 wt%, and the content of sulfur is less than or equal to 0.005 wt%. Compared with the rare earth iron alloy prepared by a consumable cathode method, the lanthanum iron alloy prepared by the method has more uniform components, and the lanthanum content can be accurately controlled.

Description

Lanthanum-iron alloy
This patent application is application number: 201611168972.7, name: lanthanum-iron alloy and a preparation method thereof, application date: division application 12/16/2016.
Technical Field
The invention belongs to the technical field of rare earth ferroalloy, and particularly relates to lanthanum ferroalloy.
Background
At present, steel is the first major metal structural material and is widely applied to the fields of buildings, energy sources, transportation, aerospace and the like. The application and research of rare earth in steel are also rapidly developed, and the rare earth added into molten steel can play roles in desulfurization, deoxidation, inclusion form change and the like, and can improve the plasticity, stamping property, wear resistance and welding property of steel. Various rare earth steels such as rare earth steel plates for automobiles, die steel, steel rails and the like are widely applied.
The method for adding rare earth in the process of producing rare earth steel is always the key point of research, the existing adding method comprises various forms such as a wire feeding method, a core-spun wire, a rare earth iron intermediate alloy and the like, and the existing adding method has obvious effect. The technology for preparing the rare-earth-iron intermediate alloy mainly comprises the following steps:
(1) a mixed dissolution method.
The mixing and dissolving method is also called as a counter-doping method, and mainly utilizes an electric arc furnace or an intermediate frequency induction furnace to mix and dissolve rare earth metals and iron to prepare alloy. The method is a commonly adopted method at present, has simple process technology, can prepare multi-element intermediate alloy or application alloy, but has the following defects: 1) the local concentration of rare earth metal in the molten iron is easy to be too high, and segregation is generated; 2) the raw materials adopted by the method are rare earth metals, particularly medium and heavy rare earth metals, the preparation process is complex, and the cost is high; 3) the smelting temperature is high, and the requirement on the smelting temperature is high due to the fact that rare earth metal and pure iron are used as raw materials.
(2) Molten salt electrolysis.
The molten salt electrolysis method for preparing the rare earth iron intermediate alloy mainly adopts an iron consumable cathode method. For example, chinese patent CN1827860 discloses a process and equipment for producing dysprosium-iron alloy by molten salt electrolysis, which proposes that under the condition of high temperature, dysprosium oxide dissolved in fluoride solution is ionized, dysprosium ions are precipitated on the surface of an iron cathode under the action of a direct current electric field and reduced into metal dysprosium, and dysprosium is alloyed with iron to form dysprosium-iron alloy. The method has low production cost and simple process, but also has the following defects: the rare earth and iron in the alloy have large distribution fluctuation and are difficult to control, and the distribution error is up to 3-5 percent, thereby influencing the consistency of products.
Disclosure of Invention
Compared with rare earth iron alloy prepared by a consumable cathode method, the lanthanum iron alloy obtained by the method has more uniform components, and the lanthanum content can be accurately controlled.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
lanthanum-iron alloy, lanthanum content is 10.04-50.05 wt% and 59.97-95.06 wt%, the rest is iron and inevitable impurities with the total amount less than 0.5 wt%, wherein oxygen is less than or equal to 0.01 wt%, carbon is less than or equal to 0.01 wt%, phosphorus is less than or equal to 0.01 wt%, and sulfur is less than or equal to 0.005 wt%.
Further: the lanthanum content is 10.04-50.03 wt%.
Further: the lanthanum content is 10.11-50.05 wt%.
Further: the content of lanthanum is 29.98-50.05 wt%.
Further: the lanthanum content is 30.05-50.05 wt%.
Further: the content of lanthanum is 59.97-69.98 wt%.
Further: in the equipment for electrolyzing the lanthanum-iron intermediate alloy, under a fluoride molten salt electrolyte system of lanthanum fluoride and lithium fluoride, lanthanum oxide is taken as an electrolysis raw material, and direct current is introduced for electrolysis to obtain the lanthanum-iron intermediate alloy; the lanthanum-iron intermediate alloy and iron are used as raw materials, and the lanthanum-iron alloy is prepared by adopting a melting method.
Further: the equipment for melting the lanthanum-iron intermediate alloy is a medium-frequency induction furnace, the melting process is carried out under the vacuum condition, and the crucible adopts a rare earth oxide crucible.
Further: the material of the receiver is iron, rare earth oxide or boron nitride.
Further: adding metal lanthanum or iron in the vacuum melting process.
The invention has the technical effects that:
compared with the prior art, the invention has the technical effects that: the invention develops a new molten salt electrolysis process aiming at the problems in the prior art, the prepared lanthanum-iron alloy has the advantages of uniform components, small segregation, low impurity content, high rare earth yield, low cost and no pollution, and the rare earth alloy applied to rare earth steel has high rare earth yield and obvious effect and is suitable for large-scale industrial production.
1. In the invention, the lanthanum-iron alloy has the advantages that:
(1) the impurity content is low.
The lanthanum-iron alloy provided by the invention adopts pure lanthanum oxide as a raw material, and the smelting crucible is made of iron and rare earth oxide substances, so that the introduced impurity content is low.
(2) The components are uniform, and the lanthanum content is controllable.
Compared with the consumable cathode, the lanthanum-iron alloy has more uniform components and accurately controllable lanthanum content. Practice proves that the alloy of the invention can be used for preparing high-performance rare earth steel products.
2. The preparation method of the lanthanum-iron alloy disclosed by the invention has the advantages that:
(1) lanthanum oxide is used as an electrolysis raw material, so that only CO, CO2 and a very small amount of fluorine-containing gas are generated in the electrolysis process, and the environmental pollution is small.
(2) The pure iron rod is used as a consumable cathode, and lanthanum and iron separated out by electrolysis form lanthanum-iron alloy with low melting point, which is beneficial to reducing the electrolysis temperature.
(3) The lanthanum-iron alloy obtained after the lanthanum-iron intermediate alloy obtained by molten salt electrolysis is subjected to vacuum melting is accurately controlled in component, and due to the fact that melting is carried out in vacuum, rare earth burning loss is small, yield is high, and product quality is high.
3. Has wide development and market prospect.
Along with the development of national economic construction, steel is required to have high strength and toughness and good corrosion resistance, and the rare earth plays a key role in the aspect. The rare earth also has important function in improving the toughness, plasticity, heat resistance, oxidation resistance and wear resistance of steel. China is the first major country of steel yield, and the reinforcement of the application of rare earth has great significance in the field with large quantity and wide range. One of the important influencing factors for limiting the industrialization process of the rare earth steel is the adding mode of the rare earth in the steel, and the most effective mode developed at present is adding the rare earth iron master alloy. Taking 500 ten thousand tons of rare earth steel plates produced annually by a steel (group) covering company as an example, 2.5 ten thousand tons of 10% rare earth ferroalloy is required to be consumed, and the economic benefit is remarkable. The implementation of the invention has certain promotion effects on improving the industrial structure of the region and promoting the scientific and technological strength of the region; on the other hand, the rare earth alloy is smelted every year and is completely applied to the rare earth steel, so that great economic benefit can be generated, the situation that the steel situation is not ideal in China can be turned, and the application prospect is wide; can find a way for cheap rare earth, and can help the healthy and sustainable development of the rare earth industry and the steel industry.
Drawings
FIG. 1 is a schematic structural view of an apparatus for electrolyzing an lanthanum-iron intermediate alloy in accordance with the present invention;
FIG. 2 is a flow chart of a process for preparing lanthanum-iron alloy according to the present invention.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
FIG. 1 is a schematic structural view of an apparatus for electrolyzing an lanthanum-iron intermediate alloy according to the present invention; FIG. 2 shows a flow chart of a lanthanum-iron alloy preparation process in the present invention.
The structure of the equipment for electrolyzing the lanthanum-iron intermediate alloy used by the invention comprises: 1 of refractory brick, 2 of iron sleeve, 3 of rare earth oxide crucible, 4 of lanthanum-iron alloy, 5 of anode plate, 6 of iron cathode, 7 of electrolyte, 8 of electrolytic bath, 9 of heat preservation layer and 10 of carbon ramming layer.
The electrolytic bath 8 is a graphite bath, and the outer side of the graphite bath body is sequentially coated with a carbon tamping layer 10, a heat insulation layer 9, a refractory brick 1 and an iron sleeve 2; an iron cathode 6 is arranged in the middle of the graphite tank; an anode plate 5 is arranged around the iron cathode 6 in the graphite groove; the rare earth oxide crucible 3 is arranged at the center of the bottom of the graphite groove, and the rare earth oxide crucible 3 is opposite to the iron cathode 6. When the lithium iron alloy crucible is used, the electrolyte 7 is filled in the graphite tank, the electrolyte 7 adopts a lanthanum fluoride and lithium fluoride molten salt electrolyte, and the lanthanum iron alloy 4 is filled in the rare earth oxide crucible 3.
The preparation process of lanthanum-iron alloy for producing rare earth steel comprises the following steps:
step 1: taking graphite as an electrolytic tank, taking a graphite plate as an anode, taking an iron rod as a consumable cathode, and arranging a receiver for containing alloy below the cathode;
the receiver material may be one of iron, rare earth oxide, and boron nitride.
Step 2: in a fluoride molten salt electrolyte system of lanthanum fluoride and lithium fluoride, lanthanum oxide is used as an electrolysis raw material, and direct current is introduced for electrolysis to obtain a lanthanum-iron intermediate alloy;
and step 3: lanthanum-iron intermediate alloy and iron are used as raw materials, and a melting method is adopted to prepare the lanthanum-iron alloy meeting the requirements.
The equipment for melting the lanthanum-iron intermediate alloy is a medium-frequency induction furnace. The melting and mixing process is carried out under vacuum condition, and the crucible adopts rare earth oxide crucible.
In the lanthanum-iron alloy, the content of lanthanum is 0-95 wt%, the balance is iron and inevitable impurities with the total amount less than 0.5 wt%, wherein the content of oxygen is less than or equal to 0.01 wt%, the content of carbon is less than or equal to 0.01 wt%, the content of phosphorus is less than or equal to 0.01 wt%, and the content of sulfur is less than or equal to 0.005 wt%.
The metal detection adopts ICP-MS test according to national standards such as GB/T18115.1-2006 and the like; the detection of C is tested by a high-frequency combustion-infrared method according to GB/T12690.13-1990; the test of O is carried out according to GB/T12690.4-2003 by using an inert gas pulse-infrared method. The standard deviation S of the chemical composition is calculated by the following formula:
Figure BDA0003011862730000051
wherein XiIs the chemical composition of the sample; the average value of X is the average value of chemical components of n points of the sample, and n is 20 in the invention.
Example 1
Adopting a round graphite electrolytic cell with the diameter of 650mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the current density of the anode is 0.5-1.0A/cm2Cathode current density of 5-20A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90 percent, the current efficiency is 80 percent, and the alloy composition results are shown in Table 1.
TABLE 1 composition analysis of lanthanum-iron master alloy/wt%
La Fe C O P S Si Mn
90.0 9.85 0.0085 0.0094 ＜0.01 ＜0.005 0.012 ＜0.005
Taking 1.7kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 13.3kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the components of the lanthanum-iron alloy obtained after smelting are shown in table 2.
TABLE 2 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
10.11 89.73 0.0080 0.0095 ＜0.01 ＜0.005 0.008 ＜0.005
Example 2
Adopting a round graphite electrolytic cell with the diameter of 650mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the current density of the anode is 0.5-1.0A/cm2Cathode current density of 5-20A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90 percent, the current efficiency is 80 percent, and the alloy composition results are shown in Table 3.
TABLE 3 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
90.0 9.85 0.0085 0.0094 ＜0.01 ＜0.005 0.012 ＜0.005
Taking 5kg of lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 10kg of iron rod, smelting in a 30kg medium-frequency vacuum induction furnace with argon as protective gas, selecting a lanthanum oxide crucible as the crucible, and obtaining lanthanum-iron components after smelting as shown in table 4.
TABLE 4 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
29.98 69.74 0.0088 0.0089 ＜0.01 ＜0.005 0.004 ＜0.005
Example 3
Adopting a round graphite electrolytic cell with the diameter of 650mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the current density of the anode is 0.5-1.0A/cm2Cathode current density of 5-20A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90 percent, the current efficiency is 80 percent, and the alloy composition results are shown in Table 5.
TABLE 5 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
90.0 9.85 0.0085 0.0094 ＜0.01 ＜0.005 0.012 ＜0.005
Taking 8.4kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 6.6kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 6.
TABLE 6 composition analysis of lanthanum-iron alloy/wt%
La Fe C O P S Si Mn
50.05 49.74 0.0074 0.0093 ＜0.01 ＜0.005 0.003 ＜0.005
Example 4
Adopting a round graphite electrolytic cell with the diameter of 650mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the current density of the anode is 0.5-1.0A/cm2Cathode current density of 5-20A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90 percent, the current efficiency is 80 percent, and the alloy composition results are shown in Table 7.
TABLE 7 composition analysis of lanthanum-iron master alloy/wt%
La Fe C O P S Si Mn
90.0 9.85 0.0085 0.0094 ＜0.01 ＜0.005 0.012 ＜0.005
Taking 11.7kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 3.3kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 8.
TABLE 8 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
70.04 29.66 0.0076 0.0086 ＜0.01 ＜0.005 0.0024 ＜0.005
Example 5
Adopting a round graphite electrolytic cell with the diameter of 650mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the current density of the anode is 0.5-1.0A/cm2Cathode current density of 5-20A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90 percent, the current efficiency is 80 percent, and the alloy composition results are shown in Table 9.
TABLE 9 composition analysis of lanthanum iron master alloy/wt.%
La Fe C O P S Si Mn
90.0 9.85 0.0085 0.0094 ＜0.01 ＜0.005 0.012 ＜0.005
Taking the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, taking 7.5kg of the lanthanum-iron intermediate alloy and adding 7.5kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron components obtained after smelting are shown in table 10.
TABLE 10 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
95.03 4.76 0.0097 0.0076 ＜0.01 ＜0.005 0.010 ＜0.005
Example 6
Adopting a round graphite electrolytic cell with the diameter of 700mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 75 wt%, the lithium fluoride accounts for 25 wt%, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm2Cathode current density of 8-25A/cm2The electrolysis temperature is maintained at 900-After 300 hours of decomposition, 2688kg of lanthanum oxide was consumed, and 2615kg of lanthanum-iron master alloy was prepared, the average lanthanum content was 85.02%, the current efficiency was 78%, and the alloy composition results are shown in table 11.
TABLE 11 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
85.02 14.84 0.0075 0.0084 ＜0.01 ＜0.005 0.017 ＜0.005
Taking 1.8kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 13.2kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 12.
TABLE 12 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
10.04 89.66 0.0070 0.0080 ＜0.01 ＜0.005 0.003 ＜0.005
Example 7
A round graphite electrolytic cell with the diameter of 700mm is adopted, the anode consists of four graphite plates, the lanthanum fluoride accounts for 75 wt%, the lithium fluoride accounts for 25 wt%, and the cathode is straightPure iron rod with diameter of 75mm, average current intensity of 5500A and anode current density of 0.4-0.8A/cm2Cathode current density of 8-25A/cm2The electrolysis temperature is maintained at 900-1050 ℃, the continuous electrolysis is carried out for 300 hours, 2688kg of lanthanum oxide is consumed, and the lanthanum-iron master alloy 2615kg is prepared, the average lanthanum content is 85.02%, the current efficiency is 78%, and the alloy composition results are shown in Table 13.
TABLE 13 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
85.02 14.84 0.0075 0.0084 ＜0.01 ＜0.005 0.017 ＜0.005
Taking 5.3kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 9.7kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 14.
TABLE 14 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
30.05 69.77 0.0070 0.0086 ＜0.01 ＜0.005 0.0024 ＜0.005
Example 8
Adopting a round graphite electrolytic cell with the diameter of 700mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 75 wt%, the lithium fluoride accounts for 25 wt%, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm2Cathode current density of 8-25A/cm2The electrolysis temperature was maintained at 900-.
TABLE 15 composition analysis of lanthanum iron master alloy/wt.%
La Fe C O P S Si Mn
85.02 14.84 0.0075 0.0084 ＜0.01 ＜0.005 0.017 ＜0.005
Taking 8.8kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 6.2kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 16.
TABLE 16 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
50.03 49.78 0.0064 0.0087 ＜0.01 ＜0.005 0.0021 ＜0.005
Example 9
Adopting a round graphite electrolytic cell with the diameter of 700mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 75 wt%, the lithium fluoride accounts for 25 wt%, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm2Cathode current density of 8-25A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and the lanthanum oxide was consumed by continuous electrolysis for 300 hours to obtain 2615kg of lanthanum-iron master alloy, the average lanthanum content was 85.02%, the current efficiency was 78%, and the alloy composition results are shown in Table 17.
TABLE 17 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
85.02 14.84 0.0075 0.0084 ＜0.01 ＜0.005 0.017 ＜0.005
Taking the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, taking 12.4kg of lanthanum intermediate alloy and adding 2.6kg of iron rod, smelting in a 30kg medium-frequency vacuum induction furnace with argon as protective gas, selecting a lanthanum oxide crucible as the crucible, and obtaining lanthanum-iron components after smelting, which are shown in table 18.
TABLE 18 composition analysis of lanthanum-iron alloy/wt.%
RE Fe C O P S Si Mn
69.98 29.74 0.0078 0.0090 ＜0.01 ＜0.005 0.0018 ＜0.005
Example 10
Adopting a round graphite electrolytic cell with the diameter of 700mm, wherein the anode consists of four graphite plates, the lanthanum fluoride accounts for 75 wt%, the lithium fluoride accounts for 25 wt%, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the current density of the anode is 0.4-0.8A/cm2Cathode current density of 8-25A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and the lanthanum oxide was consumed by continuous electrolysis for 300 hours to obtain 2615kg of lanthanum-iron master alloy, the average lanthanum content was 85.02%, the current efficiency was 78%, and the alloy composition results are shown in Table 19.
TABLE 19 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
85.02 14.84 0.0075 0.0084 ＜0.01 ＜0.005 0.017 ＜0.005
Taking 5kg of lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 10kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace with argon as protective gas, selecting a lanthanum oxide crucible as the crucible, and obtaining lanthanum-iron components after smelting as shown in table 20.
TABLE 20 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
95.06 4.69 0.0094 0.0093 ＜0.01 ＜0.005 0.0034 ＜0.005
Example 11
A round graphite electrolytic cell with the diameter of 700mm is adopted, the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm2Cathode current density of 10-20A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and continuous electrolysis was carried out for 200 hours, consuming 2030kg of lanthanum oxide, producing 1766kg of lanthanum-iron alloy, with an average lanthanum content of 95.06%, a current efficiency of 81% and alloy composition results as shown in Table 21.
TABLE 21 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
95.06 4.64 0.0042 0.0065 ＜0.01 ＜0.005 0.014 ＜0.005
Taking 3.2kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 11.8kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 22.
TABLE 22 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
19.98 79.76 0.0040 0.0071 ＜0.01 ＜0.005 0.0088 ＜0.005
Example 12
A round graphite electrolytic cell with the diameter of 700mm is adopted, the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm2Cathode current density of 10-20A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and continuous electrolysis was carried out for 200 hours, consuming 2030kg of lanthanum oxide, producing 1766kg of lanthanum-iron alloy, with an average lanthanum content of 95.06%, a current efficiency of 81% and alloy composition results as shown in Table 23.
TABLE 23 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
95.06 4.64 0.0042 0.0065 ＜0.01 ＜0.005 0.014 ＜0.005
Taking 6.3kg of the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, adding 8.7kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 24.
TABLE 24 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
40.06 59.63 0.0038 0.0072 ＜0.01 ＜0.005 0.0079 ＜0.005
Example 13
A round graphite electrolytic cell with the diameter of 700mm is adopted, the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm2Cathode current density of 10-20A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and continuous electrolysis was carried out for 200 hours, consuming 2030kg of lanthanum oxide, producing 1766kg of lanthanum-iron alloy, with an average lanthanum content of 95.06%, a current efficiency of 81% and alloy composition results as shown in Table 25.
TABLE 25 composition analysis of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
95.06 4.64 0.0042 0.0065 ＜0.01 ＜0.005 0.014 ＜0.005
Taking the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, taking 9.5kg of the lanthanum-iron intermediate alloy, adding 5.5kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, the crucible is a lanthanum oxide crucible, and the lanthanum-iron components obtained after smelting are shown in table 26.
TABLE 26 composition analysis of lanthanum-iron alloy/wt.%
La Fe C O P S Si Mn
59.97 39.62 0.0041 0.0075 ＜0.01 ＜0.005 0.0080 ＜0.005
Example 14
A round graphite electrolytic cell with the diameter of 700mm is adopted, the anode consists of four graphite plates, the lanthanum fluoride accounts for 80 wt%, the lithium fluoride accounts for 20 wt%, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm2Cathode current density of 10-20A/cm2The electrolysis temperature was maintained at 900-1050 ℃ and continuous electrolysis was carried out for 200 hours, consuming 2030kg of lanthanum oxide, producing 1766kg of lanthanum-iron alloy, with an average lanthanum content of 95.06%, a current efficiency of 81% and alloy composition results as shown in Table 27.
TABLE 27 analysis of composition of lanthanum iron master alloy/wt%
La Fe C O P S Si Mn
95.06 4.64 0.0042 0.0065 ＜0.01 ＜0.005 0.014 ＜0.005
Taking the lanthanum-iron intermediate alloy prepared in the embodiment as a raw material, taking 12.6kg of the lanthanum-iron intermediate alloy, adding 2.4kg of metal lanthanum, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron components obtained after smelting are shown in table 28.
TABLE 28 composition analysis of lanthanum-iron alloy/wt%
La Fe C O P S Si Mn
80.03 19.74 0.0046 0.0066 ＜0.01 ＜0.005 0.0079 ＜0.005
The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims (10)

1. A lanthanum-iron alloy characterized by: 10.04-50.05 wt% of lanthanum, 59.97-95.06 wt% of lanthanum, and the balance of iron and inevitable impurities with the total amount less than 0.5 wt%, wherein the total amount of oxygen is less than or equal to 0.01 wt%, carbon is less than or equal to 0.01 wt%, phosphorus is less than or equal to 0.01 wt%, and sulfur is less than or equal to 0.005 wt%.
2. The lanthanum iron alloy of claim 1, wherein: the lanthanum content is 10.04-50.03 wt%.
3. The lanthanum iron alloy of claim 1, wherein: the lanthanum content is 10.11-50.05 wt%.
4. The lanthanum iron alloy of claim 1, wherein: the content of lanthanum is 29.98-50.05 wt%.
5. The lanthanum iron alloy of claim 1, wherein: the lanthanum content is 30.05-50.05 wt%.
6. The lanthanum iron alloy of claim 1, wherein: the content of lanthanum is 59.97-69.98 wt%.
7. The lanthanum iron alloy of claim 1, wherein: in the equipment for electrolyzing the lanthanum-iron intermediate alloy, under a fluoride molten salt electrolyte system of lanthanum fluoride and lithium fluoride, lanthanum oxide is taken as an electrolysis raw material, and direct current is introduced for electrolysis to obtain the lanthanum-iron intermediate alloy; the lanthanum-iron intermediate alloy and iron are used as raw materials, and the lanthanum-iron alloy is prepared by adopting a melting method.
8. The lanthanum iron alloy of claim 7, wherein: the equipment for melting the lanthanum-iron intermediate alloy is a medium-frequency induction furnace, the melting process is carried out under the vacuum condition, and the crucible adopts a rare earth oxide crucible.
9. The lanthanum iron alloy of claim 7, wherein: the material of the receiver is iron, rare earth oxide or boron nitride.
10. The lanthanum iron alloy of claim 7, wherein: adding metal lanthanum or iron in the vacuum melting process.
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