CN113502394A - Method for recovering cobalt or nickel intermediate product - Google Patents
Method for recovering cobalt or nickel intermediate product Download PDFInfo
- Publication number
- CN113502394A CN113502394A CN202110577567.5A CN202110577567A CN113502394A CN 113502394 A CN113502394 A CN 113502394A CN 202110577567 A CN202110577567 A CN 202110577567A CN 113502394 A CN113502394 A CN 113502394A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- filter residue
- nickel
- filtrate
- leaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000013067 intermediate product Substances 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052742 iron Inorganic materials 0.000 claims abstract description 63
- 238000002386 leaching Methods 0.000 claims abstract description 52
- 239000000706 filtrate Substances 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000002893 slag Substances 0.000 claims abstract description 22
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 20
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 13
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 20
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052729 chemical element Inorganic materials 0.000 description 9
- 229910052598 goethite Inorganic materials 0.000 description 8
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 8
- 229910052935 jarosite Inorganic materials 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 229910020598 Co Fe Inorganic materials 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- 229910001447 ferric ion Inorganic materials 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 5
- 235000010262 sodium metabisulphite Nutrition 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229940001584 sodium metabisulfite Drugs 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- -1 so that Co Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- 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
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
Abstract
The invention discloses a method for recovering an intermediate product of cobalt or nickel, which comprises the following steps: adding water into the intermediate product of cobalt or nickel, pulping, and leaching with acid to obtain leachate; then carrying out solid-liquid separation on the leaching solution to obtain a first filtrate and a first filter residue; removing ferrous ions from the obtained first filtrate by adopting an oxygen pressure iron removal process, and then carrying out solid-liquid separation to obtain second filter residue and second filtrate; and extracting, evaporating, crystallizing and drying the obtained second filtrate to obtain a cobalt sulfate or nickel sulfate product, and calcining the second filter residue to recover the second filter residue as an iron-making raw material. The method has the advantages of reducing the consumption of auxiliary materials, avoiding the generation of waste iron vanadate slag and the like. The method overcomes the defects that the traditional recovery method generates harmful gas of sulfur dioxide, introduces chloride ions to corrode equipment, generates a large amount of sodium ferrous vanadium waste residues and the like, and is a method for preparing cobalt/nickel sulfate from cobalt/nickel intermediate products with simple process, low cost and high efficiency.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for recovering an intermediate product of cobalt or nickel.
Background
At present, the leaching process of the cobalt (nickel) intermediate product in industry mainly adopts sodium thiosulfate, sodium metabisulfite and sodium sulfite; ferrous sulfate; sulfur dioxide. Sodium thiosulfate, sodium metabisulfite and sodium sulfite are used as reducing agents. The disadvantages are that the harmful gas of sulfur dioxide is generated in the reaction process, the requirements on production equipment and production environment are higher, and sodium ions are introduced. In the oxidation stage of ferrous iron, sodium chlorate is mainly used for oxidizing ferrous ions in industry, sodium carbonate is added for controlling the pH value, and the iron in the solution is removed by the jarosite method to generate a large amount of iron slag. The disadvantages are that: in the iron removal process, because ferrous ions are not easy to precipitate, the ferrous ions are required to be oxidized into the ferric ions and then the pH value is required to be adjusted to precipitate the ferric ions, the common use of sodium chlorate to oxidize the ferrous ions at present has the characteristics of high efficiency and high speed, but chloride ions are introduced from the characteristics, so that the prepared cobalt sulfate product contains a large amount of chloride ions.
Meanwhile, the introduction of chloride ions can greatly accelerate the corrosion of equipment, and especially for extraction equipment and MVR evaporators, the chloride ions with high concentration can be resistant to the corrosion by using expensive titanium alloy materials to a certain extent. The iron in the solution is usually removed by a jarosite method, and the waste residue generated by the iron removal method is jarosite residue. Because of the lack of a reasonable treatment method, a large amount of jarosite slag is accumulated near a factory, which not only occupies the land, but also causes harm to the environment.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recovering an intermediate product of cobalt or nickel.
The invention is realized by the following steps:
the invention provides a method for recovering an intermediate product of cobalt or nickel, which comprises the following steps: leaching the intermediate product of cobalt or nickel to obtain leachate, carrying out solid-liquid separation to obtain a first filtrate and a first filter residue, and removing ferrous ions in the first filtrate by adopting an oxygen pressure iron removal process.
The invention has the following beneficial effects:
the invention provides a method for recovering an intermediate product of cobalt or nickel, which comprises the steps of leaching the intermediate product of cobalt or nickel to obtain a leaching solution, carrying out solid-liquid separation to obtain a first filtrate and a first filter residue, and removing ferrous ions in the first filtrate by adopting an oxygen pressure iron removal process. In the process of recovering ferrous ions, a precipitation method is not adopted, and chlorine is not introduced, so that the consumption of auxiliary materials is reduced, the generation of waste iron slag is avoided, and the like, and the obtained iron slag has high iron content and can be recycled.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic flow chart of a method for recovering a cobalt intermediate product according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a method for preparing cobalt sulfate/nickel from cobalt hydroxide/nickel with simple process, low cost and high efficiency.
The flow diagram of the method for recovering the cobalt intermediate product of the embodiment of the invention is shown in figure 1 by taking the cobalt hydroxide intermediate product as a material. The recovery process is as follows:
(1) adding water into the cobalt hydroxide intermediate product for size mixing, then adding concentrated sulfuric acid for acid dissolution to obtain a leaching solution, and filtering the leaching solution to obtain a first filtrate and a first filter residue.
In the step (1), water is added into the cobalt hydroxide intermediate product for mixing pulp, and then concentrated sulfuric acid is added for acid dissolution, without using sodium thiosulfate, sodium metabisulfite and sodium sulfite as reducing agents. The reducing agent is used for generating harmful gas of sulfur dioxide in the reaction process, so that the requirements on production equipment and production environment are high, and sodium ions are introduced. The acid leaching process of the invention overcomes the above process and reduces the use of harmful gases and auxiliary materials.
(2) And (2) performing high-acid reduction on the first filter residue in the step (1), returning the initial material for recycling, removing ferrous ions in the first filter solution in an oxygen pressure iron removal mode, and performing solid-liquid separation again to obtain a second filter residue and a second filter solution.
In the step (2), because the second filtrate contains cobalt and iron with higher contents, cheap oxygen is used as an oxidant in a high-pressure kettle, the utilization rate of the oxygen is high under the condition, meanwhile, no oxidant is added in the iron removal process, a cobalt solution with higher acid content can be obtained, and the cobalt solution can be used as a high-pressure leaching agent or can be comprehensively utilized with other cobalt raw materials to consume other acids, so that the high-efficiency and effective utilization is achieved.
(3) And (3) calcining the second filter residue in the step (2) to be used as an iron-making raw material again, extracting the second filtrate by P204 and P507, and crystallizing and drying MVR evaporation-OSLO to obtain a cobalt sulfate or nickel sulfate product.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for cobalt or nickel intermediate recovery, comprising: leaching the intermediate product of cobalt or nickel to obtain leachate, carrying out solid-liquid separation to obtain a first filtrate and a first filter residue, and removing ferrous ions in the first filtrate by adopting an oxygen pressure iron removal process.
According to the method for recovering the cobalt or nickel intermediate product, provided by the embodiment of the invention, ferrous ions in the filtrate are removed by adopting an oxygen pressure iron removal process. In the process of recovering ferrous ions, a precipitation method and a traditional jarosite method are not adopted, and in the embodiment of the invention, an oxygen pressure iron removal method is adopted to remove Fe in filtrate2+Oxidation of oxygen to Fe3+，Fe3+And sodium chlorate is not introduced in the process, so that the consumption of auxiliary materials is reduced, and the generation of waste iron slag is avoided.
In an alternative embodiment, the oxygen pressure iron removal process comprises: controlling the oxygen pressure at 0.1-0.5Mpa, the temperature at 80-140 ℃, the rotation speed at 100-.
In the process of removing iron by adopting the oxygen pressure iron removal process, the process conditions are controlled to separate out ferrous ions in the form of goethite instead of ferric hydroxide, which is caused by the following steps: the ferric hydroxide colloid is a colloidal sol which is not easy to filter, and simultaneously, because the ferric hydroxide colloid has strong adsorption capacity, other valuable metal elements, particularly cobalt element can be carried in the ferric hydroxide colloid during precipitation to cause the reduction of the recovery rate of the metal elements, because the forming temperature of the goethite is above 80 ℃, in the process of removing iron by oxygen pressure, the temperature is firstly increased to 80-140 ℃, oxygen with 99 percent concentration is introduced into the first filtrate from the bottom, the oxygen pressure is controlled to be 0.1-0.5Mpa, the reaction is carried out for 1-3h, so that ferrous ions are changed into the form of the goethite to be removed, and Fe in the process2+Is oxidized into Fe by oxygen3+，Fe3+Removing the precipitate in the form of goethite slag, mainlyThe formula is as follows: 2Fe2++1/2O2+3H2O＝2FeO(OH)↓+4H+Theoretical molar mass of Fe2+：O2＝2：1。
In an alternative embodiment, the intermediate product of cobalt or nickel is selected from crude cobalt hydroxide or crude nickel hydroxide.
Because the cobalt ore resources in China are rare, the method always depends on import. In consideration of various aspects, many enterprises process middle-low grade cobalt ores through hydrometallurgy to prepare cobalt intermediate products (mainly existing in the forms of crude cobalt hydroxide and crude cobalt carbonate), in the embodiment of the invention, the crude cobalt hydroxide or crude nickel hydroxide is used as a raw material, and copper cobalt oxide ore can be selected.
In an alternative embodiment, the preparation of the leachate comprises the following steps: adding water into the intermediate product of cobalt or nickel, pulping to obtain ore pulp, and leaching with acid to obtain leachate;
preferably, the liquid-solid ratio is controlled to be 3: 1-5: 1, mixing pulp to obtain ore pulp;
preferably, concentrated sulfuric acid is added into the ore pulp, the end point pH is controlled to be 3-5, the stirring speed is 60-300rad/min, and the reaction is carried out for 0.5-1h to carry out leaching, so as to obtain a leaching solution.
In an optional embodiment, the first filter residue is treated by a reduction process to obtain pickle liquor and water washing liquor.
In an alternative embodiment, the treatment of the first filter residue by the reduction process comprises the following steps: after the first filter residue is leached by sulfuric acid, adding glucose slurry for reduction until the solution turns pink, returning the obtained pickle liquor as the next step of leaching acid, dissolving the intermediate product of cobalt or nickel again, and returning the water washing liquor obtained by washing the first filter residue by water to the water for size mixing;
preferably, the obtained first filter residue is leached for 2-4h by using 1.5-3mol/L sulfuric acid solution at the temperature of 60-95 ℃.
Adding concentrated sulfuric acid when the intermediate product of cobalt or nickel is leached, controlling the end point pH to be 3-5, and reacting the concentrated sulfuric acid with Co, Fe, Mn and Cu in the raw material to generate sulfate, but Co contained in the material3+、Fe3+、Mn4+Cannot be dissolved out under such conditions, therefore, inThe reducing agent and the sulfuric acid are added into the first filter residue to dissolve the first filter residue, high-valence ions in the first filter residue are reduced and dissolved out, and the dissolved liquid is continuously returned to be used as leaching acid of an intermediate product of cobalt or nickel, so that Co, Fe, Mn and Cu, particularly Co elements, can be fully utilized, and the utilization rate of materials and the yield of products are improved.
In an alternative embodiment, the method further comprises: and filtering the solution after iron removal by oxygen pressure to obtain second filter residue and second filtrate.
In an optional embodiment, the obtained second filtrate is subjected to extraction, crystallization and drying to prepare a cobalt sulfate or nickel sulfate product, and the iron slag obtained after the second filter residue is calcined at the temperature of 300-400 ℃ is recycled as an iron-making raw material.
Filtering the solution after removing iron by oxygen pressure to obtain a second filter residue in the form of FeOOH (goethite, oxygen pressure precipitation), wherein the actual value of the iron content in goethite is about 55 percent (the theoretical value is 62 percent), and goethite is calcined to become Fe2O3The content of the iron after calcination is improved, so that the iron slag after calcination can be recycled as an iron-making raw material.
In the embodiment of the invention, the crude cobalt hydroxide is taken as an extraction material, and the recovery method comprises the following steps:
firstly, mixing the cobalt hydroxide intermediate product with water, and controlling the liquid-solid ratio to be 3: 1-5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 3-5, stirring at the speed of 60-300rad/min, reacting for 0.5-1h, and filtering and separating to obtain a first filtrate and a first filter residue; the obtained first filtrate enters an iron removal process, the oxygen pressure is controlled to be 0.1-0.5Mpa, the temperature is controlled to be 80-140 ℃, the rotating speed is 100 plus 300rad/min, and after the reaction time is 1-3h, the second filtrate and the second filter residue are obtained through filtration and separation; calcining the second filter residue at 400 ℃ under 300-.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The leaching process flow for preparing cobalt sulfate from the cobalt hydroxide intermediate product is shown in figure 1. The chemical element content of the crude cobalt hydroxide in this example is shown in table 1.
TABLE 1
| Element(s) | Co | Fe | Mn | Cu |
| Content of raw Material (%) | 34.68 | 0.13 | 6.41 | 0.05 |
(1) Firstly, adding water into the cobalt hydroxide intermediate product for size mixing, and controlling the liquid-solid ratio to be 4.5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 3, stirring at a speed of 60rad/min, reacting for 1h to obtain a leaching solution, filtering and separating the leaching solution to obtain a first filter residue and a first filtrate, and carrying out chemical element analysis on the first filter residue, wherein the results are shown in table 2.
TABLE 2
| Element(s) | Co | Fe | Mn | Cu |
| Content of raw Material (%) | 0.0052 | 0.0038 | 0.0320 | 0.0150 |
(2) And (2) recycling the first filter residue obtained in the step (1), leaching the first filter residue for 2 hours at 90 ℃ by using a 2mol/L sulfuric acid solution, adding glucose slurry, reducing the solution until the solution becomes pink, obtaining an acid leaching solution, returning the acid leaching solution to be used as the next step of leaching acid, dissolving cobalt hydroxide again, and returning a water washing solution obtained by washing the first filter residue with water to be used as water for size mixing.
(3) And (2) carrying out oxygen pressure iron removal on the first filtrate obtained in the step (1), controlling the oxygen pressure to be 0.3Mpa, the temperature to be 100 ℃, the rotating speed to be 280rad/min, and filtering and separating to obtain second filter residue and second filtrate after the reaction time is 2 hours.
(4) And (3) calcining the second filter residue obtained in the step (3) at 350 ℃, wherein the iron slag is shown in Table 3.
TABLE 3
| Element(s) | Co | Fe |
| Content of raw materials(％) | 0.12 | 69.56 |
(5) And (4) extracting the second filtrate obtained in the step (3) by P204 and P507, evaporating by MVR-OSLO for crystallization, and drying to obtain a cobalt sulfate product.
Example 2
The leaching process flow for preparing cobalt sulfate from the cobalt hydroxide intermediate product is shown in figure 1. The chemical element content of the cobalt hydroxide intermediate is shown in table 4.
TABLE 4
| Element(s) | Co | Fe | Mn | Cu |
| Content of raw Material (%) | 34.52 | 0.33 | 4.41 | 0.06 |
(1) Firstly, mixing the cobalt hydroxide intermediate product with water, and controlling the liquid-solid ratio to be 4.5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 4, stirring at a speed of 60rad/min, reacting for 1h, filtering and separating to obtain a first filter residue and a first filtrate, and carrying out chemical element analysis on the first filter residue, wherein the results are shown in table 5.
TABLE 5
| Element(s) | Co | Fe | Mn | Cu |
| Content of raw Material (%) | 0.0042 | 0.0024 | 0.0150 | 0.0210 |
(2) And (2) recycling the first filter residue obtained in the step (1), leaching the first filter residue for 2 hours at 90 ℃ by using a 2mol/L sulfuric acid solution, adding glucose slurry, reducing the solution until the solution becomes pink, obtaining an acid leaching solution, returning the acid leaching solution to be used as the next step of leaching acid, dissolving cobalt hydroxide again, and returning a water washing solution obtained by washing the first filter residue with water to be used as water for size mixing.
(3) And (2) carrying out oxygen pressure iron removal on the first filtrate obtained in the step (1), allowing the obtained first filtrate to enter an iron removal process, controlling the oxygen pressure to be 0.3Mpa, the temperature to be 120p, the rotating speed to be 250rad/min, and carrying out filtration separation after the reaction time is 2 hours to obtain second filter residue and second filtrate.
(4) And (3) calcining the second filter residue obtained in the step (3) at 330 ℃, and carrying out chemical element analysis, wherein the results are shown in table 6.
TABLE 6
| Element(s) | Co | Fe |
| Content of raw Material (%) | 0.12 | 70.12 |
(5) And (4) extracting the second filtrate obtained in the step (3) by P204 and P507, and crystallizing and drying MVR evaporated-OSLO to obtain a cobalt sulfate product.
Example 3
The leaching process flow for preparing nickel sulfate from the nickel hydroxide intermediate product is shown in figure 1. The chemical element contents of the crude nickel hydroxide in this example are shown in table 7.
TABLE 7
| Element(s) | Ni | Fe | Mn | Cu |
| The raw material containsAmount (%) | 17.29 | 0.19 | 2.24 | 0.04 |
(1) Adding water into the crude nickel hydroxide for size mixing, and controlling the liquid-solid ratio to be 4.5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 3, stirring at a speed of 60rad/min, reacting for 1h to obtain a leaching solution, filtering and separating the leaching solution to obtain a first filter residue and a first filtrate, and carrying out chemical element analysis on the first filter residue, wherein the results are shown in table 8.
TABLE 8
| Element(s) | Ni | Fe | Mn | Cu |
| Content of raw Material (%) | 0.0030 | 0.0300 | 0.0390 | 0.0130 |
(2) And (2) recycling the first filter residue obtained in the step (1), leaching the first filter residue for 2 hours at 90 ℃ by using 1.5mol/L sulfuric acid solution, adding glucose slurry, reducing the solution until the solution becomes light green, returning the obtained acid leaching solution to be used as the next step of leaching acid, dissolving nickel hydroxide again, and returning the water washing solution obtained by washing the first filter residue with water to be used as water for size mixing.
(3) And (2) carrying out oxygen pressure iron removal on the first filtrate obtained in the step (1), controlling the oxygen pressure to be 0.3Mpa, the temperature to be 100 ℃, the rotating speed to be 280rad/min, and filtering and separating to obtain second filter residue and second filtrate after the reaction time is 2 hours.
(4) And (3) calcining the second filter residue obtained in the step (3) at 350 ℃, wherein the iron slag is shown in Table 9.
TABLE 9
| Element(s) | Ni | Fe |
| Content of raw Material (%) | 0.069 | 69.36 |
(5) And (4) extracting the second filtrate obtained in the step (3) by P204 and C272, and then crystallizing and drying by MVR evaporation-OSLO to obtain a nickel sulfate product.
Example 4
The leaching process flow for preparing nickel sulfate from the nickel hydroxide intermediate product is shown in figure 1. The chemical element contents of the crude nickel hydroxide in this example are shown in table 10.
Watch 10
| Element(s) | Ni | Fe | Mn | Cu |
| Content of raw Material (%) | 17.57 | 0.20 | 2.08 | 0.01 |
(1) Adding water into the crude nickel hydroxide for size mixing, and controlling the liquid-solid ratio to be 4.5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 3, stirring at a speed of 60rad/min, reacting for 1h to obtain a leaching solution, filtering and separating the leaching solution to obtain a first filter residue and a first filtrate, and carrying out chemical element analysis on the first filter residue, wherein the results are shown in table 11.
TABLE 11
| Element(s) | Ni | Fe | Mn | Cu |
| Content of raw Material (%) | 0.0032 | 0.0330 | 0.0340 | 0.0050 |
(2) And (2) recycling the first filter residue obtained in the step (1), leaching the first filter residue for 2 hours at 90 ℃ by using 1.5mol/L sulfuric acid solution, adding glucose slurry, reducing the solution until the solution becomes light green, returning the obtained acid leaching solution to be used as the next step of leaching acid, dissolving nickel hydroxide again, and returning the water washing solution obtained by washing the first filter residue with water to be used as water for size mixing.
(3) And (2) carrying out oxygen pressure iron removal on the first filtrate obtained in the step (1), controlling the oxygen pressure to be 0.3Mpa, the temperature to be 100 ℃, the rotating speed to be 280rad/min, and filtering and separating to obtain second filter residue and second filtrate after the reaction time is 2 hours.
(4) And (3) calcining the second filter residue obtained in the step (3) at 350 ℃, wherein the iron slag is shown in Table 12.
TABLE 12
| Element(s) | Ni | Fe |
| Content of raw Material (%) | 0.069 | 69.89 |
(5) And (4) extracting the second filtrate obtained in the step (3) by P204 and C272, and then crystallizing and drying by MVR evaporation-OSLO to obtain a nickel sulfate product.
Comparative example 1
The procedure was the same as in example 1, except that: in the oxidation stage of ferrous ions, the temperature is lower than 80 ℃, and the obtained second filter residue comprises the following components: and (3) ferric hydroxide colloid.
Comparative example 2
The procedure was the same as in example 1, except that: in the oxidation stage of ferrous ions, the temperature exceeds 140 ℃, and the obtained second filter residue comprises the following components: and (3) ferric hydroxide colloid.
Comparative example 3
The procedure was the same as in example 1, except that: sodium chlorate is used as an oxidant in the oxidation stage of ferrous ions, and the obtained second filter residue comprises the following components: yellow sodium iron vitriol slag.
Comparative example 4
The procedure was the same as in example 1, except that: sodium pyrosulfite is used as a reducing agent, and the obtained second filter residue comprises the following components: the yellow sodium iron vitriol slag.
Further, as can be seen from examples 1 to 4 of the present invention and comparative examples 1 to 4, the iron content of goethite was more than 55%, and the iron content of the iron slag obtained by removing iron by the jarosite method was about 26%.
In summary, the embodiment of the present invention provides a method for recovering an intermediate product of cobalt or nickel. A brand-new nickel or cobalt extraction scheme is provided, the traditional extraction scheme is abandoned, and particularly the leaching and iron removal aspects are greatly improved, in the leaching stage, water is added into the cobalt or nickel intermediate product for pulp mixing, acid leaching is carried out, sodium thiosulfate, sodium metabisulfite, sodium sulfite and the like are not used as reducing agents, so that the problem of generating sulfur dioxide harmful gas does not exist; in the iron removal stage, ferrous ions in the solution are removed by adopting an oxygen pressure iron removal mode, and a method for removing iron in the solution by using a jarosite method after ferric chlorate oxidizes ferrous ions is not adopted, so that the use amount of auxiliary materials is greatly reduced by adopting the oxygen pressure iron removal mode, more importantly, chlorine is not introduced, the iron content is high, the iron slag can be recycled as an iron making raw material after being calcined, the problem of iron alum slag accumulation caused by the jarosite method is solved, and the calcined iron slag can be effectively utilized as the iron making raw material. The method has the advantages of reducing the consumption of auxiliary materials, avoiding the generation of waste iron slag and the like. The method overcomes the defects that the traditional recovery method generates harmful gas of sulfur dioxide, introduces chloride ions to corrode equipment, generates a large amount of sodium ferrous vanadium waste residues and the like, and is a method for preparing cobalt sulfate/nickel from cobalt hydroxide/nickel with simple process, low cost and high efficiency.
Compared with the prior art, the scheme of the invention has the following advantages:
(1) auxiliary materials such as sodium carbonate and sodium chlorate are not used, so that the cost is reduced;
(2) the method is energy-saving and environment-friendly, and realizes utilization of the iron slag;
(3) the corrosion of chloride ions to equipment is avoided;
(4) reducing sodium ions in the wastewater and reducing the components for treating the sodium wastewater.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recovering cobalt or nickel intermediate products is characterized by comprising the following steps: leaching the intermediate product of cobalt or nickel to obtain a leaching solution, then carrying out solid-liquid separation on the leaching solution to obtain a first filtrate and a first filter residue, and removing ferrous ions in the first filtrate by adopting an oxygen pressure iron removal process.
2. The method of claim 1, wherein the oxygen pressure iron removal process comprises: controlling the oxygen pressure at 0.1-0.5Mpa, the temperature at 80-140 ℃, the rotation speed at 100-.
3. The method according to claim 1, wherein the cobalt or nickel intermediate is selected from crude cobalt hydroxide, copper cobalt oxide ore or crude nickel hydroxide.
4. The method according to claim 1, wherein the preparation of the leachate comprises the following steps: adding water into the intermediate product of cobalt or nickel, pulping to obtain ore pulp, and leaching with acid to obtain leachate;
preferably, the liquid-solid ratio is controlled to be 3: 1-5: 1, mixing pulp to obtain ore pulp;
preferably, concentrated sulfuric acid is added into the ore pulp, the end point pH is controlled to be 3-5, the stirring speed is 60-300rad/min, and the reaction is carried out for 0.5-1h to carry out leaching, so as to obtain a leaching solution.
5. The method according to claim 1, characterized in that the first filter residue is treated by a reduction process to obtain a pickling liquid and a rinsing liquid.
6. The method according to claim 5, characterized in that the treatment of the first filter residue by a reduction process comprises the steps of: after the obtained first filter residue is leached by sulfuric acid, adding glucose slurry for reduction until the solution turns pink, returning the obtained acid leaching solution as the next step of leaching acid, dissolving the cobalt or nickel intermediate product again, and returning the water washing solution obtained by washing the first filter residue with water to the water for size mixing;
preferably, the obtained first filter residue is leached for 2-4h by using 1.5-3mol/L sulfuric acid solution at the temperature of 60-95 ℃.
7. The method of claim 1, further comprising: and filtering the solution after iron removal by oxygen pressure to obtain a second filtrate and a second filter residue.
8. The method as claimed in claim 7, wherein the second filtrate is extracted and crystallized to obtain cobalt sulfate or nickel sulfate product.
9. The method as claimed in claim 7, wherein the second filter residue is calcined at 400 ℃ and 300 ℃ to obtain iron slag;
preferably, the iron slag obtained by calcination is recovered as an iron-making raw material.
10. The method for recovering cobalt or nickel intermediate products as claimed in any one of claims 1 to 9, wherein the cobalt or nickel intermediate products containing Co, Fe, Mn and Cu are used as materials, and the recovery is carried out according to the following steps:
adding water into the crude cobalt hydroxide or the crude nickel hydroxide for size mixing, and controlling the liquid-solid ratio to be 3: 1-5: 1, slowly adding concentrated sulfuric acid, controlling the end point pH to be 3-5, stirring at the speed of 60-300rad/min, and reacting for 0.5-1h to obtain a leaching solution; filtering and separating the leachate to obtain a first filtrate and a first filter residue; the obtained first filtrate enters an iron removal process, the oxygen pressure is controlled to be 0.1-0.5Mpa, the temperature is controlled to be 80-140 ℃, the rotating speed is 100-; extracting the obtained second filtrate by P204 and P507, crystallizing and drying by MVR evaporation-OSLO to obtain a cobalt sulfate or nickel sulfate product, and calcining the second filter residue at 400 ℃ for recycling at 300-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110577567.5A CN113502394A (en) | 2021-05-26 | 2021-05-26 | Method for recovering cobalt or nickel intermediate product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110577567.5A CN113502394A (en) | 2021-05-26 | 2021-05-26 | Method for recovering cobalt or nickel intermediate product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113502394A true CN113502394A (en) | 2021-10-15 |
Family
ID=78008748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110577567.5A Pending CN113502394A (en) | 2021-05-26 | 2021-05-26 | Method for recovering cobalt or nickel intermediate product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113502394A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114058850A (en) * | 2021-11-04 | 2022-02-18 | 中南大学 | Process for leaching nickel from sintered nickel alloy body |
| CN114058844A (en) * | 2021-10-26 | 2022-02-18 | 广东佳纳能源科技有限公司 | Method for removing iron from intermediate product |
| CN114132969A (en) * | 2021-11-22 | 2022-03-04 | 四川顺应动力电池材料有限公司 | Method for preparing high-grade iron oxide by taking nickel-iron alloy as raw material |
| CN115652105A (en) * | 2022-11-18 | 2023-01-31 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138038A1 (en) * | 2007-05-14 | 2008-11-20 | Bhp Billiton Ssm Development Pty Ltd | LOW Eh LEACH WITH SULFUR RECYCLE |
| CN101736151A (en) * | 2010-01-28 | 2010-06-16 | 浙江华友钴业股份有限公司 | Method for removing iron by oxidation and neutralization in cobalt wet smelting process |
| CN107058730A (en) * | 2017-04-10 | 2017-08-18 | 中南大学 | A kind of method and its system comprehensively utilized to cu-ni sulphide ore |
| CN109518005A (en) * | 2018-10-29 | 2019-03-26 | 安徽寒锐新材料有限公司 | A kind of production method of battery grade cobalt sulfate crystal |
| US20190352740A1 (en) * | 2017-04-10 | 2019-11-21 | Central South University | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore |
| CN111575480A (en) * | 2020-05-12 | 2020-08-25 | 浙江中金格派锂电产业股份有限公司 | Method for processing cobalt intermediate product |
| CN112359225A (en) * | 2020-11-12 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Selective leaching process of rough cobalt hydroxide ore |
-
2021
- 2021-05-26 CN CN202110577567.5A patent/CN113502394A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008138038A1 (en) * | 2007-05-14 | 2008-11-20 | Bhp Billiton Ssm Development Pty Ltd | LOW Eh LEACH WITH SULFUR RECYCLE |
| CN101736151A (en) * | 2010-01-28 | 2010-06-16 | 浙江华友钴业股份有限公司 | Method for removing iron by oxidation and neutralization in cobalt wet smelting process |
| CN107058730A (en) * | 2017-04-10 | 2017-08-18 | 中南大学 | A kind of method and its system comprehensively utilized to cu-ni sulphide ore |
| US20190352740A1 (en) * | 2017-04-10 | 2019-11-21 | Central South University | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore |
| CN109518005A (en) * | 2018-10-29 | 2019-03-26 | 安徽寒锐新材料有限公司 | A kind of production method of battery grade cobalt sulfate crystal |
| CN111575480A (en) * | 2020-05-12 | 2020-08-25 | 浙江中金格派锂电产业股份有限公司 | Method for processing cobalt intermediate product |
| CN112359225A (en) * | 2020-11-12 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Selective leaching process of rough cobalt hydroxide ore |
Non-Patent Citations (3)
| Title |
|---|
| 中国有色金属工业协会: "《有金属系列丛书 中国钴业》", 31 August 2012, pages: 18 - 19 * |
| 郭学益: "废弃电路板多金属粉末低温碱性熔炼 理论及工艺研究", 冶金工业出版社, pages: 53 - 65 * |
| 陈家镛: "《湿法冶金手册》", 30 September 2005, pages: 67 - 68 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114058844A (en) * | 2021-10-26 | 2022-02-18 | 广东佳纳能源科技有限公司 | Method for removing iron from intermediate product |
| CN114058850A (en) * | 2021-11-04 | 2022-02-18 | 中南大学 | Process for leaching nickel from sintered nickel alloy body |
| CN114132969A (en) * | 2021-11-22 | 2022-03-04 | 四川顺应动力电池材料有限公司 | Method for preparing high-grade iron oxide by taking nickel-iron alloy as raw material |
| CN115652105A (en) * | 2022-11-18 | 2023-01-31 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
| CN115652105B (en) * | 2022-11-18 | 2023-12-19 | 金川集团股份有限公司 | Sectional leaching process for cobalt raw material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113502394A (en) | Method for recovering cobalt or nickel intermediate product | |
| JP5157943B2 (en) | Method for recovering nickel from sulfuric acid aqueous solution | |
| CN102121068B (en) | Method for preparing vanadium pentoxide | |
| CN110358917B (en) | Process method for treating sodium ferbamate cobalt slag | |
| CN109110826B (en) | Production method of battery-grade nickel sulfate | |
| JP6336469B2 (en) | Method for producing scandium-containing solid material with high scandium content | |
| MXPA00005341A (en) | A method of purifying acid leaching solution. | |
| RU2769875C2 (en) | Method for producing raw materials for leaching | |
| CN113265532A (en) | Method for leaching nickel-ammonia solution from nickel-iron alloy by wet method and application | |
| CN113088710A (en) | Method for separating copper and germanium from copper and germanium replacement slag | |
| WO2021119728A1 (en) | Recovery of vanadium from slag materials | |
| CN104862503B (en) | The method that scandium is extracted from lateritic nickel ore | |
| CN106904664A (en) | Hydroxyl cobaltosic oxide and preparation method thereof | |
| CN112813260A (en) | Reduction leaching method | |
| JP2008240009A (en) | Method for chlorine-leaching nickel sulfide | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| CN103194598A (en) | Method for improving recovery rate of gold ore difficult to treat by adopting sulfuric acid leaching reduction process | |
| JP2008231470A (en) | Method for controlling reaction in sulphidizing process | |
| CN113201657B (en) | Method for separating vanadium and chromium from vanadium and chromium-containing solution through co-extraction-selective back extraction | |
| CN114058844A (en) | Method for removing iron from intermediate product | |
| CN110629043B (en) | Bismuth extraction method based on phase transformation of bismuth sulfide ore | |
| JP5423973B2 (en) | Cemented carbide scrap processing method | |
| CN114164344B (en) | Method for separating and recovering zinc and cobalt from cobalt-containing zinc slag | |
| JP7354845B2 (en) | Method for producing nickel sulfate aqueous solution | |
| Pandey et al. | Co‐Extraction—Selective stripping for the recovery of nickel and copper from the leach liquor of ocean nodules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211015 |