CN115074530A - Method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under hydrochloric acid system - Google Patents
Method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under hydrochloric acid system Download PDFInfo
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- CN115074530A CN115074530A CN202210360332.5A CN202210360332A CN115074530A CN 115074530 A CN115074530 A CN 115074530A CN 202210360332 A CN202210360332 A CN 202210360332A CN 115074530 A CN115074530 A CN 115074530A
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- 238000002386 leaching Methods 0.000 title claims abstract description 90
- 239000002253 acid Substances 0.000 title claims abstract description 88
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 32
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000002739 metals Chemical class 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 72
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 72
- 238000001556 precipitation Methods 0.000 claims abstract description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 39
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 39
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 38
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 19
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 19
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 156
- 229910052742 iron Inorganic materials 0.000 claims description 45
- 238000000926 separation method Methods 0.000 claims description 25
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 22
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- 238000007865 diluting Methods 0.000 claims description 11
- 229910001447 ferric ion Inorganic materials 0.000 claims description 11
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 45
- 150000002910 rare earth metals Chemical class 0.000 abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 abstract description 28
- 239000010941 cobalt Substances 0.000 abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 28
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- -1 iron ions Chemical class 0.000 description 31
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008213 purified water Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002893 slag Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 229910003153 β-FeOOH Inorganic materials 0.000 description 1
Classifications
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- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C22B23/0423—Halogenated 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues in a hydrochloric acid system, which comprises the steps of fully dissolving the acid leaching residues by using a hydrochloric acid solution, reducing the obtained acid solution to obtain a ferrous chloride-containing solution, then adding sodium hydroxide, sodium sulfide and sodium bicarbonate in stages to realize fractional precipitation and enrichment of the valuable metals, and finally performing spray pyrolysis on the high-purity ferrous chloride solution after recovering the valuable metals to obtain alpha-Fe with spherical shape and purity of more than 99.2 percent 2 O 3 And (3) powder. The method can enrich and recover rare earth, cobalt and other elements in the neodymium iron boron waste acid leaching residue, improve the utilization value of iron element, and reduce solid residuePiling and reducing environmental pollution.
Description
Technical Field
The invention relates to the field of neodymium iron boron waste recovery, in particular to a method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under a hydrochloric acid system.
Background
With the rapid development of new energy fields, the demand of the neodymium-iron-boron magnet is rapidly increased. However, during the production process of the neodymium iron boron magnet, from raw material pretreatment to final product detection, waste materials are inevitably generated at each step; in addition, as time goes on, more and more devices using the neodymium iron boron magnet are scrapped due to the fact that the devices are out of service, and a large amount of neodymium iron boron waste materials are generated, so that the annual production amount of the neodymium iron boron waste materials is increased, for example, 2.8 ten thousand tons of waste materials are generated in 2016, and 5.0 ten thousand tons of waste materials are generated in 2021. The content of rare earth in the neodymium iron boron waste material is about 30%, the main elements comprise Ce, Pr, Nd, Gd and the like, and the rest are elements such as iron, aluminum, cobalt and the like. Therefore, the neodymium iron boron waste contains valuable elements with higher content, and has higher comprehensive recycling value.
At present, the valuable metals in the neodymium iron boron waste materials are mainly recovered by a hydrochloric acid optimum solution method in the industry, and the main processes comprise oxidizing roasting, hydrochloric acid optimum solution, extraction separation, precipitation roasting and the like. In the process of oxidizing and roasting the neodymium iron boron waste, the iron element is fully oxidized to form ferric oxide which is difficult to dissolve in acid, and the rare earth element is oxidized to be rare earth oxide; then the roasted product is put into hydrochloric acid for preferential dissolution, so that the rare earth oxide is dissolved and leached preferentially. In the preferential dissolution process of the hydrochloric acid, a certain amount of ferric oxide or incompletely oxidized ferrous oxide is still dissolved and leached into the leachate, at the moment, an oxidant is added into the leachate, the pH value of the leachate is regulated, the dissolved iron element is precipitated in the form of ferric hydroxide and enters acid leaching residue, and finally, the aim of separating most of rare earth from iron is fulfilled by filtering and washing with weak acid. However, the main component of the acid leaching residue is Fe 2 O 3 /Fe(OH) 3 However, the slag still contains a few tenths to a few percent of rare earth elements and metal elements such as cobalt. At present, the acid leaching slag in industry is added into the ferrous metallurgy process to recover the iron element, and valuable metals such as rare earth, cobalt and the like in the slag are not recovered, so that the waste of resources is caused.
There have been some studies on the comprehensive recovery of acid leaching residue, for example, wu zhan and the like, in the study on the comprehensive recovery and utilization technology of secondary waste of neodymium iron boron magnetic materials in the thesis, hydrochloric acid is adopted for complete dissolution, after metal is transferred into solution, hydrolysis of Fe is firstly carried out, beta-FeOOH is obtained by separation, and iron oxide red with the purity of 98.01% is obtained by roasting; then hydrolyzing the solution with NH 4 HCO 3 And (4) a precipitator, namely recovering the rare earth and the cobalt by fractional precipitation through pH adjustment. However, in the process of Fe/RE/Co precipitation separation, the comprehensive recovery rate of relevant valuable metals is not high, namely 89% of iron, 88% of cobalt and only 79% of rare earth. At the same time, in patent CN201610246932.3, sulfuric acid is used for decomposing acid-dissolving slag, and then Fe is reduced by scrap iron 3+ Production of Fe 2+ In the patent, rare earth/cobalt elements in acid leaching slag are recycled and enriched step by step in a solution in the processes of acid decomposition, purification and impurity removal and washing of the iron oxide red, the whole process flow is very complex, the industrial production efficiency is seriously influenced, and the requirement on equipment is high. The patent CN201810865627.1 recovers rare earth elements by a multi-stage acid washing mode, but the recovery rate is not high, the concentration of the obtained solution is low, and the rare earth is difficult to enrich; cobalt also did not collect well. CN201910009567.8 adopts flash reduction mode to separate iron and rare earth, thereby recovering rare earth and iron with high efficiency.
In summary, how to provide a method for efficiently separating valuable elements such as rare earth and iron under the condition that iron element occupies a main body for comprehensive recovery of acid leaching residue generated in the recovery process of neodymium iron boron waste, and meanwhile, high-valued utilization of iron element is performed to improve the recovery benefit of waste in industry, which is a technical problem to be solved urgently at present.
Disclosure of Invention
The invention mainly aims to develop a method for treating neodymium iron boron waste acid leaching residue so as to enrich and recover elements such as rare earth, cobalt and the like, improve the utilization value of iron elements, reduce the stockpiling of solid residue and reduce the environmental pollution.
In order to achieve the purpose, the method for comprehensively recovering the valuable metals from the neodymium iron boron waste acid leaching residue under the hydrochloric acid system specifically comprises the following steps.
(1) Acid leaching residue two-stage countercurrent acid dissolution reduction: carrying out two-stage countercurrent acid leaching on the acid leaching residue by adopting 6.0-9.0mol/L hydrochloric acid solution, controlling the temperature to be 60-90 ℃, and carrying out solid-liquid separation to obtain acid solution and acid leaching residue; then reducing agent is introduced to reduce the acid solution to obtain ferrous chloride-containing solution.
(2) And (3) precipitation and enrichment of valuable metals step by step: firstly, adding a sodium hydroxide solution into the ferrous chloride-containing solution to adjust the pH value to 3.1-3.4, then adding a sodium sulfide solution, wherein the addition amount of sodium sulfide is 3-6 times of the theoretical amount required by complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution containing sodium sulfide and sodium bicarbonate to adjust the pH value of the ferrous chloride-containing solution to 4.4-4.7, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate.
(3) Preparing iron oxide red by spray pyrolysis: diluting high-purity ferrous chloride solution to 30-60g/L (calculated by ferric ions), and then carrying out spray pyrolysis to prepare alpha-Fe 2 O 3 And (3) powder.
Further, the molar ratio of sodium sulfide to sodium bicarbonate in the mixed solution containing sodium sulfide and sodium bicarbonate is 0.2-0.45.
Further, before the step of fractional precipitation and enrichment of valuable metals, one or more of tartaric acid, malic acid, phytic acid, polyvinyl alcohol, hydroxylamine salt and citric acid are added into the ferrous chloride-containing solution.
Further, the reducing agent is waste iron sheet.
Further, the spray pyrolysis temperature is 700-.
Further, the obtained alpha-Fe 2 O 3 The powder is spherical, and the purity reaches more than 99.2%.
According to the composition and characteristics of neodymium iron boron waste acid leaching residue, in order to fully separate iron ions and other non-iron ions and better realize the recovery of valuable metals such as rare earth, cobalt and the like and the high-value utilization of iron elements, 6.0-9.0mol/L hydrochloric acid is adopted to fully dissolve the acid leaching residue at the temperature of 60-90 ℃, the obtained acid solution is reduced to obtain a ferrous chloride-containing solution, then the step-by-step precipitation and enrichment of the valuable metals are realized by adding sodium hydroxide, sodium sulfide and sodium bicarbonate, the elements such as rare earth, cobalt and the like can be recovered as much as possible by controlling the adding sequence and the using amount of a precipitator, and the loss rate of iron is reduced; before the addition of the precipitant, it is preferable to add a solution containing thionyl chlorideOne or more of tartaric acid, malic acid, phytic acid, polyvinyl alcohol, hydroxylamine salt and citric acid are added into the iron solution, so that iron ions and rare earth/cobalt ions can be separated more efficiently; finally, the obtained high-purity ferrous chloride solution is subjected to spray pyrolysis at the temperature of 700- 2 O 3 And (3) powder.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
The existing method for recovering valuable metals from neodymium iron boron waste acid-soluble slag is mainly a flash method, an acid dissolving-precipitating method and the like, but the methods have some defects, such as low recovery rate of rare earth, cobalt and the like, low purity of iron oxide red and the like, and limit the application field of the methods.
The invention provides a method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under a hydrochloric acid system, so as to realize the recovery of valuable metals such as rare earth, cobalt and the like and the high-value utilization of iron elements. The method specifically comprises the following steps.
(1) Acid leaching residue two-stage countercurrent acid dissolution reduction: carrying out two-stage countercurrent acid leaching on the acid leaching residue by adopting 6.0-9.0mol/L hydrochloric acid solution, controlling the temperature to be 60-90 ℃, and carrying out solid-liquid separation to obtain acid solution and acid leaching residue; at the moment, the leaching rate of the rare earth reaches more than 95 percent, the leaching rate of the cobalt reaches more than 98 percent, and the leaching rate of the iron exceeds 90 percent. Then reducing the acid solution by introducing a reducing agent to obtain a ferrous chloride-containing solution, wherein the solution is detected by KSCN to generate no red precipitate, and the content of ferric ions in the ferrous chloride-containing solution is less than 0.2 g/L; the preferable reducing agent is waste iron sheet, waste resources can be fully utilized, other impurities are not introduced, and the concentration of the iron element in the ferrous chloride-containing solution can be increased.
(2) And (3) precipitation and enrichment of valuable metals step by step: firstly, adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.1-3.4, and completely precipitating and hydrolyzing aluminum ions in the solution, so that the phenomenon that the existence of the aluminum ions increases the dosage of a subsequent sodium sulfate precipitator can be avoided; then adding a sodium sulfide solution, wherein the addition amount of the sodium sulfide is 3-6 times of the theoretical amount required by the complete precipitation of the cobalt ions in the ferrous chloride-containing solution, and precipitating most of the cobalt ions in the solution; finally, adding a mixed solution of sodium sulfide and sodium bicarbonate, adjusting the pH value of the ferrous chloride solution to 4.4-4.7, basically precipitating rare earth ions and residual cobalt ions, and finally performing solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate; in the whole process, the precipitation rate of rare earth and cobalt elements is more than 95%, the precipitation rate of aluminum is more than 99%, and the loss rate of ferrous ions is less than 5%. Particularly, the order of the three precipitants cannot be adjusted, otherwise, the problems of large sodium sulfide consumption, high ferrous precipitation rate, low valuable metal precipitation rate and the like are easily caused; moreover, for the mixed solution of sodium sulfide and sodium bicarbonate, the single solution of sodium sulfide or sodium bicarbonate cannot be simply used as the precipitant, because if the single solution of sodium sulfide is used as the precipitant, the rare earth ions are not completely precipitated; if sodium bicarbonate is used as a precipitator, the cobalt ions are not completely precipitated; if a large portion of the cobalt and rare earth are to be precipitated using sodium sulfide or sodium bicarbonate precipitants, the rate of iron loss is greatly increased. Meanwhile, the molar ratio of the sodium sulfide to the sodium bicarbonate in the mixed solution of the sodium sulfide and the sodium bicarbonate is 0.2-0.45, and the rare earth/cobalt and iron elements can be better separated under the condition. If the molar ratio is more than 0.45, the alkalinity of the mixed solution is higher, so that more carbonate is contained in the solution, and the precipitation rate of the iron element is increased in the precipitation process; if the molar ratio is less than 0.2, most of the precipitation of cobalt cannot be achieved while the precipitation of rare earth is complete. Particularly, before the step of fractional precipitation and enrichment of the valuable metal, one or more of tartaric acid, malic acid, phytic acid, polyvinyl alcohol, hydroxylamine salt and citric acid are preferably added into ferrous chloride. By adding the auxiliary agents, ferrous ions can be preferentially complexed more, so that the iron precipitation is reduced when rare earth or cobalt is precipitated, the yield of iron element is finally improved, and the purity of rare earth and cobalt in valuable metal concentrate is increased.
(3) Preparing iron oxide red by spray pyrolysis: diluting high-purity ferrous chloride solution to 30-60g/L, wherein the concentration is calculated by ferric ionsThen spray pyrolysis is carried out at the temperature of 700-1100 ℃, and the obtained alpha-Fe is prepared 2 O 3 And (3) powder. alpha-Fe obtained 2 O 3 The powder is spherical, and the purity reaches more than 99.2%.
The method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under a hydrochloric acid system provided by the invention will be further described by combining the embodiment.
Comparative example 1
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 8.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 80 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.6%, the cobalt leaching rate is 98.4%, and the iron leaching rate is 91.2%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.2, adding 0.4mol/L sodium sulfide solution, wherein the adding amount of the sodium hydroxide solution is 6 times of the theoretical amount required by complete precipitation of cobalt ions in the ferrous chloride-containing solution, and performing solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.1%, the precipitation rate of rare earth ions is 31.5%, the precipitation rate of cobalt ions is 90.2%, and the precipitation rate of iron ions is 0.8%. Diluting high-purity ferrous chloride solution to 45g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 800 ℃ to prepare the spherical alpha-Fe with the purity of 97.6 percent 2 O 3 And (3) powder.
Comparative example 2
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 8.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 80 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.6%, the cobalt leaching rate is 98.4%, and the iron leaching rate is 91.2%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding sodium hydroxide solution into ferrous chloride-containing solution for regulationAnd (2) when the pH value is 3.2, adding 0.4mol/L sodium sulfide solution, wherein the addition amount of the sodium sulfide solution is 6 times of the theoretical amount required by the complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution with the molar ratio of sodium sulfide to sodium bicarbonate being 0.6, adjusting the pH value of the ferrous chloride solution to be 4.6, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.2%, the precipitation rate of rare earth ions is 86.2%, the precipitation rate of cobalt ions is 96.2%, and the precipitation rate of iron ions is 9.1%. Diluting high-purity ferrous chloride solution to 45g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 800 ℃ to prepare alpha-Fe with spherical shape and 98.1% purity 2 O 3 And (3) powder.
Comparative example 3
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 8.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 80 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.6%, the cobalt leaching rate is 98.4%, and the iron leaching rate is 91.2%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.2, adding a mixed solution of sodium sulfide and sodium bicarbonate with the molar ratio of 0.4, adjusting the pH value of the ferrous chloride solution to 4.6, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.2%, the precipitation rate of rare earth ions is 96.1%, the precipitation rate of cobalt ions is 86.4%, and the precipitation rate of iron ions is 8.3%. Diluting high-purity ferrous chloride solution to 45g/L with purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 800 ℃ to prepare spherical alpha-Fe with the purity of 97.8 percent 2 O 3 And (3) powder.
Comparative example 4
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 8.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 80 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, and at the moment, the rare earth leaching rate is higher95.6 percent, the leaching rate of cobalt is 98.4 percent, and the leaching rate of iron is 91.2 percent; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.2, adding 0.4mol/L sodium sulfide solution, wherein the adding amount of the sodium hydroxide solution is 6 times of the theoretical amount required by the complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a sodium bicarbonate solution to adjust the pH value of the ferrous chloride solution to 4.6, and performing solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.2%, the precipitation rate of rare earth ions is 97.1%, the precipitation rate of cobalt ions is 83.2%, and the precipitation rate of iron ions is 6.8%. Diluting high-purity ferrous chloride solution to 45g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 800 ℃ to prepare the spherical alpha-Fe with the purity of 97.9 percent 2 O 3 And (3) powder.
Example 1
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 8.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 80 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.6%, the cobalt leaching rate is 98.4%, and the iron leaching rate is 91.2%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.2, adding 0.4mol/L sodium sulfide solution, wherein the adding amount of the sodium sulfide solution is 6 times of the theoretical amount required by complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution of sodium sulfide and sodium bicarbonate with the molar ratio of 0.4, adjusting the pH value of the ferrous chloride solution to 4.6, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.2%, the precipitation rate of rare earth ions is 96.5%, the precipitation rate of cobalt ions is 96.2%, and the precipitation rate of iron ions is 4.4%. Diluting high-purity ferrous chloride solution to 45g/L with purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 800 ℃ to prepare the shapeIs spherical alpha-Fe with purity up to 99.2% 2 O 3 And (3) powder.
Example 2
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of hydrochloric acid solution with the concentration of 7.0mol/L is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 90 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 96.4%, the cobalt leaching rate is 99.1%, and the iron leaching rate is 92.0%; and then, reducing the acid solution by using ascorbic acid until the solution detects the generation of red precipitate by using KSCN, thereby obtaining a ferrous chloride-containing solution. Adding a sodium hydroxide solution into a ferrous chloride-containing solution to adjust the pH value to 3.3, adding 0.4mol/L sodium sulfide solution, wherein the addition amount of the sodium sulfide solution is 4 times of the theoretical amount required by complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution of sodium sulfide and sodium bicarbonate with the molar ratio of 0.3, adjusting the pH value of the ferrous chloride solution to 4.5, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.2%, the precipitation rate of rare earth ions is 95.7%, the precipitation rate of cobalt ions is 96.7%, and the precipitation rate of iron ions is 4.0%. Diluting high-purity ferrous chloride solution to 55g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 1000 ℃ to prepare the spherical alpha-Fe with the purity of 99.4 percent 2 O 3 And (3) powder.
Example 3
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 9.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 70 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.6%, the cobalt leaching rate is 98.6%, and the iron leaching rate is 91.4%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding tartaric acid into ferrous chloride-containing solution to make the concentration of tartaric acid in the solution be 0.5g/L, regulating pH to 3.1 by using sodium hydroxide solution, then adding 0.4mol/L sodium sulfide solution, its addition quantity is 5 times of required theoretical dosage for completely precipitating cobalt ion in the above-mentioned ferrous chloride-containing solution, and its optimum dosage isThen adding a mixed solution with the molar ratio of sodium sulfide to sodium bicarbonate being 0.2, adjusting the pH value of the ferrous chloride solution to be 4.7, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.3%, the precipitation rate of rare earth ions is 96.9%, the precipitation rate of cobalt ions is 97.7%, and the precipitation rate of iron ions is 3.5%. Diluting high-purity ferrous chloride solution to 30g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 700 ℃ to prepare the spherical alpha-Fe with the purity of 99.5 percent 2 O 3 And (3) powder.
Example 4
10g of neodymium iron boron waste acid leaching residue is taken, 40mL of 6.0mol/L hydrochloric acid solution is adopted to carry out two-stage countercurrent leaching on the acid leaching residue, the reaction temperature is controlled to be 65 ℃, solid-liquid separation is carried out to obtain the acid solution and the acid leaching residue, at the moment, the rare earth leaching rate is 95.3%, the cobalt leaching rate is 98.9%, and the iron leaching rate is 91.8%; and then, carrying out reduction treatment on the acid solution by adopting waste iron sheets until the solution detects the generation of red precipitates by adopting KSCN (KSCN), thus obtaining a ferrous chloride-containing solution. Adding phytic acid into a ferrous chloride-containing solution to enable the concentration of the phytic acid in the solution to be 1.0g/L, adjusting the pH to be 3.4 by adopting a sodium hydroxide solution, then adding 0.4mol/L sodium sulfide solution, wherein the adding amount of the sodium sulfide solution is 3 times of the theoretical amount required by the complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution with the molar ratio of sodium sulfide to sodium bicarbonate being 0.45, adjusting the pH of the ferrous chloride solution to be 4.4, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and valuable metal concentrate, wherein the precipitation rate of aluminum ions is 99.4%, the precipitation rate of rare earth ions is 96.1%, the precipitation rate of cobalt ions is 98.7%, and the precipitation rate of iron ions is 3.2%. Diluting high-purity ferrous chloride solution to 60g/L by using purified water, wherein the concentration is calculated by ferric ions, and then carrying out spray pyrolysis at 900 ℃ to prepare the spherical alpha-Fe with the purity of 99.4 percent 2 O 3 And (3) powder.
Claims (6)
1. A method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under a hydrochloric acid system is characterized by comprising the following steps:
(1) acid leaching residue two-stage countercurrent acid dissolution reduction: carrying out two-stage countercurrent acid leaching on the acid leaching residue by adopting 6.0-9.0mol/L hydrochloric acid solution, controlling the temperature to be 60-90 ℃, and carrying out solid-liquid separation to obtain acid solution and acid leaching residue; then introducing a reducing agent to carry out reduction treatment on the acid solution to obtain a ferrous chloride-containing solution;
(2) and (3) precipitation and enrichment of valuable metals step by step: firstly, adding a sodium hydroxide solution into the ferrous chloride-containing solution to adjust the pH value to 3.1-3.4, then adding a sodium sulfide solution, wherein the addition amount of sodium sulfide is 3-6 times of the theoretical amount required by complete precipitation of cobalt ions in the ferrous chloride-containing solution, finally adding a mixed solution containing sodium sulfide and sodium bicarbonate to adjust the pH value of the ferrous chloride-containing solution to 4.4-4.7, and carrying out solid-liquid separation to obtain a high-purity ferrous chloride solution and a valuable metal concentrate;
(3) preparing iron oxide red by spray pyrolysis: diluting high-purity ferrous chloride solution to 30-60g/L (calculated by ferric ions), and then carrying out spray pyrolysis to prepare alpha-Fe 2 O 3 And (3) powder.
2. The method according to claim 1, wherein the molar ratio of sodium sulfide to sodium bicarbonate in the mixed solution containing sodium sulfide and sodium bicarbonate in the step (2) is 0.2 to 0.45.
3. The method of claim 1, wherein step (2) is preceded by the addition of one or more of tartaric acid, malic acid, phytic acid, polyvinyl alcohol, hydroxylamine salts, citric acid to the acid solution.
4. The method of claim 1, wherein the reducing agent is scrap iron.
5. The method as claimed in claim 1, wherein the spray pyrolysis temperature is 700-.
6. The method of claim 1, wherein α -Fe 2 O 3 The morphology of the powder isSpherical, and the purity reaches more than 99.2 percent.
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