CN107904613A - Method for recycling nickel-cobalt valuable metal from nickel-cobalt-iron high-temperature alloy - Google Patents

Method for recycling nickel-cobalt valuable metal from nickel-cobalt-iron high-temperature alloy Download PDF

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Publication number
CN107904613A
CN107904613A CN201711209370.6A CN201711209370A CN107904613A CN 107904613 A CN107904613 A CN 107904613A CN 201711209370 A CN201711209370 A CN 201711209370A CN 107904613 A CN107904613 A CN 107904613A
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CN
China
Prior art keywords
iron
nickel cobalt
nickel
cobalt
temperature alloy
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Pending
Application number
CN201711209370.6A
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Chinese (zh)
Inventor
崔海瑞
张恩玉
易超
鲁兴武
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Northwest Research Institute of Mining and Metallurgy
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Northwest Research Institute of Mining and Metallurgy
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Priority to CN201711209370.6A priority Critical patent/CN107904613A/en
Publication of CN107904613A publication Critical patent/CN107904613A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • 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
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • 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
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B7/006Wet processes

Abstract

The invention relates to a method for recycling valuable metals of nickel and cobalt from nickel-cobalt-iron high-temperature alloy waste. Firstly, taking nickel-cobalt-iron high-temperature alloy waste as an anode, carrying out liquid preparation in an electrochemical dissolution mode, removing iron by using a jarosite method after liquid preparation, and codepositing valuable metals of nickel and cobalt after iron removal to finally obtain high-purity nickel-cobalt mixed salt; the nickel-cobalt-iron high-temperature alloy waste treated by the method not only solves the problem that the nickel-cobalt-iron high-temperature nickel alloy waste treated by the traditional wet method is difficult to dissolve, but also effectively recycles nickel-cobalt valuable metals in the waste.

Description

A kind of method that nickel cobalt valuable metal is recycled in the iron high temperature alloy by nickel cobalt
Technical field
The present invention relates to a kind of method that nickel cobalt valuable metal is recycled in iron high-temperature alloy waste material by nickel cobalt.
Background technology
Nickel cobalt iron high-temperature alloy waste material, since it is metal alloys, it is difficult to conventional wet lay Metallurgical processing is used, and pyrogenic process work Skill also fails to large-scale application due to its high energy consumption, working condition difference.
The content of the invention
In order to solve the problems in the prior art, the purpose of the present invention is to providing, a kind of technique is simple, work situation is good, removal of impurities Thoroughly, the method that nickel cobalt valuable metal is recycled in energy consumption and the low iron high-temperature alloy waste material by nickel cobalt of alkaline consumption.
The concrete technical scheme of the present invention is as follows:
A kind of method that nickel cobalt valuable metal is recycled in iron high-temperature alloy waste material by nickel cobalt, it is characterised in that comprise the following steps:
A, nickel cobalt iron high-temperature alloy waste material is fitted into the string bag as anode, the string bag is placed in acidic electrolysis bath, use stainless steel Plate or titanium plate do cathode, are passed through direct current, current density is in 200-1000 A/m2, lead to direct current 8-16h, obtain nickel cobalt iron Mixing electricity solution;
B, the mixing electricity solution in step a is warming up to 90-95 DEG C, to it in be slowly added to sodium carbonate liquor, adjust pH value to 2, add oxidant, while add sodium carbonate liquor, make its pH stable 2, when stirring 1-2 is small after, continuously add carbonic acid Sodium completes iron removaling to pH value to 4;
C, precipitating reagent is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, is 8-9 to pH value, stirs Mix 1-2 it is small when, filtering, you can obtain high-purity nickel cobalt salt-mixture.
Acidic electrolysis bath in the step a is electrolysis of hydrochloric acid liquid or sulfuric acid electrolyte;
Oxidant in the step b is hydrogen peroxide or hypochlorite oxidation ferrous iron;
Precipitating reagent in the step c is sodium carbonate or sodium hydroxide solution.
The invention has the advantages that:
Nickel cobalt iron high-temperature alloy waste material is done anode by the present invention first, liquid making is carried out by the way of electrochemistry holds solution, after liquid making Using yellow modumite method iron removaling, nickel cobalt valuable metal is co-deposited after iron removaling, finally obtains high-purity nickel cobalt salt-mixture;Pass through the method The nickel cobalt iron high-temperature alloy waste material of processing, not only solves conventional wet mode and handles nickel cobalt iron high temperature nickel alloy waste material indissoluble solution The problem of, and effectively recycled the nickel cobalt valuable metal in waste material.
Embodiment
Embodiment 1
Nickel cobalt iron high temperature alloy composition mainly has nickel 29.82%, cobalt 17.35%, copper 0.51%, iron 52.16% and argentiferous 1206.9g/ T, the method by recycling nickel cobalt valuable metal in the nickel cobalt iron high-temperature alloy waste material, comprises the following steps:
A, nickel cobalt iron high-temperature alloy waste material is fitted into the string bag as anode, the string bag is placed in sulfuric acid electrolyte, use stainless steel Plate does cathode, is passed through direct current, current density is in 200 A/m2, lead to direct current 16h, obtain the mixing electricity solution of nickel cobalt iron;
B, the mixing electricity solution in step a is warming up to 90 DEG C, to it in be slowly added to sodium carbonate liquor, adjust pH value to 2, then Add and iron content molar ratio 1.1 in solution:2 hydrogen peroxide, while add sodium carbonate liquor, makes its pH stable 2, stirring 2 it is small when after, continuously add sodium carbonate to pH value to 4, complete iron removaling;
C, sodium carbonate is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, is 8 to pH value, stirring 1.5 it is small when, filtering, you can obtain high-purity nickel cobalt mixed carbonate of the nickel cobalt content 47.94%.
Embodiment 2
4J29 high temperature alloy compositions mainly have nickel 28.67%, cobalt 17.51%, manganese 0.13% and iron 53.69%, are closed by the 4J29 high temperature The method that nickel cobalt valuable metal is recycled in golden waste material, comprises the following steps:
A, 4J29 high-temperature alloy waste materials are fitted into the string bag as anode, the string bag is placed in electrolysis of hydrochloric acid liquid, the moon is done with titanium plate Pole, is passed through direct current, current density is in 500 A/m2, lead to direct current 10h, obtain the mixing electricity solution of nickel cobalt iron;
B, by the mixing electricity solution supplying and iron molar ratio 1.1 in step a:1 sodium sulphate, then electric solution is warming up to 95 DEG C, Sodium carbonate liquor is slowly added in it, pH value is adjusted to 2, adds and iron content molar ratio 1.1 in solution:2 hypochlorous acid Sodium, while add sodium carbonate liquor, makes its pH stable 2, when stirring 1 is small after, continuously add sodium carbonate to pH value to 4, it is complete Into iron removaling;
C, sodium hydroxide is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, it is left for 8.5 to pH value The right side, when stirring 1 is small, filtering, you can obtain High Purity Hydrogen cobalt nickel oxide salt-mixture of the nickel cobalt content 62.59%.
Embodiment 3
Nickel cobalt iron high temperature alloy composition mainly has nickel 29.11%, cobalt 17.25%, copper 0.17% and iron 53.37%, high by the nickel cobalt iron The method that nickel cobalt valuable metal is recycled in temperature alloy waste material, comprises the following steps:
A, nickel cobalt iron high-temperature alloy waste material is fitted into the string bag as anode, the string bag is placed in sulfuric acid electrolyte, made of titanium plate Cathode, is passed through direct current, current density is in 800 A/m2, lead to direct current 13h, obtain the mixing electricity solution of nickel cobalt iron;
B, the mixing electricity solution in step a is warming up to 95 DEG C, to it in be slowly added to sodium carbonate liquor, adjust pH value to 2, then Add and iron content molar ratio 1.1 in solution:2 sodium hypochlorite, while add sodium carbonate liquor, makes its pH stable stir 2 Mix 1.5 it is small when after, continuously add sodium carbonate to pH value to 4, complete iron removaling;
C, sodium hydroxide is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, is 9 to pH value, stirs Mix 1 it is small when, filtering, you can obtain High Purity Hydrogen cobalt nickel oxide salt-mixture of the nickel cobalt content 61.94%.
Embodiment 4
Nickel cobalt iron high temperature alloy composition mainly has nickel 29.47%, cobalt 16.98%, copper 0.11%, molybdenum 0.18% and iron 53.26%, by this The method that nickel cobalt valuable metal is recycled in nickel cobalt iron high-temperature alloy waste material, comprises the following steps:
A, nickel cobalt iron high-temperature alloy waste material is fitted into the string bag as anode, the string bag is placed in electrolysis of hydrochloric acid liquid, uses stainless steel Plate does cathode, is passed through direct current, current density is in 1000 A/m2, lead to direct current 8h, obtain the mixing electricity solution of nickel cobalt iron;
B, by the mixing electricity solution supplying and iron molar ratio 1.1 in step a:1 sodium sulphate, then electric solution is warming up to 90 DEG C, Sodium carbonate liquor is slowly added in it, pH value is adjusted to 2, adds and iron content molar ratio 1.1 in solution:2 hydrogen peroxide, Add sodium carbonate liquor at the same time, make its pH stable 2, when stirring 2 is small after, continuously add sodium carbonate to pH value to 4, complete to remove Iron;
C, sodium carbonate is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, it is left for 8.5 to pH value The right side, when stirring 1 is small, filtering, you can obtain high-purity nickel cobalt mixed carbonate of the nickel cobalt content 47.38%.

Claims (4)

1. the method for nickel cobalt valuable metal is recycled in a kind of iron high-temperature alloy waste material by nickel cobalt, it is characterised in that including following step Suddenly:
A, nickel cobalt iron high-temperature alloy waste material is fitted into the string bag as anode, the string bag is placed in acidic electrolysis bath, use stainless steel Plate or titanium plate do cathode, are passed through direct current, current density is in 200-1000 A/m2, lead to direct current 8-16h, obtain nickel cobalt iron Mixing electricity solution;
B, the mixing electricity solution in step a is warming up to 90-95 DEG C, to it in be slowly added to sodium carbonate liquor, adjust pH value to 2, add oxidant, while add sodium carbonate liquor, make its pH stable 2, when stirring 1-2 is small after, continuously add carbonic acid Sodium completes iron removaling to pH value to 4;
C, precipitating reagent is slowly added in the mixing electricity solution at a temperature of 60 DEG C into step b after iron removaling, is 8-9 to pH value, stirs Mix 1-2 it is small when, filtering, you can obtain high-purity nickel cobalt salt-mixture.
2. recycling the method for nickel cobalt valuable metal in a kind of iron high-temperature alloy waste material by nickel cobalt as claimed in claim 1, it is special Sign is:Acidic electrolysis bath in the step a is electrolysis of hydrochloric acid liquid or sulfuric acid electrolyte.
3. recycling the method for nickel cobalt valuable metal in a kind of iron high-temperature alloy waste material by nickel cobalt as claimed in claim 1, it is special Sign is:Oxidant in the step b is hydrogen peroxide or hypochlorite oxidation ferrous iron.
4. recycling the method for nickel cobalt valuable metal in a kind of iron high-temperature alloy waste material by nickel cobalt as claimed in claim 1, it is special Sign is:Precipitating reagent in the step c is sodium carbonate or sodium hydroxide solution.
CN201711209370.6A 2017-11-27 2017-11-27 Method for recycling nickel-cobalt valuable metal from nickel-cobalt-iron high-temperature alloy Pending CN107904613A (en)

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Cited By (7)

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CN109518225A (en) * 2019-01-16 2019-03-26 北京矿冶科技集团有限公司 A kind of method of ferrous iron and cobalt nickel in separation solution
CN109913667A (en) * 2019-03-20 2019-06-21 东北大学 A method of the Call Provision from nickel base superalloy waste cut materials
CN110117714A (en) * 2019-05-29 2019-08-13 北京科技大学 A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium
CN111334666A (en) * 2020-03-31 2020-06-26 中国科学院金属研究所 Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste
CN113215589A (en) * 2021-04-15 2021-08-06 中国恩菲工程技术有限公司 Method for separating iron and other metal elements in iron alloy
CN113373311A (en) * 2021-06-08 2021-09-10 金川镍钴研究设计院有限责任公司 Method for fully soaking copper-nickel alloy powder in sulfuric acid at normal temperature and normal pressure
WO2023061038A1 (en) * 2021-10-11 2023-04-20 荆门市格林美新材料有限公司 Combined treatment method for nickel-iron alloy material and nickel-containing raw material

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CN105958148A (en) * 2016-05-17 2016-09-21 长沙理工大学 Method for recovering valuable metal from waste lithium nickel cobalt manganese oxide battery material
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109518225A (en) * 2019-01-16 2019-03-26 北京矿冶科技集团有限公司 A kind of method of ferrous iron and cobalt nickel in separation solution
CN109913667A (en) * 2019-03-20 2019-06-21 东北大学 A method of the Call Provision from nickel base superalloy waste cut materials
CN110117714A (en) * 2019-05-29 2019-08-13 北京科技大学 A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium
CN110117714B (en) * 2019-05-29 2020-03-17 北京科技大学 Method for leaching vanadium by anode electrolysis in normal-temperature saturated oxalic acid solution
CN111334666A (en) * 2020-03-31 2020-06-26 中国科学院金属研究所 Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste
CN113215589A (en) * 2021-04-15 2021-08-06 中国恩菲工程技术有限公司 Method for separating iron and other metal elements in iron alloy
CN113373311A (en) * 2021-06-08 2021-09-10 金川镍钴研究设计院有限责任公司 Method for fully soaking copper-nickel alloy powder in sulfuric acid at normal temperature and normal pressure
WO2023061038A1 (en) * 2021-10-11 2023-04-20 荆门市格林美新材料有限公司 Combined treatment method for nickel-iron alloy material and nickel-containing raw material

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Application publication date: 20180413