CN112708779B - Preparation method of cobalt sulfate solution - Google Patents
Preparation method of cobalt sulfate solution Download PDFInfo
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- CN112708779B CN112708779B CN202011444452.0A CN202011444452A CN112708779B CN 112708779 B CN112708779 B CN 112708779B CN 202011444452 A CN202011444452 A CN 202011444452A CN 112708779 B CN112708779 B CN 112708779B
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- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 37
- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 37
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 123
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000002386 leaching Methods 0.000 claims abstract description 64
- 238000005406 washing Methods 0.000 claims abstract description 51
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 48
- 239000011777 magnesium Substances 0.000 claims abstract description 48
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- 239000011734 sodium Substances 0.000 claims abstract description 44
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 43
- 238000000605 extraction Methods 0.000 claims abstract description 41
- 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 claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000344 soap Substances 0.000 claims abstract description 40
- 238000005191 phase separation Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 22
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 claims abstract description 21
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 239000012071 phase Substances 0.000 claims description 55
- 239000003350 kerosene Substances 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 15
- 239000011575 calcium Substances 0.000 description 15
- 229910052791 calcium Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- -1 fluorine ions Chemical class 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000004065 wastewater treatment Methods 0.000 description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910018920 CoO(OH) Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of a cobalt sulfate solution, which comprises the following steps: leaching the nickel cobalt hydroxide material by concentrated sulfuric acid and water to obtain a nickel cobalt sulfate leaching solution; reacting the P204 sodium soap organic phase with a nickel sulfate cobalt leaching solution, and then extracting and phase-separating to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium; washing the P204 loaded organic phase to obtain a nickel-washed P204 loaded organic phase; reacting the C272 sodium soap organic phase with a nickel sulfate solution containing high cobalt and magnesium, and then performing countercurrent extraction and phase separation to obtain a C272 loaded organic phase and a nickel-containing raffinate; washing the C272 loaded organic phase to obtain a washed C272 loaded organic phase; and washing the washed C272 loaded organic phase by using a sulfuric acid solution to obtain a cobalt sulfate strip liquor. The method has the advantages of simple and reliable process, strong operability, good impurity removal effect and good nickel-cobalt separation effect.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal smelting, and particularly relates to a preparation method of a cobalt sulfate solution.
Background
Cobalt sulfate (CoSO) 4 ·6H 2 O), rose red crystal, dehydrated to be red powder, dissolved in water and methanol, slightly dissolved in ethanol, used for ceramic glaze and paint drier, used for electroplating, alkaline battery, producing cobalt-containing pigment and other cobalt products, and used for catalyst, analytical reagent, feed additive, tyre adhesive, lithopone additive, etc. The nickel-cobalt hydroxide material contains polyvalent metal elements, and the solution leached by sulfuric acid contains nickel, cobalt, copper, manganese, zinc, iron, lead and calciumAnd metal impurities such as magnesium. A cobalt sulfate solution with high purity is extracted from a cobalt nickel hydroxide material, calcium, magnesium, iron, lead and the like in the solution are removed by a chemical precipitation method, copper, manganese and zinc in the solution are separated by P204 extraction, and then the nickel and the cobalt are separated by a P507 extraction process. The main defects of the prior art are that sodium fluoride is required to be added when calcium and magnesium are removed by a chemical precipitation method, calcium and magnesium slag formed by removing calcium and magnesium by sodium fluoride cannot be treated as solid waste, and fluorine ions have high requirements on equipment in the evaporation process of subsequent finished products.
Disclosure of Invention
In order to overcome the defects of the calcium and magnesium removal technology in the prior art, the invention respectively removes nickel, copper, manganese, zinc, iron, lead, calcium and magnesium ions in the solution by using leaching control and an extraction method, and performs nickel-cobalt separation to obtain a qualified cobalt sulfate solution so as to meet the requirement of producing a cobalt sulfate product.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a cobalt sulfate solution, characterized by comprising the steps of:
(1) Leaching the nickel cobalt hydroxide material by concentrated sulfuric acid and water, and filtering to obtain nickel cobalt sulfate leaching solution with cobalt ion concentration of 2-6 g/L and leaching residues;
(2) Adding sulfonated kerosene into P204, then adding NaOH solution, adjusting the hydrogen ion concentration of the P204 added with the sulfonated kerosene from 0.5 mol/L-0.6 mol/L to 0.2 mol/L-0.3 mol/L, and separating phases to obtain a P204 sodium soap organic phase;
(3) Reacting the P204 sodium soap organic phase with a nickel cobalt sulfate leaching solution, and then extracting and splitting the phases to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium;
(4) Washing the P204 loaded organic phase with dilute hydrochloric acid at normal temperature to obtain a nickel-washed P204 loaded organic phase and a nickel washing solution;
(5) Carrying out back extraction on the P204 loaded organic phase after nickel washing by using hydrochloric acid to obtain a chloride salt back extraction solution with nickel, cobalt and magnesium removed;
(6) Adding sulfonated kerosene into the C272, adding NaOH solution, adjusting the hydrogen ion concentration of the C272 added with the sulfonated kerosene from 0.5mol/L to 0.6mol/L to 0.2mol/L to 0.3mol/L, and performing phase separation to obtain a C272 sodium soap organic phase;
(7) Reacting the C272 sodium soap organic phase with a nickel sulfate solution containing high cobalt and magnesium, and then extracting and splitting the phases to obtain a C272 loaded organic phase and a nickel-containing raffinate;
(8) Washing the C272 loaded organic phase with dilute sulfuric acid to obtain a washed C272 loaded organic phase and a washing phase;
(9) And (4) washing and back-extracting the washed C272 loaded organic phase by using sulfuric acid to obtain a cobalt sulfate back-extraction solution.
The preparation method of the cobalt sulfate solution is characterized in that the cobalt nickel hydroxide material in the step (1) comprises the following components in percentage by mass: 25 to 35 percent of Ni, 2.0 to 3.5 percent of Co, 0.01 to 0.03 percent of Cu, 3.0 to 5.0 percent of Mn, 2.5 to 4.5 percent of Mg2, 0.0003 percent of Cd, 0.01 to 0.025 percent of Na and 45 percent of water; the leaching process conditions are as follows: the leaching pH is 3.5-4.0, the leaching temperature is 60-80 ℃, and the leaching time is 1.5-2.5 h.
The preparation method of the cobalt sulfate solution is characterized in that the mass percentage concentration of the concentrated sulfuric acid in the step (1) is 93-98%; the mass percentage concentration of the NaOH solution in the step (2) and the NaOH solution in the step (6) is 25-30%.
The preparation method of the cobalt sulfate solution is characterized in that in the step (3), the P204 sodium soap organic phase is reacted with the nickel cobalt sulfate leaching solution, and then the phase separation is carried out after 6-9 levels of countercurrent extraction is carried out at 30-40 ℃; the ratio of the P204 sodium soap organic phase to the nickel sulfate cobalt leaching solution is (1-2): 1.
The preparation method of the cobalt sulfate solution is characterized in that in the step (4), the P204 loaded organic phase is subjected to 7-10 stages of countercurrent washing by dilute hydrochloric acid with the concentration of 1.0-2.0 mol/L at normal temperature.
The preparation method of the cobalt sulfate solution is characterized in that hydrochloric acid with the concentration of 2-4 mol/L is used for carrying out back extraction on the P204 loaded organic phase after nickel washing in the step (5), and the phase ratio of the P204 loaded organic phase after nickel washing to the hydrochloric acid solution with the concentration of 2-4 mol/L is (10-15): 1.
The preparation method of the cobalt sulfate solution is characterized in that in the step (7), the C272 sodium soap organic phase is reacted with a nickel sulfate solution containing high cobalt and magnesium, and then the phase separation is carried out after 6-10 levels of countercurrent extraction is carried out at the temperature of 30-40 ℃; the phase ratio of the C272 sodium soap organic phase to the nickel sulfate solution containing high cobalt and magnesium is (1-2): 1.
The method for preparing a cobalt sulfate solution is characterized in that in the step (8), the C272 loaded organic phase is washed by 7-10 stages with dilute sulfuric acid with the concentration of 1.0-2.0 mol/L.
The preparation method of the cobalt sulfate solution is characterized in that in the step (9), the washed C272 loaded organic phase is washed by 6-10 grades with sulfuric acid with the concentration of 0.1-0.4 mol/L, and the phase ratio of the washed C272 loaded organic phase to the sulfuric acid with the concentration of 0.1-0.4 mol/L is (15-30): 1; and (3) carrying out 6-10 grade countercurrent back extraction on the washed C272 loaded organic phase by using sulfuric acid with the concentration of 1.0-2.0 mol/L, wherein the phase ratio of the washed C272 loaded organic phase to the sulfuric acid with the concentration of 1.0-2.0 mol/L is (15-30): 1.
The invention has the beneficial technical effects that: the invention circularly leaches the cobalt nickel hydroxide material by using the concentrated sulfuric acid, can promote the leaching efficiency of cobalt, forbids the addition of sodium sulfite and improves the working environment. The invention uses extraction method to separate cobalt and magnesium, which replaces sodium fluoride to remove calcium and magnesium. The sequence of extracting metals by using an extracting agent P204 is that impurities such as copper, zinc, manganese, calcium, magnesium and the like in a solution are separated from a leaching solution of a nickel cobalt hydroxide material, and a nickel washing section is arranged in the P204 extraction process to ensure that nickel and cobalt are remained in a raffinate as much as possible, so that the recovery of nickel and cobalt is facilitated. And then analyzing nickel, magnesium and cobalt by using C272, and in the process of extracting by using C272, arranging a nickel washing section and a magnesium washing section to ensure that the finally back-extracted loaded organic contains no nickel and magnesium ions as much as possible, firstly separating nickel into raffinate, then washing magnesium, and finally back-extracting to obtain a purer cobalt sulfate solution. And finally, the content of copper, zinc, manganese and calcium in the cobalt sulfate solution is lower than 0.004g/L, the content of nickel is lower than 0.05g/L, the content of magnesium is lower than 0.1g/L, and the quality of the produced cobalt sulfate product meets the requirement of industrial cobalt sulfate (GB/T26523-2011). The method has the advantages of obviously shortened process flow, simple and reliable operation, strong operability, good nickel and cobalt separation effect, good removal effect of various impurities such as copper, zinc, manganese, calcium, magnesium and the like, no introduction of new impurities and good economic value.
Detailed Description
A preparation method of a cobalt sulfate solution comprises the following steps:
(1) Leaching with concentrated sulfuric acid: the method comprises the steps of leaching a nickel cobalt hydroxide material by using concentrated sulfuric acid with the mass percentage concentration of 93-98%, wherein the purpose of leaching the nickel cobalt hydroxide material by using concentrated sulfuric acid is to promote the leaching rate of cobalt by using the concentrated sulfuric acid. The nickel hydroxide cobalt material comprises the following components in percentage by mass: 25 to 35 percent of Ni, 2.0 to 3.5 percent of Co, 0.01 to 0.03 percent of Cu, 3.0 to 5.0 percent of Mn, 2.5 to 4.5 percent of Mg2, 0.0003 percent of Cd, 0.01 to 0.025 percent of Na and 45 percent of water. The concentrated sulfuric acid leaching method comprises the following steps: directly adding a nickel cobalt hydroxide material into concentrated sulfuric acid, pulping the nickel cobalt hydroxide material by using water to adjust the pH value of the solution, controlling the pH value of a leaching end point to 3.5-4.0, controlling the leaching reaction temperature to be 60-80 ℃, controlling the total time of acid leaching reaction to be 1.5-2.5 h, and filtering to obtain a nickel cobalt sulfate leaching solution and leaching residues with the cobalt ion concentration of 2-6 g/L; and recycling the leaching slag with concentrated sulfuric acid. And (3) removing iron and lead from the nickel hydroxide cobalt material by adjusting the pH value in the concentrated sulfuric acid leaching process, removing copper, zinc, manganese and calcium by P204 extraction, and extracting and separating nickel and magnesium by C272 to obtain a qualified cobalt sulfate solution.
(2) Preparing an organic phase: p204 extraction separation of copper, manganese, zinc and calcium: adding sulfonated kerosene into P204 by taking the sulfonated kerosene as a diluent to ensure that the concentration of hydrogen ions in the P204 added with the sulfonated kerosene is 0.5-0.6 mol/L, then adding NaOH solution into the P204 added with the sulfonated kerosene for reaction for 5min to ensure that the concentration of the hydrogen ions in the P204 added with the sulfonated kerosene is adjusted from 0.5-0.6 mol/L to 0.2-0.3 mol/L, and carrying out phase separation to obtain a P204 sodium soap organic phase; the mass percentage concentration of the NaOH solution is 25-30%.
(3) Reacting a P204 sodium soap organic phase with a nickel sulfate cobalt leaching solution, performing 6-9 grade countercurrent extraction at 30-40 ℃, then splitting the phase, extracting copper, manganese, zinc and calcium into the organic phase, leaving nickel, cobalt and magnesium in a raffinate, performing open circuit on the raffinate, and splitting the phase to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium; the ratio of the P204 sodium soap organic phase to the nickel sulfate cobalt leaching solution is (1-2): 1.
(4) Carrying out 7-10 grade countercurrent washing on the P204 loaded organic phase by using dilute hydrochloric acid with the concentration of 1.0-2.0 mol/L at normal temperature to remove nickel, so that nickel, cobalt and magnesium in the organic phase are transferred to the aqueous phase to be produced in a form of nickel chloride solution, merging the nickel chloride solution into an extraction feeding grade, and washing to obtain the nickel-washed P204 loaded organic phase and nickel washing liquid.
(5) Carrying out back extraction on the P204 loaded organic phase after nickel washing by using a hydrochloric acid solution with the concentration of 2-4 mol/L, producing copper, zinc, manganese and calcium in the organic phase in a chloride form to obtain a chloride back extraction solution with nickel, cobalt and magnesium removed, and opening a back extraction solution; the phase ratio of the P204 loaded organic phase after nickel washing to the hydrochloric acid solution with the concentration of 2-4 mol/L is (10-15): 1.
(6) C272 extraction separation of nickel, magnesium and cobalt: adding sulfonated kerosene into C272 by taking the sulfonated kerosene as a diluent, so that the concentration of hydrogen ions in the C272 after the sulfonated kerosene is added is 0.5-0.6 mol/L, then adding NaOH solution into the C272 after the sulfonated kerosene is added, so that the concentration of the hydrogen ions in the C272 after the sulfonated kerosene is added is adjusted from 0.5-0.6 mol/L to 0.2-0.3 mol/L, and carrying out phase separation to obtain a C272 sodium soap organic phase; the mass percentage concentration of the NaOH solution is 25-30%.
(7) Reacting C272 sodium soap organic phase with nickel sulfate solution containing high cobalt and magnesium, performing 6-10 grade countercurrent extraction at 30-40 ℃, then splitting the phase, extracting the cobalt and the magnesium into the organic phase, leaving the nickel in raffinate, performing open circuit on the raffinate, and splitting the phase to obtain a C272 loaded organic phase and nickel-containing raffinate; the phase ratio of the C272 sodium soap organic phase to the nickel sulfate solution containing high cobalt and magnesium is (1-2): 1.
(8) Washing the C272 loaded organic phase by using dilute sulfuric acid with the concentration of 1.0-2.0 mol/L for 7-10 levels, transferring the nickel in the organic phase to the aqueous phase to be produced in a nickel sulfate solution form, and merging the nickel into an extraction feeding level; washing to obtain a washed C272 loaded organic phase and a washed phase;
(9) And (3) carrying out 6-10 grade magnesium washing on the washed C272 loaded organic phase by using a sulfuric acid solution with the concentration of 0.1-0.4 mol/L, carrying the magnesium in the loaded organic phase into the magnesium washing solution, and opening a circuit, wherein the phase ratio of the washed C272 loaded organic phase to the sulfuric acid solution with the concentration of 0.1-0.4 mol/L is (15-30): 1. And (3) carrying out 6-10 grade countercurrent back extraction on the washed C272 loaded organic phase by using a sulfuric acid solution with the concentration of 1.0-2.0 mol/L at normal temperature, producing cobalt in the washed C272 loaded organic phase in the form of cobalt sulfate, and obtaining a cobalt sulfate back extraction solution for removing nickel, copper, iron, manganese, zinc, calcium and magnesium, wherein the phase ratio of the washed C272 loaded organic phase to the sulfuric acid solution with the concentration of 1.0-2.0 mol/L is (15-30): 1.
The extraction mechanism of the invention is as follows:
Ni(OH) 2 +H 2 SO 4 →NiSO 4 +H 2 O
Co(OH) 2 +H 2 SO 4 →CoSO 4 +2H 2 O
CoO(OH)+H 2 SO 4 (concentrated sulfuric acid) → CoSO 4 +O 2 ↑+H 2 O
HX+NaOH→Na 2 X+H 2 O (in the formula, HX represents P204 and C272)
NiX+M 2+ →MX+Ni 2+ (wherein M represents a metal to be extracted)
Example 1
Leaching the nickel cobalt hydroxide material by using concentrated sulfuric acid with the mass percentage concentration of 93%, wherein the liquid-solid mass ratio of the concentrated sulfuric acid to the nickel cobalt hydroxide material is 10:1, reacting for 30min. Pulping the nickel cobalt hydroxide material by using water, adjusting the pH value of the solution at 80 ℃, controlling the pH value of the leaching end point to be 3.5, controlling the total time of acid leaching reaction to be 1.5h, and filtering to obtain nickel cobalt sulfate leaching solution and leaching residues with the cobalt ion concentration of 4.25 g/L.
Sulfonated kerosene is used as a diluting agent, the sulfonated kerosene is added into P204, the concentration of hydrogen ions in the P204 after the sulfonated kerosene is added is 0.50mol/L, 10.0L of the P204 after the sulfonated kerosene is added into 260mL of NaOH solution with the mass percent concentration of 30 percent for reaction, phase separation is carried out after the reaction, and a P204 sodium soap organic phase and a water phase are obtained and are discharged out of a wastewater treatment system.
And (3) reacting the P204 sodium soap organic phase with 5L of nickel sulfate cobalt leaching solution, performing 9-stage countercurrent extraction, then separating the phases to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium, and using the water phase after phase separation as a raw material for C272 extraction for later use.
Sulfonated kerosene is used as a diluent, the sulfonated kerosene is added into C272, the concentration of hydrogen ions in the C272 after the sulfonated kerosene is added is 0.50mol/L, 10.0L of the C272 after the sulfonated kerosene is added into 250mL of NaOH solution with the mass percent concentration of 30% for reaction, phase separation is carried out after the reaction, a C272 sodium soap organic phase and a water phase are obtained, and the water phase is discharged out of a wastewater treatment system.
The C272 sodium soap organic phase reacts with nickel sulfate solution containing high cobalt and magnesium, then phase separation is carried out, and a C272 loaded organic phase and nickel-containing raffinate are obtained after phase separation. And (3) washing the C272 loaded organic phase by 10 grades of dilute sulfuric acid with the concentration of 1.0mol/L, wherein the pH of an outlet is =4, and obtaining the washed C272 loaded organic phase and a washed phase after washing. And (3) carrying out 10-stage washing on the washed C272 loaded organic phase by using a sulfuric acid solution with the concentration of 0.15mol/L at normal temperature, carrying out phase separation, and opening a water phase.
Carrying out 6-stage countercurrent back extraction on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 1.0mol/L, wherein the phase ratio is 15: co:32.63g/L, ni:0.012g/L, cu:0.0028g/L, zn:0.00044g/L, mn:0.0009g/L, ca:0.0039g/L, mg:0.073g/L.
Example 2
Leaching the nickel cobalt hydroxide material by concentrated sulfuric acid with the mass percentage concentration of 95%, wherein the liquid-solid mass ratio of the concentrated sulfuric acid to the nickel cobalt hydroxide material is 10:1, reacting for 30min. Pulping the nickel cobalt hydroxide material by using water, adjusting the pH value of the solution at 75 ℃, controlling the pH value of the leaching end point to be 4.0, controlling the total time of acid leaching reaction to be 1.5h, and filtering to obtain nickel cobalt sulfate leaching solution and leaching residues with the cobalt ion concentration of 3.68 g/L.
Sulfonated kerosene is used as a diluent, the sulfonated kerosene is added into P204, the hydrogen ion concentration of the P204 added with the sulfonated kerosene is 0.55mol/L, 10.0L of the P204 added with the sulfonated kerosene is added with 300mL of NaOH solution with the mass percent concentration of 30% for reaction, phase separation is carried out, a P204 sodium soap organic phase and a water phase are obtained, and the water phase is discharged out of the wastewater treatment system.
And reacting the P204 sodium soap organic phase with 7.5L of nickel sulfate cobalt leaching solution, then carrying out phase separation to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium, and using the water phase after phase separation as a raw material for C272 extraction for later use.
Sulfonated kerosene is used as a diluting agent, the sulfonated kerosene is added into C272, the concentration of hydrogen ions in the C272 after the sulfonated kerosene is added is 0.55mol/L, 10.0L of the C272 after the sulfonated kerosene is added into 280mL of NaOH solution with the mass percent concentration of 30% for reaction, phase separation is carried out after the reaction, and a C272 sodium soap organic phase and a water phase are obtained, and the water phase is discharged out of a wastewater treatment system.
The C272 sodium soap organic phase reacts with nickel sulfate solution containing high cobalt and magnesium, then phase separation is carried out, and a C272 loaded organic phase and nickel-containing raffinate are obtained after phase separation. And (3) washing the C272 loaded organic phase by 8-stage washing with dilute sulfuric acid with the concentration of 1.5mol/L, wherein the pH of an outlet is =4.5, and obtaining the washed C272 loaded organic phase and a washed phase after washing. And (3) carrying out 7-stage countercurrent washing on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 0.2mol/L, carrying out phase separation, and opening a water phase.
Carrying out 7-stage countercurrent back extraction on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 1.5mol/L, wherein the phase ratio is 20: co:30.74g/L, ni:0.023g/L, cu:0.0025g/L, zn:0.00052g/L, mn:0.0008g/L, ca:0.0032g/L, mg:0.083g/L.
Example 3
Leaching the nickel cobalt hydroxide material by using concentrated sulfuric acid with the mass percent concentration of 96%, wherein the liquid-solid mass ratio of the concentrated sulfuric acid to the nickel cobalt hydroxide material is 10:1, reacting for 30min. And then slurrying the nickel cobalt hydroxide material with water, adjusting the pH value of the solution at 60 ℃, controlling the pH value of the leaching end point to be 4.0, controlling the total time of acid leaching reaction to be 2.0h, and filtering to obtain nickel cobalt sulfate leaching solution and leaching slag with the cobalt ion concentration of 4.52 g/L.
Sulfonated kerosene is used as a diluent, the sulfonated kerosene is added into P204, the hydrogen ion concentration of the P204 added with the sulfonated kerosene is 0.60mol/L, 10.0L of the P204 added with the sulfonated kerosene is added with 300mL of NaOH solution with the mass percentage concentration of 30% for reaction, phase separation is carried out, a P204 sodium soap organic phase and a water phase are obtained, and the water phase is discharged out of the wastewater treatment system.
And (3) reacting the P204 sodium soap organic phase with 8L of nickel sulfate cobalt leaching solution, then carrying out phase separation to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium, and using the water phase after phase separation as a raw material for C272 extraction for later use.
Sulfonated kerosene is used as a diluting agent, the sulfonated kerosene is added into C272, the concentration of hydrogen ions in the C272 after the sulfonated kerosene is added is 0.60mol/L, 10.0L of the C272 after the sulfonated kerosene is added into 300mL of NaOH solution with the mass percentage concentration of 30% for reaction, phase separation is carried out, a C272 sodium soap organic phase and a water phase are obtained after the phase separation, and the water phase is discharged out of a wastewater treatment system.
The C272 sodium soap organic phase reacts with nickel sulfate solution containing high cobalt and magnesium, then phase separation is carried out, and a C272 loaded organic phase and nickel-containing raffinate are obtained after phase separation. And (3) washing the C272 loaded organic phase by 8-stage washing with dilute sulfuric acid with the concentration of 1.5mol/L, wherein the pH of an outlet is =4.0, and obtaining the washed C272 loaded organic phase and a washed phase after washing. And (3) carrying out 7-stage countercurrent washing on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 0.3mol/L, carrying out phase separation, and opening a water phase.
Carrying out 6-stage countercurrent back extraction on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 1.5mol/L, wherein the phase ratio is 25: co:40.74g/L, ni:0.035g/L, cu:0.0015g/L, zn:0.0006g/L, mn:0.0007g/L, ca:0.0028g/L, mg:0.057g/L.
Example 4
Leaching the nickel cobalt hydroxide material by using concentrated sulfuric acid with the mass percent concentration of 98%, wherein the liquid-solid mass ratio of the concentrated sulfuric acid to the nickel cobalt hydroxide material is 10:1, reacting for 30min. And then slurrying the nickel cobalt hydroxide material with water, adjusting the pH value of the solution at 75 ℃, controlling the pH value of the leaching end point to be 4.0, controlling the total time of acid leaching reaction to be 2.0h, and filtering to obtain nickel cobalt sulfate leaching solution and leaching slag with the cobalt ion concentration of 5.6 g/L.
Sulfonated kerosene is used as a diluting agent, the sulfonated kerosene is added into P204, the concentration of hydrogen ions in the P204 after the sulfonated kerosene is added is 0.56mol/L, 10.0L of the P204 after the sulfonated kerosene is added into 280mL of NaOH solution with the mass percent concentration of 30 percent for reaction, phase separation is carried out after the reaction, and a P204 sodium soap organic phase and a water phase are obtained and are discharged out of a wastewater treatment system.
And (3) reacting the P204 sodium soap organic phase with 10L of nickel sulfate cobalt leaching solution, then carrying out phase separation to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium, and using the water phase after phase separation as a raw material for C272 extraction for later use.
Sulfonated kerosene is used as a diluting agent, the sulfonated kerosene is added into C272, the concentration of hydrogen ions in the C272 after the sulfonated kerosene is added is 0.54mol/L, 10.0L of the C272 after the sulfonated kerosene is added into 280mL of NaOH solution with the mass percent concentration of 30% for reaction, phase separation is carried out after the reaction, and a C272 sodium soap organic phase and a water phase are obtained, and the water phase is discharged out of a wastewater treatment system.
The C272 sodium soap organic phase reacts with nickel sulfate solution containing high cobalt and magnesium, and then phase separation is carried out to obtain a C272 loaded organic phase and nickel-containing raffinate. And (3) washing the C272 loaded organic phase by 8-stage washing with dilute sulfuric acid with the concentration of 1.5mol/L, wherein the pH of an outlet is =4.5, and obtaining the washed C272 loaded organic phase and a washed phase after washing. And (3) washing the washed C272 loaded organic phase by using a sulfuric acid solution with the concentration of 0.30mol/L at normal temperature for 6-stage washing, carrying out phase separation, and opening a water phase.
Carrying out 6-stage countercurrent back extraction on the washed C272 loaded organic phase at normal temperature by using a sulfuric acid solution with the concentration of 2mol/L, wherein the phase ratio is 30: co:45.74g/L, ni:0.027g/L, cu:0.0009g/L, zn:0.0009g/L, mn:0.0008g/L, ca:0.0032g/L, mg:0.078g/L.
Claims (9)
1. A method for preparing a cobalt sulfate solution, comprising the steps of:
(1) Leaching the nickel cobalt hydroxide material by concentrated sulfuric acid and water, and filtering to obtain nickel cobalt sulfate leaching solution with cobalt ion concentration of 2-6 g/L and leaching slag;
(2) Adding sulfonated kerosene into P204, then adding NaOH solution, adjusting the hydrogen ion concentration of the P204 added with the sulfonated kerosene from 0.5 mol/L-0.6 mol/L to 0.2 mol/L-0.3 mol/L, and separating phases to obtain a P204 sodium soap organic phase;
(3) Reacting the P204 sodium soap organic phase with a nickel cobalt sulfate leaching solution, and then extracting and splitting the phases to obtain a P204 loaded organic phase and a nickel sulfate solution containing high cobalt and magnesium;
(4) Washing the P204 loaded organic phase with dilute hydrochloric acid at normal temperature to obtain a nickel-washed P204 loaded organic phase and a nickel washing solution;
(5) Carrying out back extraction on the P204 loaded organic phase after nickel washing by using hydrochloric acid to obtain a chloride salt back extraction solution with nickel, cobalt and magnesium removed;
(6) Adding sulfonated kerosene into the C272, adding NaOH solution, adjusting the hydrogen ion concentration of the C272 added with the sulfonated kerosene from 0.5mol/L to 0.6mol/L to 0.2mol/L to 0.3mol/L, and performing phase separation to obtain a C272 sodium soap organic phase;
(7) Reacting the C272 sodium soap organic phase with a nickel sulfate solution containing high cobalt and magnesium, and then extracting and splitting the phases to obtain a C272 loaded organic phase and a nickel-containing raffinate;
(8) Washing the C272 loaded organic phase with dilute sulfuric acid to obtain a washed C272 loaded organic phase and a washing phase;
(9) And (4) washing and back-extracting the washed C272 loaded organic phase by using sulfuric acid to obtain a cobalt sulfate back-extraction solution.
2. The method for preparing a cobalt sulfate solution according to claim 1, wherein the cobalt nickel hydroxide material in step (1) comprises the following components in percentage by mass: 25 to 35 percent of Ni, 2.0 to 3.5 percent of Co, 0.01 to 0.03 percent of Cu, 3.0 to 5.0 percent of Mn, 2.5 to 4.5 percent of Mg, 0.0003 percent of Cd, 0.01 to 0.025 percent of Na and 45 percent of water; the leaching process conditions are as follows: the leaching pH is 3.5-4.0, the leaching temperature is 60-80 ℃, and the leaching time is 1.5-2.5 h.
3. The method for preparing the cobalt sulfate solution according to claim 2, wherein the mass percentage concentration of the concentrated sulfuric acid in the step (1) is 93-98%; the mass percentage concentration of the NaOH solution in the step (2) and the NaOH solution in the step (6) is 25-30%.
4. The method for preparing the cobalt sulfate solution according to claim 1, wherein in the step (3), the P204 sodium soap organic phase is reacted with the nickel cobalt sulfate leaching solution, and then the phase separation is carried out after 6-9 stages of countercurrent extraction is carried out at 30-40 ℃; the ratio of the P204 sodium soap organic phase to the nickel sulfate cobalt leaching solution is (1-2): 1.
5. The method for preparing a cobalt sulfate solution according to claim 1, wherein the P204-loaded organic phase is subjected to 7-10 stage counter-current washing with dilute hydrochloric acid having a concentration of 1.0-2.0 mol/L at room temperature in step (4).
6. The method for preparing the cobalt sulfate solution according to claim 1, wherein the step (5) is implemented by back-extracting the P204 loaded organic phase after nickel washing with hydrochloric acid with the concentration of 2mol/L-4mol/L, and the ratio of the P204 loaded organic phase after nickel washing to the hydrochloric acid solution with the concentration of 2mol/L-4mol/L is (10-15): 1.
7. The method for preparing the cobalt sulfate solution according to claim 1, wherein in the step (7), the C272 sodium soap organic phase is reacted with the nickel sulfate solution containing high cobalt and magnesium, and then the phase separation is carried out after 6-10 levels of countercurrent extraction is carried out at 30-40 ℃; the phase ratio of the C272 sodium soap organic phase to the nickel sulfate solution containing high cobalt and magnesium is (1-2): 1.
8. The method for preparing a cobalt sulfate solution according to claim 1, wherein the C272-loaded organic phase is washed with dilute sulfuric acid having a concentration of 1.0mol/L to 2.0mol/L in step (8) at stage 7 to 10.
9. The method for preparing the cobalt sulfate solution as claimed in claim 1, wherein the step (9) is carried out 6-10 grade washing of the washed C272 loaded organic phase with sulfuric acid with concentration of 0.1-0.4 mol/L, and the phase ratio of the washed C272 loaded organic phase to the sulfuric acid with concentration of 0.1-0.4 mol/L is (15-30): 1; and (3) carrying out 6-10 stages of counter-current back extraction on the washed C272 loaded organic phase by using sulfuric acid with the concentration of 1.0-2.0 mol/L, wherein the phase ratio of the washed C272 loaded organic phase to the sulfuric acid with the concentration of 1.0-2.0 mol/L is (15-30): 1.
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| CN114314698A (en) * | 2021-12-31 | 2022-04-12 | 金川集团镍盐有限公司 | Method for producing nickel protoxide by preparing low-sulfur nickel chloride through extraction method |
| CN114990355A (en) * | 2022-05-30 | 2022-09-02 | 金川集团镍盐有限公司 | Method for producing cobalt solution by removing magnesium from high-magnesium low-cobalt solution |
| CN115893530A (en) * | 2022-11-30 | 2023-04-04 | 宁波力勤资源科技股份有限公司 | Combined treatment method for nickel cobalt hydroxide raw material |
| CN116835675A (en) * | 2023-06-12 | 2023-10-03 | 浙江路加新材料有限公司 | Method for obtaining battery grade nickel sulfate solution by one-step half extraction of nickel cobalt sulfate leaching solution |
| CN116903051B (en) * | 2023-07-13 | 2023-12-12 | 科立鑫(珠海)新能源有限公司 | Method for producing cobalt chloride by using low-grade cobalt slag |
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