CN110846502A - Method for recovering waste high-temperature alloy through melt extraction - Google Patents

Method for recovering waste high-temperature alloy through melt extraction Download PDF

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CN110846502A
CN110846502A CN201911030571.9A CN201911030571A CN110846502A CN 110846502 A CN110846502 A CN 110846502A CN 201911030571 A CN201911030571 A CN 201911030571A CN 110846502 A CN110846502 A CN 110846502A
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extraction
nickel
melt
temperature alloy
waste
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王亲猛
唐鼎轩
郭学益
王松松
田庆华
李栋
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005Separation by a physical processing technique only, e.g. by mechanical breaking
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/005Preliminary treatment of scrap
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The invention discloses a method for recovering waste high-temperature alloy by melt extraction, which comprises the following steps: extracting the crushed nickel-based high-temperature alloy waste by using an extraction medium to obtain an extracted low-melting-point eutectic and extraction residues; the extraction medium is metal magnesium or zinc melt, or binary or multi-element metal melt containing magnesium and zinc; and carrying out vacuum distillation on the extracted low-melting-point eutectic to obtain a distillation product nickel metal or nickel-cobalt alloy and a condensed extraction medium. The invention provides a clean and efficient method for recycling waste high-temperature alloy, which has the advantages of short process flow, recyclable extraction medium, clean and environment-friendly process.

Description

Method for recovering waste high-temperature alloy through melt extraction
Technical Field
The invention belongs to the technical field of resource circulation, and particularly relates to a method for recovering waste high-temperature alloy by melt extraction.
Background
The nickel-based high-temperature alloy is an excellent high-temperature material with excellent high-temperature strength and good comprehensive properties of fatigue resistance, oxidation resistance, gas corrosion resistance and the like, and is widely applied to the fields of aerospace, nuclear power generation, petrochemical industry, ship manufacturing and the like. The nickel-based superalloy contains a large number of valuable elements such as molybdenum, rhenium, titanium, molybdenum and the like besides main metal elements such as nickel, cobalt, chromium and iron. Therefore, the recovery treatment of the waste high-temperature alloy has good industrial prospect.
There are many known methods for recovering valuable components from high temperature alloys, and the methods are mainly classified into hydrometallurgy, pyrometallurgy, and a method of combining pyrometallurgy and wet process.
The hydrometallurgical recovery method mainly comprises the following steps: acid dissolution-ion adsorption-solvent extraction, electrochemical dissolution extraction, electrochemical deposition and the like. After the high-temperature alloy is dissolved by strong acid or strong alkali, valuable metals are selectively recovered by means of adsorption or solvent extraction. Although the hydrometallurgical method can realize the selective separation and purification of valuable metals in the waste high-temperature alloy, the process is complicated, the flow is long, and the problems of secondary pollution such as waste water, waste residues and the like can be caused.
The pyrometallurgical method mainly adopts a high-temperature means to melt waste high-temperature alloy into liquid state, and then recovers part of metal through selective treatment. Chinese patent '201310070067.8' proposes a method for recovering waste nickel-based high-temperature alloy, which comprises atomizing alloy waste into metal powder by melting atomization process, oxidizing, chlorinating, and separating metals by using saturated vapor pressure difference of different metal chlorides. Chinese patent '201711209034.1' proposes that waste alloy is oxidized and roasted, and then inorganic salt is added to carry out molten salt reaction to obtain plate-shaped WC-Co composite powder, thereby realizing the recovery of the waste alloy. The above treatment methods are all essentially different from the "melt extraction" of the present invention.
The method combining the pyrometallurgical method and the wet method integrates the advantages of pyrometallurgy and wet metallurgy, can thoroughly recover the waste high-temperature alloy, has high comprehensive utilization rate, and still avoids the problem of secondary pollution.
In summary, there are many methods for recovering nickel-cobalt alloy from high-temperature alloy return materials, but some of these methods have long recovery process flow and complex working procedures, and are easy to generate the problems of waste water and waste residues; or other compounds are introduced, so that the cost is high and the subsequent recovery difficulty is high; or the process adaptability is poor, the requirements on raw materials are limited, and the method has certain limitations.
Disclosure of Invention
The invention aims to solve the technical problems that the defects and shortcomings in the background technology are overcome, the method for cleanly and efficiently recycling the waste high-temperature alloy is provided, the process flow is short, the extraction medium can be recycled, and the process is clean and environment-friendly.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for recovering waste high-temperature alloy by melt extraction comprises the following steps:
s1, extracting the crushed nickel-based high-temperature alloy waste by using an extraction medium to obtain an extracted low-melting-point eutectic and extraction residues; the extraction medium is metal magnesium or zinc melt, or binary or multi-element metal melt containing magnesium and zinc;
s2, carrying out vacuum distillation on the extracted low-melting-point eutectic obtained in the step S1 to obtain a distillation product nickel metal or nickel-cobalt alloy and a condensed extraction medium.
Further, the nickel-based superalloy scrap material of S1 contains 20 wt% -70 wt% of nickel element and 3 wt% -15 wt% of cobalt element.
Further, when the extraction medium adopted in S1 is a metal zinc melt, the distillation product obtained is nickel metal; when the extraction medium is metal magnesium or binary or multi-element metal melt containing magnesium and zinc, the obtained distillation product is nickel-cobalt alloy.
Further, the mass ratio of the nickel-based superalloy scrap to the extraction medium of S1 is 1: 2-1: 4.
further, the extraction treatment temperature of S1 is 900-1100 ℃, and the extraction treatment time is 2-5 h.
Further, in the step S2, the vacuum degree of the vacuum distillation treatment is 100-240 Pa, the temperature is 1000-1300 ℃, and the distillation treatment time is 0.5-2 h.
Further, separating and insulating the condensed extraction medium in the S2 to obtain a circulating extraction medium.
Further, the heat preservation temperature is 800-900 ℃.
Further, the circulating extraction medium is returned to S1 for multiple times of circulating extraction until the nickel and cobalt in the nickel-based superalloy scrap are completely extracted.
The design idea of the invention is that the nickel-based high-temperature alloy is mostly a solid solution strengthening type alloy, and the metal magnesium and zinc melt can form a low-melting-point alloy with nickel and cobalt in the high-temperature alloy and do not react with high-melting-point metals such as iron, chromium, molybdenum and the like; meanwhile, the capability of the austenitic structure in the high-temperature alloy can be damaged by metal magnesium and zinc melts; because magnesium and zinc have different saturated vapor pressures and volatility with nickel and cobalt, the vacuum distillation method can separate the two.
Compared with the prior art, the invention has the following advantages:
the invention relates to a method for efficiently recovering waste nickel-based high-temperature alloy, which comprises the following steps: recovering nickel and cobalt in the waste nickel-based high-temperature alloy by a melt extraction-vacuum distillation process, wherein the obtained technical indexes are as follows: the extraction recovery rate of nickel is more than or equal to 99 percent, the loss rate is less than or equal to 1 percent, the extraction recovery rate of cobalt is more than or equal to 95 percent, the loss rate is less than or equal to 5 percent, and the recovery rate of extraction medium is more than or equal to 98 percent.
The method for recovering the waste nickel-based high-temperature alloy has the advantages of short flow and simple process: the melt of zinc, magnesium and other monobasic or binary metals is used as extraction medium, and can form eutectic with nickel and cobalt in nickel-base high-temperature alloy at high temperature. The difference of saturated vapor pressure of different metals is utilized to carry out vacuum distillation on the eutectic so as to separate the extraction medium from the nickel-cobalt alloy.
The invention relates to an environment-friendly, green and recyclable waste nickel-based high-temperature alloy recovery method, which comprises the following steps: can successfully and effectively separate nickel and cobalt from the nickel-based high-temperature alloy, and simultaneously, the metal extraction medium melt used in the process can be continuously recycled. The final products in the method are divided into two types, the extracted multi-metal powder can be used as an alloy additive, and the nickel-cobalt alloy can be used as a new alloy raw material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention for recovering nickel and cobalt from waste nickel-based superalloys.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The method for recovering the waste high-temperature alloy by melt extraction uses monobasic or polybasic metal melts of zinc, magnesium and the like as extraction media, mixes the monobasic or polybasic metal melts with the waste nickel-based high-temperature alloy and processing waste materials, performs extraction reaction at high temperature, can form low-melting-point eutectic with nickel and cobalt in the nickel-based high-temperature alloy by the extraction media, and effectively traps the nickel and the cobalt out of the nickel-based high-temperature alloy so as to separate the nickel and the cobalt from other elements. And then, the extracted eutectic is subjected to vacuum distillation by utilizing the difference of saturated vapor pressures of different metals, so that nickel and cobalt are separated from magnesium and zinc, and an extraction medium and nickel and cobalt alloy can be separated. The extraction medium of the metal magnesium and zinc melt can be returned to the working procedure for circular extraction, and the nickel-cobalt powder can be used as an alloy processing material.
In one embodiment, the method for recovering nickel and cobalt from nickel-base superalloy by melt extraction comprises the following steps:
step one, crushing and mechanical activation: and crushing the nickel-based high-temperature alloy waste and the processing scraps to obtain the high-temperature alloy crushed material. The waste material and the machining chips of the nickel-based high-temperature alloy contain 20-70 percent of main metal nickel element, 3-15 percent of cobalt element and other elements such as iron, chromium, tungsten, molybdenum, titanium and the like.
Step two, melt extraction: and mixing the crushed material with an extraction medium, melting the extraction medium, and extracting the high-temperature alloy crushed material to obtain an extracted low-melting-point eutectic and extraction residues.
The extraction medium is monobasic or polybasic metal melt of magnesium metal, zinc metal, etc. Preferably, the mass ratio of the crushed material to the extraction medium is 1: 2-1: 4.
the extraction medium is metal magnesium, the melting point is 648.8 ℃, and the boiling point is 1107 ℃. And the solubility of nickel in the magnesium melt is 55 wt%, the solubility of cobalt in the magnesium melt is 33 wt%, and other elements in the high-temperature alloy are basically insoluble in the magnesium melt. Therefore, the extracted alloy melt is a low-melting-point eutectic body formed by melting magnesium and nickel and cobalt.
The extraction medium is metallic zinc, the melting point is 419.4 ℃, and the boiling point is 907 ℃. And nickel has a solubility of 33 wt.% in the zinc melt, while the other elements in the superalloy are essentially insoluble in the zinc melt. Therefore, the extracted alloy melt is a low-melting-point eutectic body formed by melting zinc and nickel.
The melt extraction equipment is a well-type resistance furnace and a vacuum smelting furnace, the preferred extraction treatment temperature is 900-1100 ℃, and the extraction treatment time is 2-5 h.
Step three, vacuum distillation separation: and D, distilling the co-melt extracted in the step two under a certain vacuum degree to obtain a condensed metal medium melt and a distillation product nickel metal or nickel-cobalt alloy.
The vacuum distillation equipment is a vacuum distillation furnace, the distillation treatment vacuum degree is preferably 100-240 Pa, the temperature is 1000-1300 ℃, and the distillation treatment time is 0.5-2 h. The vapor pressure difference between the magnesium, zinc and nickel and cobalt is large, and the separation can be carried out under the designed distillation condition.
Step four, recovering the metal extraction medium: and (4) separating and insulating the condensed metal extraction medium in the third step to obtain a circulating metal extraction medium.
Separating the condensed magnesium melt extraction medium, preferably performing heat preservation treatment at about 800-900 ℃, wherein the heat preservation equipment is a well type resistance furnace.
Step five, circulating extraction: and returning the extraction medium in the fourth step to the second step for multiple times of circulating extraction until the nickel and cobalt in the waste high-temperature alloy are completely extracted.
Example 1
In this embodiment, the waste nickel-based superalloy to be recycled is given a brand number of K435, which includes elements such as nickel, cobalt, chromium, molybdenum, titanium, niobium, and the like, and the components of the elements are as follows, with reference to fig. 1, the method for extracting nickel and cobalt from the waste nickel-based superalloy in this embodiment includes the following steps:
element(s) Ni Co Fe Cr Mo Ti Nb
K435 57.7 11.3 - 14.5 3.3 2.0 0.2
Firstly, crushing waste nickel-based high-temperature alloy into alloy crushed material with the granularity of 2-5 meshes;
and step two, adopting magnesium metal as an extraction medium, melting the magnesium metal and extracting the high-temperature alloy crushed material to obtain the low-melting-point eutectic and the extraction residue after extraction. The mass ratio of the crushed material to the metal magnesium is 1: 2, the extraction treatment temperature is 900-980 ℃, and the extraction treatment time is 2-3 h.
And step three, distilling the co-melt extracted in the step two under a certain vacuum degree to obtain condensed magnesium and a distillation product nickel-cobalt alloy. The distillation vacuum degree is 100-120 Pa, the temperature is 1100-1200 ℃, and the distillation time is 1.5-2 h.
And step four, separating and preserving heat of the condensed magnesium in the step three to obtain a circulating magnesium melt extraction medium. The heat preservation treatment temperature is 900 ℃.
And step five, returning the magnesium melt recycled in the step four to the step two for multiple times of extraction until the nickel and cobalt in the reaction system are completely extracted.
The technical indexes obtained in this embodiment are: the extraction recovery rate of nickel is more than or equal to 99 percent, and the loss rate is less than or equal to 1 percent; the extraction recovery rate of cobalt is more than or equal to 95 percent, the loss rate is less than or equal to 5 percent, and the recovery rate of extraction medium magnesium is more than or equal to 98 percent.
Example 2
In this embodiment, a waste nickel-based superalloy to be recycled is given a designation GH2984, which includes elements such as nickel, iron, chromium, molybdenum, titanium, and niobium, and the components are as follows, and with reference to fig. 1, the method for extracting nickel from the waste nickel-based superalloy in this embodiment includes the following steps:
element(s) Ni Co Fe Cr Mo Ti Nb
GH2984 45.2 - 33.0 19.0 1.8 2.0 0.2
Crushing waste nickel-based high-temperature alloy into alloy crushed material with the granularity of 1-4 meshes;
and step two, adopting metal zinc as an extraction medium, melting the metal zinc and extracting the high-temperature alloy crushed material to obtain an extracted alloy melt and extraction residues. The mass ratio of the crushed material to the metal zinc is 1: and 4, the extraction treatment temperature is 1000-1100 ℃, and the extraction treatment time is 3-5 h.
And step three, distilling the eutectic body extracted in the step two under a certain vacuum degree to obtain condensed zinc and a distillation product nickel metal. The distillation vacuum degree is 200-240 Pa, the temperature is 1100-1200 ℃, and the distillation time is 1.5-2 h.
And step four, separating and preserving the condensed zinc in the step three to obtain a circulating zinc melt extraction medium. The heat preservation treatment temperature is 800 ℃.
And step five, returning the zinc melt circulated in the step four to the step two for multiple times of extraction until the nickel in the reaction system is completely extracted.
The technical indexes obtained in this embodiment are: the extraction recovery rate of nickel is more than or equal to 99.5 percent, the loss rate is less than or equal to 0.5 percent, and the recovery rate of extraction medium zinc is more than or equal to 98 percent.
Example 3
In this embodiment, the waste nickel-based superalloy to be recycled is of a brand Udimet, which includes elements such as nickel, cobalt, chromium, molybdenum, and titanium, and the components of the elements are as follows, and with reference to fig. 1, the method for extracting nickel and cobalt from the waste nickel-based superalloy in this embodiment includes the following steps:
element(s) Ni Co Fe Cr Mo Ti Nb
Udimet 56.9 18.5 - 18.0 4.0 2.9 -
Firstly, crushing waste nickel-based high-temperature alloy into alloy crushed material with the granularity of 2-5 meshes;
and step two, melting magnesium and zinc metal and extracting the high-temperature alloy crushed material by taking a magnesium-zinc binary metal melt (the mass ratio of magnesium to zinc is 1: 1) as an extraction medium to obtain an extracted low-melting-point eutectic and extraction residues. The mass ratio of the crushed material to the metal magnesium is 1: and 3, the extraction treatment temperature is 980-1100 ℃, and the extraction treatment time is 2-3 h.
And step three, distilling the co-melt extracted in the step two under a certain vacuum degree to obtain condensed magnesium-zinc and a distillation product nickel-cobalt alloy. The distillation vacuum degree is 120-180 Pa, the temperature is 1100-1200 ℃, and the distillation time is 1.5-2 h.
And step four, separating and preserving heat of the magnesium and the zinc condensed in the step three to obtain a circulating magnesium-zinc melt extraction medium. The heat preservation treatment temperature is 900 ℃.
And step five, returning the magnesium-zinc melt circulated in the step four to the step two for multiple times of extraction until the nickel and cobalt in the reaction system are completely extracted.
The technical indexes obtained in this embodiment are: the extraction recovery rate of nickel is more than or equal to 99.5 percent, and the loss rate is less than or equal to 0.5 percent; the extraction recovery rate of cobalt is more than or equal to 96 percent, the loss rate is less than or equal to 4 percent, and the recovery rate of the extraction medium magnesium-zinc binary metal melt is more than or equal to 98 percent.
Example 4
The method for recovering nickel and cobalt from waste high-temperature alloy by melt extraction in the embodiment is basically the same as that in the embodiment 3, and is different in that: the waste nickel-based superalloy adopted in the embodiment is of a mark Mar-M247, and comprises the following components:
element(s) Ni Co Fe Cr Mo Ti Nb
Mar-M247 61.8 10.0 - 8.4 0.8 1.0 1.75
In addition, because the waste high-temperature alloy contains higher nickel and cobalt, the mass ratio of the waste high-temperature alloy to the magnesium-zinc binary extraction medium (the mass ratio of magnesium to zinc is 1: 1) is 1: 4.
the technical indexes obtained in this embodiment are: the extraction recovery rate of nickel is more than or equal to 99 percent, and the loss rate is less than or equal to 1 percent; the extraction recovery rate of cobalt is more than or equal to 95 percent, the loss rate is less than or equal to 5 percent, and the recovery rate of the extraction medium magnesium-zinc binary metal melt is more than or equal to 98 percent.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.

Claims (9)

1. A method for recovering waste high-temperature alloy by melt extraction is characterized by comprising the following steps:
s1, extracting the crushed nickel-based high-temperature alloy waste by using an extraction medium to obtain an extracted low-melting-point eutectic and extraction residues; the extraction medium is metal magnesium or zinc melt, or binary or multi-element metal melt containing magnesium and zinc;
s2, carrying out vacuum distillation on the extracted low-melting-point eutectic obtained in the step S1 to obtain a distillation product nickel metal or nickel-cobalt alloy and a condensed extraction medium.
2. The method for recovering the waste superalloy through melt extraction according to claim 1, wherein the nickel-based superalloy scrap at S1 contains 20 wt% to 70 wt% of nickel and 3 wt% to 15 wt% of cobalt.
3. The method for recovering the waste high-temperature alloy through melt extraction according to claim 1 or 2, wherein the distillation product obtained when the extraction medium adopted in S1 is a metal zinc melt is nickel metal; when the extraction medium is metal magnesium or binary or multi-element metal melt containing magnesium and zinc, the obtained distillation product is nickel-cobalt alloy.
4. The method for recovering the waste high-temperature alloy through melt extraction as claimed in claim 1, wherein the mass ratio of the nickel-based high-temperature alloy scrap to the extraction medium in S1 is 1: 2-1: 4.
5. the method for recovering the waste high-temperature alloy through melt extraction according to claim 1 or 4, wherein the extraction treatment temperature of S1 is 900-1100 ℃, and the extraction treatment time is 2-5 hours.
6. The method for recovering the waste high-temperature alloy through melt extraction according to claim 1, wherein the vacuum distillation processing vacuum degree of S2 is 100-240 Pa, the temperature is 1000-1300 ℃, and the distillation processing time is 0.5-2 h.
7. The method for recovering the waste high-temperature alloy through melt extraction as claimed in claim 1 or 6, wherein the condensed extraction medium of S2 is subjected to separation and heat preservation to obtain a circulating extraction medium.
8. The method for recovering the waste high-temperature alloy through melt extraction according to claim 7, wherein the heat preservation temperature is 800-900 ℃.
9. The method for recovering the waste and old high-temperature alloy through melt extraction as claimed in claim 7, wherein the circulating extraction medium is returned to S1 for multiple times of circulating extraction until the nickel cobalt in the nickel-based high-temperature alloy scrap is completely extracted.
CN201911030571.9A 2019-10-28 2019-10-28 Method for recovering waste high-temperature alloy through melt extraction Pending CN110846502A (en)

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CN112626356A (en) * 2020-11-03 2021-04-09 中南大学 Method for separating nickel and iron from nickel-iron alloy

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111621650A (en) * 2020-06-12 2020-09-04 中南大学 Method for extracting metallic nickel from laterite-nickel ore
CN112626356A (en) * 2020-11-03 2021-04-09 中南大学 Method for separating nickel and iron from nickel-iron alloy
CN112626356B (en) * 2020-11-03 2022-03-18 中南大学 Method for separating nickel and iron from nickel-iron alloy

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