CN115286021A - Method for recovering magnesium oxide from nickel-cobalt intermediate leaching solution - Google Patents
Method for recovering magnesium oxide from nickel-cobalt intermediate leaching solution Download PDFInfo
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- CN115286021A CN115286021A CN202210964288.9A CN202210964288A CN115286021A CN 115286021 A CN115286021 A CN 115286021A CN 202210964288 A CN202210964288 A CN 202210964288A CN 115286021 A CN115286021 A CN 115286021A
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 103
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 100
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 title claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 135
- 238000005406 washing Methods 0.000 claims abstract description 107
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 100
- 239000011777 magnesium Substances 0.000 claims abstract description 88
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 83
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 73
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 50
- 239000012535 impurity Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 230000036571 hydration Effects 0.000 claims abstract description 11
- 238000006703 hydration reaction Methods 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 78
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 40
- 238000007127 saponification reaction Methods 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- FZZVPKMLJITWNS-UHFFFAOYSA-J [Mg++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Mg++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FZZVPKMLJITWNS-UHFFFAOYSA-J 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 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 description 11
- 239000012071 phase Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- NCTHNHPAQAVBEB-WGCWOXMQSA-M sodium ferulate Chemical compound [Na+].COC1=CC(\C=C\C([O-])=O)=CC=C1O NCTHNHPAQAVBEB-WGCWOXMQSA-M 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 7
- 238000009854 hydrometallurgy Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 2
- 239000000347 magnesium hydroxide Substances 0.000 abstract 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 86
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 34
- 239000003921 oil Substances 0.000 description 25
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 16
- 235000019341 magnesium sulphate Nutrition 0.000 description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 10
- 239000001095 magnesium carbonate Substances 0.000 description 10
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 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 description 2
- 238000000658 coextraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DCNGHDHEMTUKNP-UHFFFAOYSA-L diazanium;magnesium;disulfate Chemical compound [NH4+].[NH4+].[Mg+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DCNGHDHEMTUKNP-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UGLUPDDGTQHFKU-UHFFFAOYSA-M [NH4+].S(=O)(=O)([O-])[O-].[Mg+] Chemical compound [NH4+].S(=O)(=O)([O-])[O-].[Mg+] UGLUPDDGTQHFKU-UHFFFAOYSA-M 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZVTLFGTXSNWHAW-UHFFFAOYSA-H magnesium cobalt(2+) nickel(2+) trisulfate Chemical compound S(=O)(=O)([O-])[O-].[Co+2].[Ni+2].[Mg+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] ZVTLFGTXSNWHAW-UHFFFAOYSA-H 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, and relates to the technical field of hydrometallurgy. Firstly, extracting and enriching magnesium by using an acidic phosphorus-containing extractant, carrying out back extraction by using hydrochloric acid to obtain a high-concentration magnesium chloride solution, purifying the magnesium chloride solution to remove impurities and remove Ni and Co impurities in the magnesium chloride solution, carrying out pyrolysis on the purified magnesium chloride solution to obtain primary magnesium oxide and hydrogen chloride tail gas, washing and absorbing the hydrogen chloride tail gas to produce dilute hydrochloric acid, and returning the dilute hydrochloric acid to an extraction system for use. And (3) carrying out crushing, pure water hydration washing and transformation on the magnesium oxide product produced by spray pyrolysis to form magnesium hydroxide, carrying out solid-liquid separation on the magnesium hydroxide, and drying and roasting the washed solid slag at high temperature to produce a high-purity magnesium oxide product. The method can prepare high-purity magnesium oxide, has considerable economic benefit in the whole process, and is suitable for large-scale industrial production; in addition, in the process, carbon-containing raw and auxiliary materials are not introduced, so that the process is a low-carbon green process.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution.
Background
At present, a nickel-cobalt intermediate product is used as a raw material, a hydrometallurgical process is adopted to prepare a nickel-cobalt sulfate product, and the raw material contains various metal elements such as nickel, cobalt, copper, manganese, magnesium and the like, so that when the metal is actually produced and recovered, the magnesium is mainly recovered in the industry to prepare industrial-grade magnesium carbonate or magnesium sulfate and other low value-added products, and no economic benefit can be realized.
Taking rough nickel cobalt hydroxide raw materials produced from African copper cobalt ores and Indonesian laterite-nickel ores as an example, when 1t nickel cobalt salt product with metal content is produced, magnesium materials with metal content of about 0.056t are produced, and the produced magnesium products are low-value and low-chemical-purity magnesium carbonate, magnesium sulfate, ammonium magnesium sulfate and the like, so that the economic benefit and the environmental protection benefit are not ideal. At present, magnesium removal elements through extraction and enrichment in the industry are mainly produced magnesium sulfate solution, wherein the magnesium sulfate solution contains ionic elements such as nickel, cobalt, ammonium radicals and sodium, metal ions such as nickel and cobalt are removed through chemical precipitation before products such as magnesium carbonate and magnesium sulfate are prepared, and then magnesium products are prepared. If the magnesium sulfate solution is extracted and enriched, heavy metals such as nickel and cobalt are removed through sulfide precipitation, magnesium carbonate is precipitated through carbonization, and then the magnesium carbonate is calcined to prepare a magnesium oxide product, the problems that magnesium carbonate sulfate radical is not completely removed, the sulfur content of the magnesium oxide product exceeds the standard, the main MgO content can only reach 95%, the product cannot be sold on the market and the like are solved through production verification.
Therefore, in the prior art in the industry, products such as magnesium carbonate, magnesium oxide and the like produced from hydrometallurgy of nickel-cobalt intermediate products lack competitive advantages in the aspects of market value, product purity, processing cost and the like, and magnesium element treatment and recovery of the nickel-cobalt intermediate products are basically investment of enterprises in the aspect of environmental protection, so that the economic benefit is low.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, and aims to prepare a high-purity magnesium oxide product and improve the economic benefit of magnesium recovery.
The invention is realized by the following steps:
in a first aspect, the invention provides a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, which comprises the following steps:
extracting the magnesium-nickel sulfate solution by using an acidic phosphorus-containing extractant to enrich magnesium, wherein the magnesium extraction comprises extraction and back extraction, and the back extraction is to obtain a magnesium chloride solution by back extraction of enriched magnesium by using hydrochloric acid; wherein the magnesium sulfate nickel solution is a nickel-cobalt intermediate leaching solution;
purifying the magnesium chloride solution to remove impurities, so as to remove impurities of Ni and Co and oil to obtain a purified magnesium chloride solution;
pyrolyzing the purified magnesium chloride solution to obtain primary magnesium oxide and hydrochloric acid, mixing the primary magnesium oxide and water, carrying out hydration washing and solid-liquid separation to obtain filtered residues, and roasting the filtered residues at high temperature to obtain a magnesium oxide product.
In an alternative embodiment, the process of extracting and enriching magnesium is divided into a plurality of sections, which are extraction, washing and back extraction in sequence, the extraction flow ratio O/A is 1-3, the washing flow ratio is 3-25, the flow ratio of pure water washing chlorine is 15-30, and the organic load Na is washed + 、NH 4 + The acid of the magnesium-rich counter-extracted catalyst is dilute sulfuric acid, the hydrochloric acid concentration of the magnesium counter-extracted catalyst is 4-6.5 mol/L, and the counter-extraction flow ratio O/A is 15-30;
optionally, the acidic phosphorus-containing extractant is selected from any one of C272 and P507;
wherein, when the C272 is used for magnesium extraction and enrichment of magnesium in a magnesium-nickel sulfate solution, the concentration of the extracting agent is 10-15%; when the P507 is used for extracting magnesium from a magnesium-nickel sulfate solution to enrich magnesium, the concentration of an extracting agent is 15% -25%, the saponification alkali is any one of ammonia water and liquid alkali, and the saponification rate is 40% -60%;
optionally, in the washing acid, the volume ratio of 1mol/L sulfuric acid to the sulfur washing pure water is 15-30% and 70-85% respectively;
optionally, in the process of extracting magnesium, the C272 extraction system controls the equilibrium pH of extraction to be 5.5-5.8, and according to the flow direction of an oil phase, an extraction production line comprises 1-level saponification, 6-level soap conversion, 7-level extraction, 8-level washing, 3-level sulfur washing, 6-level back extraction and 3-level chlorine washing;
optionally, in the magnesium extraction process, the P507 extraction system controls the equilibrium pH of extraction to be 5.8-6.2, and the extraction production line comprises 1-level saponification, 9-level extraction, 5-level washing, 3-level sulfur washing, 5-level back extraction and 3-level chlorine washing according to the flow direction of an oil phase;
optionally, the pH of the obtained magnesium chloride solution is 3 to 4, and the chemical composition is as follows: mg content of 40-78 g/L, cl content of 71-213 g/L, ni content of 0.5-5 g/L, co content of 0.2-1.5 g/L, na and NH 4+ The content is 0.01 g/L-0.2 g/L, the oil content is 30 ppm-150 ppm, and the temperature is 35 ℃ to 45 ℃.
In an optional embodiment, the magnesium sulfate nickel solution is a leaching solution after impurity removal and cobalt removal;
optionally, the magnesium nickel sulfate solution is raffinate of the nickel cobalt intermediate leaching solution after impurity removal by P204 and cobalt extraction by P507.
In an alternative embodiment, the process of purifying comprises: extracting by using a carboxylic acid extracting agent, adding magnesium oxide hydrated ore pulp in the process to control the pH value of the extraction process to be 6.5-6.8, removing oil from the obtained magnesium chloride raffinate, and then treating by using a heavy metal catching agent to deeply remove impurities of Ni and Co;
optionally, the carboxylic acid extractant is any one of BC196 or BC 191.
In an optional embodiment, in the process of extraction by using the extractant BC196, the concentration of the organic phase extractant is controlled to be 5-25%, the saponification rate is 30-40%, the flow ratio O/A of an extraction section is 0.3-4, the solid content of magnesium oxide hydrated pulp for saponification is 10-30%, the extraction equilibrium pH is adjusted to be 6.2-6.8 by adding chemically pure magnesium oxide, the washing flow ratio is 3-25, the washing acid is dilute hydrochloric acid, the concentration of back extraction sulfuric acid is 1-2.8 mol/L, and the back extraction flow ratio O/A is 4-25;
optionally, the volume ratio of 1mol/L hydrochloric acid in the washing acid to pure chlorine-washing water is 25% -50% and 50% -75%, respectively, and the extraction production line comprises 1-stage saponification, 6-stage extraction, 5-stage washing, 2-stage chlorine-washing, 5-stage back-extraction and 2-stage sulfur-washing according to the flow direction of the oil phase.
In alternative embodiments, the oil removal is adsorption with resin or activated carbon;
alternatively, after degreasing with resin or activated carbon, the chemical composition of the magnesium chloride solution is as follows: oil content of 1ppm to 5ppm, mg content of 20g/L to 78g/L, cl content of 71g/L to 213g/L, ni content of 0.01g/L to 0.05g/L, co content of 0.01g/L to 0.05g/L, na, NH 4+ The content is 0.01 g/L-0.2 g/L, the pH is 3-7, and the temperature is 20-45 ℃.
In an optional embodiment, the adding amount of the sodium ferulate is controlled to be 0.8 to 2 times of the theoretical amount in the treatment process of the sodium ferulate, the pH value is 3 to 7, and the treatment temperature is 10 to 45 ℃;
optionally, the purified magnesium chloride solution obtained after treatment with sodium ferometalate has the following composition: the oil content is 1ppm to 5ppm, the Mg content is 20g/L to 78g/L, the Cl content is 71g/L to 213g/L, the Ni content is 0.0002g/L to 0.001g/L, the Co content is 0.0002g/L to 0.001g/L, the Na content is 0.01g/L to 0.25g/L, the pH is 3 to 7, and the temperature is 20 ℃ to 45 ℃.
In an optional embodiment, in the process of pyrolyzing the purified magnesium chloride solution, the pyrolysis temperature is controlled to be 400-800 ℃, and the pyrolysis time is 3-120 min;
optionally, spray pyrolysis is employed;
more optionally, after the spray pyrolysis, the mass fraction of the byproduct hydrochloric acid is 18% to 20%, and the obtained primary magnesium oxide comprises the following chemical components: the content of MgO is 97-99%, the content of Cl is 0.05-1%, the content of Na is 0.02-0.2%, and the content of Ni and Co is less than or equal to 0.005%.
In an optional embodiment, in the process of hydration washing by mixing primary magnesium oxide and water, the solid-to-solid ratio of the washing liquid is controlled to be 1-4, the hydration washing temperature is 20-60 ℃, and the washing time is 0.5-3 h.
In an optional embodiment, the obtained filter slag is dried and crushed firstly and then is roasted at a high temperature;
optionally, in the drying and crushing process, the drying temperature is controlled to be 100-300 ℃, the drying time is 1-120 min, the granularity of the crushed slag is 1-150 μm, and the temperature is 100-200 ℃.
In an optional embodiment, the high-temperature roasting temperature is 400-900 ℃, and the roasting time is 0.5-3 h;
optionally, crushing after high-temperature roasting, and controlling the particle size of the crushed magnesium oxide product to be 1-90 μm;
optionally, the purity of the magnesium oxide product obtained after crushing is 98-99.4%.
The invention has the following beneficial effects: firstly, extracting the leachate to be treated by using an acidic phosphorus-containing extractant to enrich magnesium, and back-extracting the enriched magnesium by using hydrochloric acid in the magnesium extraction and enrichment process to obtain a magnesium chloride solution; after purifying and removing impurities from the magnesium chloride solution, pyrolyzing the purified magnesium chloride solution to obtain primary magnesium oxide, mixing the primary magnesium oxide with water, carrying out hydration washing and solid-liquid separation to obtain filter residues, and roasting the filter residues at high temperature to obtain a magnesium oxide product. The process can be used for preparing high-purity magnesium oxide, has considerable economic benefit in the whole process, and is suitable for large-scale industrial production; in addition, in the process, carbon-containing raw and auxiliary materials are not introduced, so that the process is a low-carbon green process.
Specifically, the process flow provided by the invention has the following advantages:
(1) The working section of magnesium enrichment adopts hydrochloric acid for back extraction, so that the concentration of magnesium can be improved, and the volume of magnesium enrichment solution is reduced compared with the magnesium sulfate process under the condition of the same mass metal quantity, namely the production load of the subsequent working procedure can be reduced;
(2) The magnesium oxide preparation process can directly carry out spray pyrolysis on the purified magnesium chloride solution, the prepared high-purity magnesium oxide product has high added value, the whole process has considerable economic benefit, and the method is suitable for large-scale industrial production; in addition, in the process, carbon-containing raw and auxiliary materials are not introduced, so that the invention belongs to a low-carbon green production process compared with the traditional magnesium oxide industry.
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 process flow diagram of the recovery of magnesium oxide from a nickel cobalt intermediate leaching solution 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 recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, and please refer to fig. 1, which comprises the following steps:
s1, preparing magnesium chloride solution
The method provided by the embodiment of the invention is used for treating the leachate to be treated, namely the solution obtained by performing two conventional processes of Co extraction and impurity removal on the nickel-cobalt intermediate product leaching solution. The preparation process of the nickel-cobalt intermediate leaching solution comprises the following steps: adding water to the raw material for size mixing → adding sulfuric acid for leaching → chemically purifying iron-removing aluminum silicon → P204 for extracting copper, manganese, zinc, calcium and other impurities → P507 for extracting and removing cobalt → magnesium nickel sulfate solution (the raw material solution of the embodiment of the invention).
The method for preparing the magnesium oxide solution provided by the embodiment of the invention comprises the following steps: extracting magnesium from a magnesium nickel sulfate solution (namely a leaching solution to be treated) by using an acidic phosphorus-containing extractant to enrich magnesium, and performing back extraction on the enriched magnesium by using hydrochloric acid in the magnesium extraction and enrichment process to obtain a magnesium chloride solution; wherein the magnesium sulfate nickel solution is raffinate of the nickel-cobalt intermediate leaching solution after impurity removal by P204 and cobalt extraction by P507. In the magnesium extraction enrichment working section, hydrochloric acid is used for back extraction, so that the concentration of magnesium can be improved, the volume of magnesium solution can be reduced under the condition of the same metal amount, and the production load of the subsequent working procedure can be reduced.
In the actual operation process, the process of extracting and enriching magnesium is divided into a plurality of sections, which are extraction, washing and back extraction in sequence, wherein the extraction is to enrich magnesium in an organic phase, the washing mainly has the function of removing impurities such as ammonium radicals, and the back extraction is to make the magnesium in the organic phase return to a water phase again.
In order to improve the purity of the magnesium oxide solution and fully enrich magnesium, the inventor optimizes the operation parameters in the magnesium extraction and enrichment process: the process of extracting and enriching magnesium is divided into a plurality of sections, which are extraction, washing and back extraction in sequence, the flow ratio of extraction O/A is 1-3, the flow ratio of washing is 3-25, the flow ratio of pure water washing chlorine is 15-30, and organic load Na is washed + 、NH 4 + The acid of the method is dilute sulphuric acid, the hydrochloric acid concentration of the back extraction magnesium is 4 mol/L-6.5 mol/L, and the back extraction flow ratio O/A is 15-30.
Specifically, in the process of extracting and enriching magnesium, the hydrochloric acid concentration of the back extraction magnesium can be 4mol/L, 4.5mol/L, 5.0mol/L, 5.5mol/L, 6.0mol/L and 6.5mol/L; the extraction flow ratio O/A can be 1, 2, 3, etc.; the wash stream ratio can be 3, 5, 7, 10, 12, 15, 20, etc., the strip stream ratio O/A can be 15, 20, 25, 30, etc., and the wash chlorine stream ratio O/A can be 15, 20, 25, 30, etc.
In some embodiments, the acidic phosphorus-containing extractant is selected from any one of C272 and P507, which are effective in enriching magnesium. C272 is used for extracting and separating magnesium and nickel from a nickel magnesium sulfate mixed solution of a high nickel-magnesium ratio solution (the concentration ratio of Ni to Mg is 10-20)), and P507 is used for extracting and separating magnesium and nickel from a nickel magnesium sulfate mixed solution of a low nickel-magnesium ratio solution (the concentration ratio of Ni to Mg is less than 1).
C272 and P507 apply under different conditions:
c272 when the magnesium sulfate nickel solution is used for extracting and enriching magnesium, the concentration of the extracting agent is 10-15%; when the P507 is used for extracting and enriching magnesium from the magnesium sulfate nickel solution, the concentration of an extracting agent is 15-25%, the saponification alkali is any one of ammonia water and liquid alkali, and the saponification rate is 40-60%.
In the process of extracting magnesium, the C272 extraction system controls the balance pH of extraction to be 5.5-5.8, and according to the flow direction of an oil phase, an extraction production line comprises 1-level saponification, 6-level soap conversion, 7-level extraction, 8-level washing, 3-level sulfur washing, 6-level back extraction and 3-level chlorine washing; in the process of extracting magnesium, the P507 extraction system controls the balance pH of extraction to be 5.8-6.2, and an extraction production line comprises 1-level saponification, 9-level extraction, 5-level washing, 3-level sulfur washing, 5-level back extraction and 3-level chlorine washing according to the flow direction of an oil phase.
It should be noted that, the above description of the extraction production line is based on the flow sequence of the oil phase, the saponification stage of the C272 extraction system adopts a 1-stage saponification process, the soap conversion stage adopts a 6-stage soap conversion process, and the extraction stage adopts a 7-stage extraction process, etc. to achieve better extraction effect.
In some embodiments, the washing acid is typically sulfuric acid, since the washed solution is returned to the nickel cobalt intermediate leaching system, which is a sulfuric acid system. In the actual operation process, dilute sulfuric acid and pure water can be respectively injected into the last stage of sodium ammonium washing and the last stage of sulfate radical washing (the sequence is arranged according to the organic flow direction), and the volume ratio of 1mol/L sulfuric acid to the sulfur washing pure water can be controlled to be 15-30 percent and 70-85 percent respectively, so that the hydrogen ion concentration of the washing acid meets the requirement.
The inventor finds that the pH value of the magnesium chloride solution obtained after the magnesium extraction and enrichment process is 3-4, and the chemical composition is as follows: mg content of 40-78 g/L, cl content of 71-213 g/L, ni content of 0.5-5 g/L, co content of 0.2-1.5 g/L, na and NH 4+ The content is 0.01 g/L-0.2 g/L, the oil content is 30 ppm-150 ppm, and the temperature is 35 ℃ to 45 ℃. At the moment, the nickel and cobalt contents in the system are high, and the nickel and cobalt need to be removed in S2.
S2, purifying and removing impurities
The magnesium chloride solution is purified to remove impurities such as Ni and Co to obtain the purified magnesium chloride solution, and the purification and impurity removal mode is not limited, and impurities such as Ni and Co can be removed more fully.
In order to remove impurities such as Ni, co and the like more fully, the inventor optimizes the purification and impurity removal process, and the purification and impurity removal process comprises the following steps: including extraction, deoiling and deep removal of Ni and Co. Specifically, the following process steps can be adopted: extracting with carboxylic acid extractant (such as BC196 or BC 191), adding magnesium oxide hydrated ore pulp to control pH value of the extraction process to 6.2-6.8, deoiling the obtained magnesium chloride raffinate, and treating with sodium fermet to deeply remove impurities of Ni and Co. Most of Ni and Co impurities can be removed through the extractant BC196, and the Ni and Co impurities are deeply removed by utilizing sodium ferometalate after oil removal.
It should be noted that, compared with the sulfidation precipitation method, the method for extracting and purifying nickel-cobalt metal from magnesium chloride solution by BC196 has the following two advantages; firstly, the working environment is improved; secondly, the nickel-cobalt sulfate solution with higher purity and concentration can be obtained and can be directly returned to the main smelting process for utilization.
The inventor optimizes the process of BC196 extraction to remove Ni and Co impurities more fully: in the process of extracting by using the extractant BC196, the concentration of the organic phase extractant is controlled to be 5-25 percent, the saponification rate is controlled to be 30-40 percent, the flow ratio O/A of an extraction section is 0.3-4, the solid content of magnesium oxide hydrated ore pulp for saponification is 10-30 percent, the extraction equilibrium pH is adjusted to be 6.2-6.8 by adding chemically pure magnesium oxide, the washing flow ratio is 3-25, washing acid is dilute hydrochloric acid, the concentration of back extraction sulfuric acid is 1-2.8 mol/L, and the back extraction flow ratio O/A is 4-25.
Specifically, the concentration of the organic phase extracting agent can be controlled to be 5%, 10%, 15%, 20%, 25% and the like, and the extraction section flow ratio O/A can be controlled to be 0.3, 0.5, 1.0, 2.0, 3.0, 4.0 and the like; the solid content of the magnesium oxide hydration ore pulp for saponification can be 10%, 15%, 20%, 25%, 30% and the like; wash stream ratios can be 3, 5, 10, 15, 20, etc.; the concentration of the back extraction sulfuric acid can be 1mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 2.8mol/L and the like; the stripping ratio O/A may be 4, 5, 10, 15, 20, 25, etc.
According to the flow direction of the oil phase, the extraction production line comprises 1-level saponification, 6-level extraction, 5-level washing, 2-level chlorine washing, 5-level back extraction and 2-level sulfur washing. The washing acid adopts hydrochloric acid solution, and is injected into the last stage of magnesium and the last stage of washing chlorine radical in the actual operation process (the stage sequence is arranged according to the organic flow direction), the volume ratio of 1mol/L hydrochloric acid to pure chlorine washing water is controlled to be 25-50% and 50-75%, so that the hydrogen ion concentration is controlled better, and the over-large and over-small acidity is prevented.
In some embodiments, the degreasing is adsorption using resin or activated carbon, but the degreasing is not limited thereto. The inventor finds that after degreasing by resin or activated carbon, the chemical composition of the magnesium chloride solution is as follows: oil content of 1ppm to 5ppm, mg content of 20g/L to 78g/L, cl content of 71g/L to 213g/L, ni content of 0.01g/L to 0.05g/L, co content of 0.01g/L to 0.05g/L, na and NH 4 + The content is 0.01 g/L-0.2 g/L, the pH is 3-7, and the temperature is 20-45 ℃. After extraction and deoiling, the oil content and the Ni and Co content are both obviously reduced.
In some embodiments, the addition amount of the sodium ferulate is controlled to be 0.8-2 times of the theoretical amount (the theoretical amount refers to the theoretical amount of the reaction between the sodium ferulate and the total amount of Ni and Co in the magnesium chloride solution), the pH value is 3-7, and the treatment temperature is 10-45 ℃. The removal effect of Ni and Co impurities can be further improved by further controlling the parameters such as the dosage of sodium fermet, the treatment temperature and the like.
Specifically, the sodium ferbamate removes Ni and Co impurities by utilizing the chelating capacity thereof, and the addition amount of the sodium ferbamate can be 0.8 time, 1.0 time, 1.5 times, 2.0 times and the like of the theoretical amount, so that the aim of deeply removing the Ni and Co impurities can be achieved; the pH value can be controlled to be 3, 4, 5, 6, 7 and the like in the treatment process; the treatment temperature may be 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, etc.
The content of the purified magnesium chloride solution obtained after the treatment with the sodium ferbamate is tested by the inventor as follows: the oil content is 1ppm to 5ppm, the Mg content is 20g/L to 78g/L, the Cl content is 71g/L to 213g/L, the Ni content is 0.0002g/L to 0.001g/L, the Co content is 0.0002g/L to 0.001g/L, the Na content is 0.01g/L to 0.25g/L, the pH is 3 to 7, and the temperature is 20 ℃ to 45 ℃. At the moment, the oil content and the Ni and Co impurity content are both obviously reduced, so that the subsequent preparation of high-purity magnesium oxide is facilitated.
S3, preparing a magnesium oxide product
Pyrolyzing the purified magnesium chloride solution to obtain primary magnesium oxide and hydrochloric acid, mixing the primary magnesium oxide with water, pulping, washing, carrying out solid-liquid separation to obtain filter residue, and roasting the filter residue at high temperature to obtain a magnesium oxide product. The process for preparing the magnesium oxide provided by the embodiment of the invention directly carries out spray pyrolysis on the purified magnesium chloride solution to prepare the magnesium oxide, shortens the process flow, does not release greenhouse gases in the process, and can return the byproduct hydrochloric acid to back extraction for enriching magnesium for utilization.
Specifically, the hydrochloric acid is diluted hydrochloric acid generated by washing and absorbing hydrogen chloride tail gas generated by pyrolysis, and can be returned to an extraction system for use.
In some embodiments, in the process of pyrolyzing the purified magnesium chloride solution, the pyrolysis temperature is controlled to be 400-800 ℃, the pyrolysis time is 3-120 min, and a spray pyrolysis mode can be adopted. Specifically, the pyrolysis temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ and the like. The inventor detects that after spray pyrolysis, the mass fraction of the byproduct hydrochloric acid is 18-20%, and the obtained primary magnesium oxide comprises the following chemical components: the MgO content is 97-99%, the Cl content is 0.05-1%, the Na content is 0.02-0.2%, the Ni and Co contents are less than or equal to 0.005%, and the obtained primary magnesium oxide has high purity.
In order to further improve the purity of the magnesium oxide product, in the process of primary magnesium oxide and water mixing for pulping and washing, the solid-to-solid ratio of the washing liquid is controlled to be 1-4 (such as 1, 2, 3, 4 and the like), the washing temperature is controlled to be 20-60 ℃ (such as 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like), and the washing time can be 0.5-3 h (such as 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0 and the like). The solid-to-solid ratio of the washing liquid refers to the ratio of the volume of the washing liquid to the mass of the primary magnesium oxide.
In some embodiments, the obtained filter slag is dried and crushed firstly and then is roasted at high temperature, surface moisture and impurities are removed through drying, and the crushed filter slag enters a high-temperature roasting stage with smaller particle size, so that the uniformity of the product is promoted.
Further, in the drying and crushing process, the drying temperature is controlled to be 100-300 ℃, the drying time is 1-120 min, the granularity of crushed slag is 1-150 mu m, and the temperature is 100-200 ℃; the high-temperature roasting temperature is 400-900 ℃, and the roasting time is 0.5-3 h. The operation parameters of the drying and crushing process and the high-temperature roasting process are optimized, so that the purity of the product is further improved.
Specifically, the drying temperature may be 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃ or the like; the drying time can be flexible, and can be 1min, 5min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, etc., to meet the requirement of full drying. The operation temperature of the high-temperature roasting stage can be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ and the like; the roasting time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h and the like.
In some embodiments, the high temperature roasting may be followed by crushing, and the particle size of the crushed magnesia product is controlled to be 1 μm to 90 μm. The detection of the inventor shows that the purity of the magnesium oxide product obtained after crushing is 98-99.4%, the iodine absorption value is 130-150, the specific surface area is 30-170 m2/g, and the loose specific gravity is 0.35-0.6 g/cm 3 The ignition loss is less than 3 percent, the chlorine content is less than 0.25 percent, the sulfate content is less than 0.15 percent, the Ni and Co contents are less than or equal to 0.005 percent, the Na content is less than 0.05 percent, the N content is less than 0.003 percent, and the temperature is 20-40 ℃. The final magnesium oxide product has high purity and better market competitiveness, and the overall process obviously increases the economic benefit of the magnesium recovery process.
The features and properties of the present invention are described in further detail below with reference to examples.
The leachate to be treated in the following examples refers to: the magnesium sulfate nickel-cobalt solution is prepared by performing two conventional processes of Co extraction and impurity removal on a nickel-cobalt intermediate leaching solution, and specifically comprises the following components: 0.02-0.1 g/L, ni 1-120 g/L, mg: 1-7 g/L, cu and Mn < 0.0002, cl.
Example 1
The embodiment provides a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, which comprises the following steps:
(1) Preparation of magnesium chloride solution
Extracting and enriching magnesium from a leachate to be treated by using an acidic phosphorus-containing extractant P507, wherein the process of extracting and enriching magnesium is divided into a plurality of sections, which are extraction, washing and back extraction in turn, and the volume ratio of the extractant to diluent No. 260 solvent oil is 1:3, the saponification equivalent of the extractant is 0.3, the magnesium concentration of the magnesium-containing solution is 6g/L, the nickel concentration is 1g/L, the pH value of the feed liquid is 5.8, the hydrochloric acid concentration of the back extraction magnesium is 5mol/L, the extraction flow ratio O/A is 1.45, the washing flow ratio O/A is 22, the volume ratio of 1mol/L sulfuric acid and sulfur washing pure water in the washing acid is 25 percent and 75 percent respectively, the hydrochloric acid of 6.5mol/L is used for back extraction magnesium, and the back extraction flow ratio O/A is 20.
Through detection: the stripping solution contains 75g/L magnesium, 3g/L nickel and pH3.5;
(2) Purifying and impurity removing
The magnesium chloride solution obtained by back extraction is adjusted to pH6.5 by adopting magnesium oxide, and is extracted and nickel is removed by adopting a carboxylic acid extractant BC196, wherein the volume ratio of the extractant BC196 to the diluent No. 260 solvent oil is 1:3, the saponification rate is 30%, the saponified alkaline magnesium salt is magnesium oxide ore pulp, and the solid ratio of the magnesium oxide ore pulp is 1:2.4, the extraction flow ratio O/A is 2.8, the washing flow ratio O/A is 25, and the volume ratio of hydrochloric acid with the concentration of 1mol/L hydrogen ions in washing acid to washing pure water for washing chlorine is 50 percent respectively; carrying out back extraction on the washed loaded organic by adopting 2mol/L sulfuric acid, wherein the back extraction flow ratio O/A is 18; and washing the organic matters after the back extraction by pure water to remove organic sulfate radicals, wherein the washing flow ratio O/A is 20.
And (3) detection: magnesium chloride raffinate contains 75g/L magnesium, 0.05g/L nickel and 0.05g/L cobalt, and has a pH value of 6.5.
Sodium dimethyl dithiocarbamate is added into the magnesium chloride raffinate to deeply remove nickel and cobalt, the addition of the sodium dimethyl dithiocarbamate is 1.4 times of the theoretical addition, the nickel and cobalt removal reaction time is 30min, and the reaction temperature is 40 ℃. Through detection: the concentration of nickel and cobalt in the reacted liquid is 1ppm, and the pH value is 7;
and (3) degreasing the magnesium chloride solution after deep purification by using active carbon, and then entering the next stage.
(3) Preparation of magnesium oxide products
After the magnesium oxide solution (the concentration of magnesium chloride is 4.3 mol/L) is preheated and concentrated by spray pyrolysis high-temperature tail gas, the temperature after preheating is 95 ℃, the magnesium oxide and hydrogen chloride tail gas is produced by spray pyrolysis process treatment, the temperature of spray pyrolysis is 800 ℃, the hydrogen chloride tail gas is washed and absorbed to produce 20% hydrochloric acid, and the hydrochloric acid returns to an extraction system for use. After the magnesium oxide product produced by spray pyrolysis is subjected to solid-liquid separation by crushing, pure water hydration transformation, washing and solid-liquid separation, the solid-liquid ratio of a primary magnesium oxide washing liquid is 4, and the washed solid slag is dried and roasted at high temperature (the temperature of high-temperature roasting is 800 ℃ and the roasting time is 2 hours) to produce a high-purity magnesium oxide product;
through detection: mgO:98.5 percent, the iodine absorption value is 150, the specific surface area is 123 square meters per gram, and the loose specific gravity is 0.35g/cm 3 The ignition loss is 2.8 percent, the chlorine content is 0.15 percent, the sulfate content is 0.15 percent, the Ni and Co contents are 0.005 percent, the Na content is 0.02 percent, the N content is 0.002 percent, and the temperature is 20-60 ℃.
Example 2
The embodiment provides a method for recovering magnesium oxide from a nickel-cobalt intermediate leaching solution, which comprises the following steps:
(1) Preparation of magnesium chloride solution
Extracting and enriching magnesium from the leachate to be treated by using an acidic phosphorus-containing extractant C272, wherein the volume ratio of the extractant to diluent No. 260 solvent oil is 1:5.5, the saponification equivalent of the extracting agent is 0.21, the magnesium concentration of the magnesium-containing solution is 6g/L, the nickel concentration is 1g/L, the pH value of the feed liquid is 5.5, the extraction flow ratio O/A is 2.9, the washing flow ratio O/A is 30, the volume ratio of 1mol/L sulfuric acid in washing acid to sulfur-washing pure water is 25 percent and 75 percent respectively, 6mol/L hydrochloric acid is used for magnesium stripping, and the stripping flow ratio O/A is 25.
And (3) detection: the stripping solution contains 65g/L magnesium, 2.6g/L nickel and pH4.
(2) Purifying and impurity removing
The magnesium chloride solution obtained by back extraction is adjusted to pH6.5 by adopting magnesium oxide, a carboxylic acid extractant BC196 is adopted to extract and remove nickel, and the volume ratio of the extractant BC196 to the diluent No. 260 solvent oil is 1:3, the saponification rate is 25%, the saponified alkaline magnesium salt is magnesium oxide ore pulp, and the solid ratio of the magnesium oxide ore pulp is 1:2.4, the extraction flow ratio O/A is 2.2, the washing flow ratio O/A is 25, and the volume ratio of hydrochloric acid with the hydrogen ion concentration of 1mol/L in washing acid to washing pure water for washing chlorine is 50 percent respectively; the washed load organic is subjected to back extraction by adopting 2mol/L sulfuric acid, and the back extraction flow ratio O/A is 18; and washing the organic matters after the back extraction by pure water to remove organic sulfate radicals, wherein the washing flow ratio O/A is 20.
Through detection: the magnesium chloride raffinate contained 75g/L magnesium, 0.05g/L nickel and 6.5 pH.
Sodium ferometalate is added into raffinate to deeply remove nickel and cobalt, the adding amount of the sodium ferometalate is 1.3 times of the theoretical adding amount, the reaction time for removing nickel and cobalt is 30min, and the reaction temperature is 40 ℃. Through detection: the nickel-cobalt concentration of the liquid after the reaction was 1ppm and the pH was 7.
The magnesium chloride solution after deep purification enters the next stage after being degreased by active carbon.
(3) Preparation of magnesium oxide products
After the magnesium oxide solution (the concentration of magnesium chloride is 4.3 mol/L) is preheated and concentrated by spray pyrolysis high-temperature tail gas, the temperature after preheating is 95 ℃, the magnesium oxide and hydrogen chloride tail gas is produced by spray pyrolysis process treatment, the temperature of spray pyrolysis is 750 ℃, and the hydrogen chloride tail gas is washed and absorbed to produce 20% hydrochloric acid and returns to an extraction system for use. After the magnesium oxide product produced by spray pyrolysis is subjected to solid-liquid separation by crushing, pure water hydration transformation, washing and washing, the solid slag after washing with a magnesium oxide washing liquid-solid ratio of 4 is dried and roasted at high temperature (the temperature of high-temperature roasting is 900 ℃ and the roasting time is 2 hours), and a high-purity magnesium oxide product is produced;
through detection: mgO:99 percent, iodine absorption value of 150, specific surface area of 145 square meters per gram and loose specific gravity of 0.37g/cm 3 The ignition loss is 2.9 percent, the chlorine content is 0.14 percent, the sulfate content is 0.13 percent, the Ni and Co contents are 0.004 percent, the Na content is 0.01 percent, the N content is 0.001 percent, and the temperature is 20-60 ℃.
Comparative example 1
The prior art for recovering magnesium products in the nickel-cobalt smelting industry comprises the following steps:
in the extraction section, magnesium element is back extracted and enriched into magnesium sulfate solution by sulfuric acid, heavy metal impurities such as nickel and cobalt in the magnesium sulfate solution containing nickel and cobalt impurities are removed through ammonium sulfide precipitation, then the magnesium sulfate solution is transformed into magnesium carbonate through carbonization precipitation, and the magnesium carbonate is washed, dried and then calcined at high temperature to prepare active magnesium oxide.
The process has the following defects: (1) When the magnesium is extracted by the sulfuric acid stripping process, the water yield of the system is relatively large due to the relatively low solubility of the magnesium sulfate; (2) In the process of removing heavy metal nickel and cobalt by ammonium sulfide precipitation, the operation environment is poor, and the protection of the occupational health and sanitation of staff is not facilitated; (3) The transformed magnesium carbonate has high sulfate radical content, the magnesium oxide produced after high-temperature calcination has high sulfur content and low purity, the MgO content can only reach about 95 percent, and the product cannot be sold in the market; (4) A large amount of carbon dioxide is produced in the process of calcining magnesium carbonate, which is not beneficial to environmental protection policies related to carbon emission reduction; (5) The whole process is long, the cost is high, and the economic and technical feasibility is not available.
Comparative example 2
The only difference from example 1 is: the magnesium sulfate solution after extraction and enrichment is subjected to oil removal treatment after nickel-cobalt heavy metals are removed, then the magnesium sulfate and ammonium sulfate mixed solution after oil removal is subjected to evaporative crystallization, centrifugal filtration, drying, packaging and other procedures to prepare ammonium magnesium sulfate mixed salt for external sale, evaporative condensate water is returned to a production system for use after being treated, and in order to ensure the quality of ammonium sulfate magnesium salt, the circulated evaporative mother liquor with high impurity content is discharged after being subjected to quantitative open-circuit sewage removal treatment.
The process has the following defects: (1) When the magnesium is extracted by the sulfuric acid stripping process, because the solubility item of the magnesium sulfate is relatively low, the volume of the magnesium sulfate solution produced by the system is relatively large, the treatment capacity of the subsequent evaporation crystallization process and the cost of each item of unit product are high, the product sales price is exceeded, and the economy is not realized; (2) In the process, part of the evaporation crystallization mother liquor needs to be discharged as sewage, so that the environmental protection benefit is poor; (3) In addition, the product is mixed salt of ammonium and magnesium sulfate, the market demand and the price are much smaller than those of ammonium sulfate, ammonium and magnesium are not completely separated in the technical process, and the benefit of the whole ammonium sulfate system is reduced.
The above description is only an alternative embodiment of the present invention, and is not intended to limit the present invention, and various modifications and variations of the present invention may 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 magnesium oxide from a nickel-cobalt intermediate leaching solution is characterized by comprising the following steps:
extracting the magnesium-nickel sulfate solution by using an acidic phosphorus-containing extractant to enrich magnesium, wherein the magnesium extraction comprises extraction and back extraction, and the back extraction is to obtain a magnesium chloride solution by back extraction of enriched magnesium by using hydrochloric acid; wherein the magnesium sulfate nickel solution is a nickel-cobalt intermediate leaching solution;
purifying the magnesium chloride solution to remove impurities so as to remove impurities of Ni and Co and oil to obtain a purified magnesium chloride solution;
pyrolyzing the purified magnesium chloride solution to obtain primary magnesium oxide and hydrochloric acid, mixing the primary magnesium oxide and water, carrying out hydration washing and solid-liquid separation to obtain filter residue, and roasting the filter residue at high temperature to obtain a magnesium oxide product.
2. The method of claim 1, wherein the process of extracting enriched magnesium is divided into multiple stages, including extraction, washing and stripping, with the extraction flow ratio O/A of 1-3, washing flow ratio of 3-25, pure water washing chlorine flow ratio O/A of 15-30, washing organic loaded Na + 、NH 4 + The acid of the magnesium is dilute sulphuric acid, the hydrochloric acid concentration of the back extraction magnesium is 4 mol/L-6.5 mol/L, the back extraction flow ratio O/A is 15-30,
optionally, the acidic phosphorus-containing extractant is selected from any one of C272 and P507;
wherein, when the C272 is used for extracting and enriching magnesium from the magnesium sulfate nickel solution, the concentration of the extracting agent is 10-15 percent; when the P507 is used for extracting and enriching magnesium from the magnesium sulfate nickel solution, the concentration of an extracting agent is 15-25%, the saponification alkali is any one of ammonia water and liquid alkali, and the saponification rate is 40-60%;
optionally, in the washing acid, the volume ratio of 1mol/L sulfuric acid to sulfur washing pure water is 15-30% and 70-85%, respectively;
optionally, in the process of extracting magnesium, the C272 extraction system controls the equilibrium pH of extraction to be 5.5-5.8, and according to the flow direction of an oil phase, an extraction production line comprises 1-level saponification, 6-level soap conversion, 7-level extraction, 8-level washing, 3-level sulfur washing, 6-level back extraction and 3-level chlorine washing;
optionally, in the magnesium extraction process, the P507 extraction system controls the equilibrium pH of extraction to be 5.8-6.2, and the extraction production line comprises 1-level saponification, 9-level extraction, 5-level washing, 3-level sulfur washing, 5-level back extraction and 3-level chlorine washing according to the flow direction of an oil phase;
optionally, the pH of the obtained magnesium chloride solution is 3 to 4, and the chemical composition is as follows: mg content of 40-78 g/L, cl content of 71-213 g/L, ni content of 0.5-5 g/L, co content of 0.2-1.5 g/L, na and NH 4+ The content is 0.01 g/L-0.2 g/L, the oil content is 30 ppm-150 ppm, and the temperature is 35 ℃ to 45 ℃.
3. The method for recovering magnesium oxide from a nickel cobalt intermediate leaching solution according to claim 1 or 2, characterized in that the magnesium nickel sulfate solution is a leaching solution after impurity removal and cobalt removal;
optionally, the magnesium nickel sulfate solution is raffinate of the nickel cobalt intermediate leaching solution after impurity removal by P204 and cobalt extraction by P507.
4. The method of claim 1 for recovering magnesium oxide from a nickel cobalt intermediate leach solution, wherein the step of purifying comprises: extracting by using a carboxylic acid extracting agent, adding magnesium oxide hydrated ore pulp in the process to control the pH value of the extraction process to be 6.5-6.8, removing oil from the obtained magnesium chloride raffinate, and then treating by using a heavy metal catching agent to deeply remove impurities of Ni and Co;
optionally, the carboxylic extractant is any one of BC196 or BC 191;
optionally, in the process of extraction by using the extractant BC196, the concentration of the organic phase extractant is controlled to be 5-25%, the saponification rate is 30-40%, the flow ratio O/A of an extraction section is 0.3-4, the solid content of magnesium oxide hydrated ore pulp for saponification is 10-30%, the extraction equilibrium pH is adjusted to be 6.2-6.8 by adding chemically pure magnesium oxide, the washing flow ratio is 3-25, the washing acid is dilute hydrochloric acid, the concentration of back extraction sulfuric acid is 1-2.8 mol/L, and the back extraction flow ratio O/A is 4-25;
optionally, the volume ratio of 1mol/L hydrochloric acid in the washing acid to pure chlorine-washing water is 25% -50% and 50% -75%, respectively, and the extraction production line comprises 1-stage saponification, 6-stage extraction, 5-stage washing, 2-stage chlorine-washing, 5-stage back-extraction and 2-stage sulfur-washing according to the flow direction of the oil phase.
5. The method for recovering magnesium oxide from a nickel cobalt intermediate leaching solution according to claim 4, wherein the degreasing is adsorption with resin or activated carbon;
alternatively, after degreasing with resin or activated carbon, the chemical composition of the magnesium chloride solution is as follows: oil content of 1ppm to 5ppm, mg content of 20g/L to 78g/L, cl content of 71g/L to 213g/L, ni content of 0.01g/L to 0.05g/L, co content of 0.01g/L to 0.05g/L, na and NH 4 + The content is 0.01 g/L-0.2 g/L, the pH is 3-7, and the temperature is 20-45 ℃.
6. The method for recovering the magnesium oxide from the nickel cobalt intermediate leaching solution according to claim 4, wherein the adding amount of the sodium ferulate is controlled to be 0.8 to 2 times of the theoretical amount during the treatment with the sodium ferulate, the pH value is 3 to 7, and the treatment temperature is 10 to 45 ℃;
optionally, the purified magnesium chloride solution obtained after treatment with sodium ferometalate has the following composition: the oil content is 1ppm to 5ppm, the Mg content is 20g/L to 78g/L, the Cl content is 71g/L to 213g/L, the Ni content is 0.0002g/L to 0.001g/L, the Co content is 0.0002g/L to 0.001g/L, the Na content is 0.01g/L to 0.25g/L, the pH is 3 to 7, and the temperature is 20 ℃ to 45 ℃.
7. The method for recovering the magnesium oxide from the nickel cobalt intermediate leaching solution according to claim 1, wherein in the process of pyrolyzing the purified magnesium chloride solution, the pyrolysis temperature is controlled to be 400-800 ℃, and the pyrolysis time is 3-120 min;
optionally, spray pyrolysis is employed;
more optionally, after the spray pyrolysis, the mass fraction of the byproduct hydrochloric acid is 18% to 20%, and the obtained primary magnesium oxide comprises the following chemical components: the content of MgO is 97-99%, the content of Cl is 0.05-1%, the content of Na is 0.02-0.2%, and the content of Ni and Co is less than or equal to 0.005%.
8. The method for recovering the magnesium oxide from the nickel cobalt intermediate leaching solution according to claim 1, wherein in the process of mixing the primary magnesium oxide and water for hydration washing, the solid-to-solid ratio of the washing solution is controlled to be 1-4, the hydration washing temperature is 20-60 ℃, and the washing time is 0.5-3 h.
9. The method for recovering the magnesium oxide from the nickel cobalt intermediate leaching solution according to claim 8, characterized in that the obtained filter residue is dried and crushed and then roasted at a high temperature;
optionally, in the drying and crushing process, the drying temperature is controlled to be 100-300 ℃, the drying time is 1-120 min, the granularity of the crushed slag is 1-150 μm, and the temperature is 100-200 ℃.
10. The method for recovering the magnesium oxide from the nickel cobalt intermediate leaching solution according to claim 1 or 9, characterized in that the high-temperature roasting temperature is 400-900 ℃ and the roasting time is 0.5-3 h;
optionally, crushing after high-temperature roasting, and controlling the particle size of the crushed magnesium oxide product to be 1-90 μm;
optionally, the purity of the magnesium oxide product obtained after crushing is 98-99.4%.
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