CN115505742B - Samarium cobalt recovery method of samarium cobalt magnetic material - Google Patents
Samarium cobalt recovery method of samarium cobalt magnetic material Download PDFInfo
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- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000696 magnetic material Substances 0.000 title claims abstract description 35
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000004090 dissolution Methods 0.000 claims abstract description 53
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 51
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 51
- 239000010941 cobalt Substances 0.000 claims abstract description 51
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000002386 leaching Methods 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 239000011343 solid material Substances 0.000 claims abstract description 28
- 239000002893 slag Substances 0.000 claims abstract description 16
- 238000011978 dissolution method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 229910052598 goethite Inorganic materials 0.000 claims description 5
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 239000000428 dust Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 4
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 53
- 238000001914 filtration Methods 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000000956 alloy Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017076 Fe Zr Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- -1 leaching Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22B7/00—Working 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
- C22B59/00—Obtaining rare earth metals
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- 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
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- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a samarium cobalt recovery method of a samarium cobalt magnetic material. The samarium cobalt recovery method comprises the following steps: step S1, crushing a samarium cobalt magnetic material by adopting an electrochemical dissolution method to obtain a decomposed solid material and an electrolyzed solution; s2, carrying out acid dissolution on the decomposed solid material to obtain leaching liquid and leaching slag; s3, precipitating samarium in the leaching solution to obtain samarium double salt precipitate and a samarium-removed solution; step S4, deironing the samarium-removed solution to obtain iron-containing slag and a deironing solution; s5, extracting the solution after iron removal to obtain a cobalt-containing solution; and step S6, electrolyzing the cobalt-containing solution to obtain electrolytic cobalt. The samarium cobalt magnetic material is changed into granular material or even powder material by an electrochemical method, and then subsequent acid dissolution treatment is carried out. The electrochemical dissolution method does not need mechanical power to participate, so that the power consumption is less, and the process is wet operation, does not generate dust, and is more beneficial to construction.
Description
Technical Field
The invention relates to the field of samarium cobalt alloy recovery, in particular to a samarium cobalt recovery method of a samarium cobalt magnetic material.
Background
With the continuous development of industrial production technology, cobalt becomes an important raw material for producing battery materials, high-temperature alloys, hard alloys, magnetic materials and catalysts. However, the cobalt resources in China are relatively poor, and besides various grades of cobalt ores are reasonably utilized, the secondary recovery and utilization of cobalt are also significant. The samarium cobalt magnetic material mainly comprises samarium and cobalt, and a small amount of copper, iron, zirconium and other elements, wherein the content of the samarium and the cobalt is more than 70%, and the samarium cobalt magnetic material has high recovery value.
The method for recovering cobalt from samarium cobalt magnetic materials is mainly divided into a pyrogenic process and a wet process. Because of the disadvantages of large investment, high running cost, impure recovered products and the like of the fire method, the wet method is generally adopted to treat and recover the samarium cobalt magnetic material.
The wet method is adopted to recycle the samarium cobalt magnetic material, and cobalt salt is obtained after the rare earth is precipitated and purified by acid leaching. The patent application with publication number CN103555950A discloses a method for recycling samarium cobalt magnetic waste, which adopts hydrochloric acid leaching, oxalic acid precipitation of rare earth samarium, iron removal, cobalt precipitation and heating burning to obtain cobalt oxide. The product obtained by the samarium cobalt recovery technology is cobalt salt or cobalt oxide, and the recovered cobalt product has low added value. In the technological process, oxalic acid is adopted to precipitate samarium, iron is removed, and then oxalic acid is adopted to precipitate cobalt. The oxalic acid precipitates samarium and the impurity elements precipitate, so that the recovered samarium product has low grade.
The patent application with the publication number of CN 108251649A discloses a hydrometallurgical treatment process for recycling samarium cobalt alloy resources. The treatment process discloses processes of crushing and ball milling of samarium cobalt alloy, leaching, samarium removal, iron removal, extraction, impurity removal and the like, and the processes of recovering samarium, cobalt and heavy metals in the samarium cobalt alloy. Although the process can obtain high-grade samarium and cobalt, the crushing ball milling consumes more power, so that the industrial application has higher power cost and dust pollution is easy to cause.
Disclosure of Invention
The invention mainly aims to provide a samarium cobalt recovery method of a samarium cobalt magnetic material, which aims to solve the problems that in the prior art, the dynamic cost of a hydrometallurgical treatment process for recovering and utilizing samarium cobalt alloy resources is high and dust pollution is easy to cause.
In order to achieve the above object, according to one aspect of the present invention, there is provided a samarium cobalt recovery method of a samarium cobalt magnetic material, the samarium cobalt recovery method comprising: step S1, crushing a samarium cobalt magnetic material by adopting an electrochemical dissolution method to obtain a decomposed solid material and an electrolyzed solution; s2, carrying out acid dissolution on the decomposed solid material to obtain leaching liquid and leaching slag; s3, precipitating samarium in the leaching solution to obtain samarium double salt precipitate and a samarium-removed solution; step S4, deironing the samarium-removed solution to obtain iron-containing slag and a deironing solution; s5, extracting the solution after iron removal to obtain a cobalt-containing solution; and step S6, electrolyzing the cobalt-containing solution to obtain electrolytic cobalt.
Further, in the step S1, samarium cobalt magnetic materials are adopted as an anode, graphite or titanium is adopted as a cathode, and neutral solution is adopted as electrolyte.
Further, the electrolyte is an aqueous sodium sulfate solution.
Further, the electrochemical dissolution temperature in the step S1 is 30-50 ℃.
Further, the current density of the electrochemical dissolution in the step S1 is 5 to 20A/dm 2.
Further, in the step S2, sulfuric acid is adopted to carry out acid dissolution on the decomposed solid material, preferably, the molar quantity of H 2SO4 in the sulfuric acid is 1.3-1.7 times of the molar quantity of metal elements in the samarium cobalt magnetic material, preferably, the liquid-solid ratio is controlled to be 8:1-20:1 during acid dissolution, preferably, the acid dissolution temperature is 60-90 ℃, and the acid dissolution time is 4-6 hours.
Further, in the step S3, samarium in the leaching solution is precipitated by sodium sulfate, preferably the molar quantity of sodium sulfate is 3-5 times of the molar quantity of samarium in the leaching solution, and the precipitation temperature in the step S3 is preferably 60-90 ℃.
Further, the step S4 is to remove iron by goethite iron removal.
Further, the extractant used in the step S5 is P204, and preferably the extraction is multistage extraction.
Further, the current density used for the electrolysis in the above step S6 is 300 to 500A/m 2.
By applying the technical scheme of the invention, the samarium cobalt magnetic material is changed into a granular material or even a powder material by an electrochemical method; so that after separating the decomposed solid material from the solution after electrolysis, the decomposed solid material can be subjected to subsequent acid dissolution treatment. The electrochemical dissolution method does not need mechanical power to participate, so that the power consumption is less, and the process is wet operation, does not generate dust, and is more beneficial to construction.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed by the background technology of the application, the samarium cobalt alloy is crushed by adopting crushing ball milling in the prior art, so that the power consumption is high, the industrial application power cost is high, dust pollution is easy to cause, and in order to solve the problem, the application provides a samarium cobalt recovery method of the samarium cobalt magnetic material. The samarium cobalt recovery method comprises the following steps: step S1, crushing a samarium cobalt magnetic material by adopting an electrochemical dissolution method to obtain a decomposed solid material and an electrolyzed solution; s2, carrying out acid dissolution on the decomposed solid material to obtain leaching liquid and leaching slag; s3, precipitating samarium in the leaching solution to obtain samarium double salt precipitate and a samarium-removed solution; step S4, deironing the samarium-removed solution to obtain iron-containing slag and a deironing solution; s5, extracting the solution after iron removal to obtain a cobalt-containing solution; and step S6, electrolyzing the cobalt-containing solution to obtain electrolytic cobalt.
At present, most of the crushing modes of alloy materials are mechanical, and samarium cobalt magnetic waste materials have magnetism, so that the power consumption is higher. In order to solve the problem, the application analyzes the processed samarium cobalt magnetic material, and discovers that although the content of samarium and cobalt in the material is more than 70 percent, the material also contains other metal elements such as copper, iron and the like, and the samarium cobalt material is taken as an anode, so that the samarium cobalt magnetic material is changed into granules or even powder by an electrochemical method; so that after separating the decomposed solid material from the solution after electrolysis, the decomposed solid material can be subjected to subsequent acid dissolution treatment. The electrochemical dissolution method does not need mechanical power to participate, so that the power consumption is less, and the process is wet operation, does not generate dust, and is more beneficial to construction.
The electrochemical dissolution method can use the known electrochemical principle to break up the samarium cobalt material by selecting a proper electrochemical material, and in a preferred embodiment of the present application, the samarium cobalt magnetic material is used as an anode, graphite or titanium is used as a cathode, and a neutral solution is used as an electrolyte in the step S1. Preferably, the electrolyte is an aqueous solution of sodium sulfate.
In order to enhance the efficiency of the electrochemical dissolution and to secure the safety of the electrochemical dissolution, it is preferable that the temperature of the electrochemical dissolution in the above step S1 is 30 to 50 ℃. Further preferably, the current density of the electrochemical dissolution in the step S1 is 5 to 20A/dm 2.
Step S2 of the present application preferably uses sulfuric acid to acid dissolve the decomposed solids to form sulfate, thereby facilitating the formation of samarium double salts in the next step. In order to improve the sufficient dissolution of each metal element in the decomposed solid material and control the pH value and cobalt content of the obtained leaching solution, the molar amount of H 2SO4 in sulfuric acid is preferably 1.3-1.7 times that of the metal element in the samarium cobalt magnetic material. In order to increase the utilization ratio of sulfuric acid, the liquid-solid ratio is preferably controlled to 8:1 to 20:1 during acid dissolution. Further, in order to improve the acid dissolution efficiency, the acid dissolution temperature is preferably 60 to 90 ℃, more preferably 65 to 85 ℃, and the acid dissolution time is preferably 4 to 6 hours.
In one embodiment of the present application, the step S3 uses sodium sulfate to precipitate samarium in the leachate, preferably, the molar amount of sodium sulfate is 3-5 times that of samarium in the leachate, so as to achieve sufficient precipitation of samarium on the basis of saving the sodium sulfate dosage as much as possible. Further, in order to improve the precipitation efficiency, the precipitation temperature in step S3 is preferably 60 to 90 ℃.
The iron removal method in the step S4 can refer to a common iron removal process in the prior art, and the iron removal method in the step S4 is preferably adopted for iron removal in the application. To obtain goethite iron for further processing applications thereof.
The solution obtained after iron removal also contains impurity ions such as calcium and magnesium to affect the further recovery of cobalt, and in order to improve the effect of removing the impurity ions, the extracting agent used in the step S5 is preferably P204, and the extraction is preferably multistage extraction, for example, 3-5 stages of extraction.
After the above treatment, the cobalt content in the obtained cobalt-containing solution is low, and in order to improve the recovery efficiency of cobalt, it is preferable that the current density for the electrolysis in the above step S6 is 300 to 500A/m 2. High purity cobalt metal is obtained by electrolysis.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The main components of the samarium cobalt magnetic waste are shown in table 1:
TABLE 1
| Element(s) | Sm | Co | Cu | Fe | Zr |
| Content (wt.) | 25 | 51 | 3 | 17 | 2.93 |
Example 1
Step S1, crushing the samarium cobalt magnetic waste by adopting an electrochemical dissolution method, and filtering to obtain a decomposed solid material with the particle size of 5-300 microns and an electrolyzed solution, wherein the samarium cobalt magnetic material is used as an anode, a graphite plate is used as a cathode, a sodium sulfate aqueous solution is used as an electrolyte, the electrochemical dissolution temperature is controlled to be 40 ℃, the current density is 10A/dm 2, and the time is 4 hours;
s2, carrying out acid dissolution on the decomposed solid material, and filtering to obtain leaching liquid and leaching slag, wherein the liquid-solid ratio is controlled to be 8:1, the acid dissolution temperature is 80 ℃, the acid dissolution time is 4 hours, the concentration is more than 241kg/t of 95% sulfuric acid, and the molar quantity of the sulfuric acid is 1.5 times of the metal content;
s3, precipitating samarium in the leaching solution, filtering to obtain samarium double salt precipitate and samarium-removed solution, wherein the molar quantity of sodium sulfate is 4 times of that of the samarium in the leaching solution, and the precipitation temperature is 80 ℃;
S4, deironing the samarium-removed solution by adopting a goethite deironing method, filtering to obtain iron-containing slag and a deironing solution, wherein ferrous iron in the filtrate in the S3 is oxidized into ferric iron by using an oxidant, then an alkaline solution such as sodium carbonate is added into the solution, the temperature is controlled at 85-95 ℃, and the pH value is controlled at 3.0-4.5, so that the obtained goethite intermediate product can be used as a raw material for preparing iron oxide red;
s5, extracting the solution after iron removal to obtain a cobalt-containing solution and raffinate, wherein the extractant is P204, and performing 5-level extraction, wherein the concentration of cobalt in the cobalt-containing solution is 28g/L;
And S6, electrolyzing the cobalt-containing solution to obtain electrolytic cobalt, wherein an electrolytic anode is graphite, a cathode is titanium, and the current density is 400A/m 2.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 2
And S1, crushing the samarium cobalt magnetic waste by adopting an electrochemical dissolution method, and filtering to obtain a decomposed solid material with the particle size of 5-300 and an electrolyzed solution, wherein the samarium cobalt magnetic material is used as an anode, a graphite plate is used as a cathode, a sodium sulfate solution is used as an electrolyte, the electrochemical dissolution temperature is controlled to be 30 ℃, the current density is controlled to be 20A/dm 2, and the time is controlled to be 2 hours.
Step S2, carrying out acid dissolution on the decomposed solid material, filtering to obtain leaching liquid and leaching slag, wherein the liquid-solid ratio is controlled to be 8:1, the acid dissolution temperature is 80 ℃, the acid dissolution time is 4 hours, the molar quantity of sulfuric acid is 1.5 times of the total metal quantity, and the rest steps are the same as those of the embodiment 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 3
And S1, crushing the samarium cobalt magnetic waste by adopting an electrochemical dissolution method, and filtering to obtain a decomposed solid material with the particle size of 5-300 and an electrolyzed solution, wherein the samarium cobalt magnetic material is used as an anode, a graphite plate is used as a cathode, a sodium sulfate solution is used as an electrolyte, the electrochemical dissolution temperature is controlled to be 50 ℃, the current density is controlled to be 5A/dm 2, and the time is controlled to be 5 hours.
Step S2, acid dissolution is carried out on the decomposed solid material, leaching liquid and leaching slag are obtained after filtration, wherein the liquid-solid ratio is controlled to be 8:1, the acid dissolution temperature is 80 ℃, the acid dissolution time is 4 hours, and the molar quantity of sulfuric acid is 1.5 times of the total molar quantity of metal
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 4
And S1, crushing the samarium cobalt magnetic waste by adopting an electrochemical dissolution method, and filtering to obtain a decomposed solid material with the particle size of 5-300 microns and an electrolyzed solution, wherein the samarium cobalt magnetic material is used as an anode, a graphite plate is used as a cathode, a sodium sulfate aqueous solution is used as an electrolyte, the electrochemical dissolution temperature is controlled to be 25 ℃, the current density is controlled to be 25A/dm 2, and the time is controlled to be 2 hours.
And S2, carrying out acid dissolution on the decomposed solid material, and filtering to obtain leaching liquid and leaching slag, wherein the liquid-solid ratio is controlled to be 8:1, the acid dissolution temperature is 80 ℃, the acid dissolution time is 4 hours, and the molar quantity of sulfuric acid is 1.5 times of the total molar quantity of metal.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 5
Step S1 is the same as in example 1;
And S2, carrying out acid dissolution on the decomposed solid material, and filtering to obtain leaching liquid and leaching slag, wherein the liquid-solid ratio is controlled to be 10:1, the acid dissolution temperature is 90 ℃, the acid dissolution time is 6 hours, and the molar quantity of sulfuric acid is 1.5 times of the total metal quantity.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 6
Step S1 is the same as in example 1;
s2, carrying out acid dissolution on the decomposed solid material, and filtering to obtain leaching liquid and solid slag, wherein the liquid-solid ratio is controlled to be 15:1, the acid dissolution temperature is 60 ℃, the acid dissolution time is 4 hours, and the molar quantity of sulfuric acid is 1.5 times of the total metal quantity; the leaching rates and concentrations of the acid-soluble samarium, cobalt and iron in the step S2 are shown in Table 2, and the concentration of cobalt in the cobalt-containing solution obtained in the step S5 is 23g/L.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 7
Step S1 is the same as in example 1;
and S2, carrying out acid dissolution on the decomposed solid material, and filtering to obtain leaching liquid and solid slag, wherein the liquid-solid ratio is controlled to be 20:1, the acid dissolution temperature is 70 ℃, the acid dissolution time is 3 hours, and the molar quantity of sulfuric acid is 1.5 times of the total metal quantity.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 8
Step S1 and step S2 are the same as in example 1;
and S3, precipitating samarium in the leaching solution, filtering to obtain samarium double salt precipitate and samarium-removed solution, wherein the weight of sodium sulfate is 3 times of the molar weight of the samarium in the leaching solution, and the precipitation temperature is 90 ℃.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 9
Step S1 and step S2 are the same as in example 1;
and S3, precipitating samarium in the leaching solution, filtering to obtain samarium double salt precipitate and samarium-removed solution, wherein the molar quantity of sodium sulfate is 5 times that of the samarium in the leaching solution, and the precipitation temperature is 60 ℃.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Example 10
Step S1 and step S2 are the same as in example 1;
And S3, precipitating samarium in the leaching solution, filtering to obtain samarium double salt precipitate and samarium-removed solution, wherein the molar quantity of sodium sulfate is 6 times that of the samarium in the leaching solution, and the precipitation temperature is 50 ℃.
The remaining steps were the same as in example 1.
The leaching rates of the acid-soluble samarium, cobalt and iron in step S2 are shown in Table 2.
Comparative example 1
The difference from example 1 is that step S1 adopts a crushing ball milling mode to crush the samarium cobalt magnetic material to the grain size of 5-300 microns. The leaching rates of the resulting dissolved samarium, cobalt and iron after the treatment of step S2 of example 1 are shown in table 2.
TABLE 2
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
At present, most of the crushing modes of alloy materials are mechanical, and samarium cobalt magnetic waste materials have magnetism, so that the power consumption is higher. In order to solve the problem, the application analyzes the processed samarium cobalt magnetic material, and discovers that although the content of samarium and cobalt in the material is more than 70 percent, the material also contains other metal elements such as copper, iron and the like, and the samarium cobalt material is taken as an anode, so that the samarium cobalt magnetic material is changed into granules or even powder by an electrochemical method; so that after separating the decomposed solid material from the solution after electrolysis, the decomposed solid material can be subjected to subsequent acid dissolution treatment. The electrochemical dissolution method does not need mechanical power to participate, so that the power consumption is less, and the process is wet operation, does not generate dust, and is more beneficial to construction.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. The samarium cobalt recovery method of the samarium cobalt magnetic material is characterized by comprising the following steps of:
step S1, crushing a samarium cobalt magnetic material by adopting an electrochemical dissolution method to obtain a decomposed solid material and an electrolyzed solution;
S2, carrying out acid dissolution on the decomposed solid materials to obtain leaching liquid and leaching slag;
s3, precipitating the samarium in the leaching solution to obtain samarium double salt precipitation and a samarium-removed solution;
Step S4, deironing the samarium-removed solution to obtain iron-containing slag and deironing solution;
S5, extracting the solution after iron removal to obtain a cobalt-containing solution; and
S6, electrolyzing the cobalt-containing solution to obtain electrolytic cobalt;
The step S1 adopts the samarium cobalt magnetic material as an anode, graphite or titanium as a cathode and neutral solution as electrolyte.
2. The method of claim 1, wherein the electrolyte is an aqueous sodium sulfate solution.
3. The samarium cobalt recovery method according to claim 1, wherein the electrochemical dissolution temperature in the step S1 is 30-50 ℃.
4. The method of claim 1, wherein the electrochemical dissolution in step S1 has a current density of 5-20 a/dm 2.
5. The samarium cobalt recovery method according to claim 1, wherein the step S2 is to acid-dissolve the decomposed solid materials with sulfuric acid.
6. The method of claim 5, wherein the molar amount of H 2SO4 in the sulfuric acid is 1.3-1.7 times the molar amount of the metal element in the samarium cobalt magnetic material.
7. The samarium cobalt recovery method according to claim 5, wherein the liquid-solid ratio is controlled to be 8:1-20:1 during acid dissolution.
8. The method of claim 5, wherein the acid dissolution temperature is 60-90 ℃.
9. The method of claim 5, wherein the acid dissolution time is 4-6 hours.
10. The method of claim 1 wherein step S3 precipitates samarium in the leachate using sodium sulfate.
11. The method of claim 10, wherein the molar amount of sodium sulfate is 3-5 times the molar amount of samarium in the leachate.
12. The samarium cobalt recovery method according to claim 10, wherein the precipitation temperature in the step S3 is 60 to 90 ℃.
13. The samarium cobalt recovery method according to claim 1, wherein the step S4 is iron removal by goethite iron removal.
14. The method of claim 1, wherein the extractant used in step S5 is P204.
15. The method of claim 14 wherein the extraction is a multistage extraction.
16. The method of claim 1, wherein the current density used in the electrolysis in step S6 is 300-500 a/m 2.
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