CN105238932B - Method for separating and recovering cobalt and manganese in cobalt-manganese waste - Google Patents
Method for separating and recovering cobalt and manganese in cobalt-manganese waste Download PDFInfo
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- CN105238932B CN105238932B CN201510847883.4A CN201510847883A CN105238932B CN 105238932 B CN105238932 B CN 105238932B CN 201510847883 A CN201510847883 A CN 201510847883A CN 105238932 B CN105238932 B CN 105238932B
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- 239000010941 cobalt Substances 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011572 manganese Substances 0.000 title claims abstract description 54
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 50
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000011084 recovery Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- WRWZNPYXEXPBAY-UHFFFAOYSA-N azane cobalt Chemical compound N.[Co] WRWZNPYXEXPBAY-UHFFFAOYSA-N 0.000 claims abstract description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 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 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 21
- 230000029087 digestion Effects 0.000 claims description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011656 manganese carbonate Substances 0.000 claims description 8
- 235000006748 manganese carbonate Nutrition 0.000 claims description 8
- 229940093474 manganese carbonate Drugs 0.000 claims description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 8
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 7
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 7
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- -1 and its physics Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000008236 heating water Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 5
- 229940039790 sodium oxalate Drugs 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000003513 alkali Substances 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
- C22B47/0009—Obtaining manganese from spent catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for separating and recovering cobalt and manganese in cobalt-manganese waste, which comprises the steps of pretreating the cobalt-manganese waste, adding ammonia water, carrying out a complex reaction on cobalt and ammonia to form a cobalt-ammonia complex, dissolving the cobalt-ammonia complex in an aqueous solution, adding hydrogen peroxide after reacting for a certain time, oxidizing bivalent manganese ions in the solution to generate more stable manganese dioxide, filtering, and separating cobalt and manganese; adding a sodium carbonate solution into the filtrate for secondary manganese precipitation, removing residual manganese ions in the solution, and filtering to obtain a cobalt-ammonium complex solution with higher purity; recovering cobalt from the cobalt-ammonia complex solution. The method has simple process, high recovery rate of cobalt and manganese, high recovery rate of cobalt up to more than 95%, and high recovery rate of manganese up to more than 99%.
Description
Technical field
The present invention relates to the separation and recovery method of cobalt and manganese in a kind of cobalt manganese waste material.
Background technology
Containing substantial amounts of cobalt, manganese element in caused useless cobalt-manganese catalyst in PTA productions, wherein cobalt content is about 10 %,
Manganese content is about 20 %.Cobalt is a kind of important strategy metal, and its physics, chemical property are excellent, is production heat-resisting alloy, hard
Alloy, anti-corrosion alloy, the important source material of magnetic alloy and various cobalt salts；And China's cobalt ore resource famine, but the year of cobalt
Consumption figure increases year by year, and domestic cobalt resource can not meet productive consumption demand, and most of cobalt raw material relies on import.Manganese is a kind of
Transition metal, property is hard and crisp, and moist place can aoxidize, and the most important purposes of manganese is manufacture manganese alloy.
At present, both at home and abroad the method for conventional separation and recovery cobalt-manganese catalyst mainly have chemical precipitation method, solvent extraction,
Electrolysis and ion-exchange etc..Chemical precipitation method is easy to operate, technological process is simple, but easily equipment is caused to corrode,
Need to optimize.Solvent extraction can efficiently separate out cobalt, cheap, but organic solvent easily causes to endanger to environment
Evil, and the condition control reacted requires also higher.Electrolysis can reclaim to obtain the high electrolytic cobalt of purity, but with electricity
Solve the defects of liquid is unstable.Ion-exchange can reach rich product and the purpose of purification, storng-acid cation exchange resin tool simultaneously
There is the characteristics of absorption appearance is maximum, and adsorption rate is fast, but ion exchange resin needs regular regeneration, produces a large amount of alkaline waste waters,
Environment is polluted.
On chemical precipitation method, Chinese patent literature CN 1236735A（Application number 98111313.3）Disclose a kind of cobalt
The separation and refining method of Mn mixture, vulcanized sodium will be first added after compound acidolysis and is co-precipitated cobalt manganese, then passes through cobalt, manganese sulphur
The solubility product difference of compound first dissolves manganese, then the cobalt sulfide with mixed-acid dissolution indissoluble.This method can efficiently separate cobalt,
Manganese is simultaneously reclaimed, but acid dissolution consumes a large amount of acid solutions three times, and the discharge of acid solution can cause greatly to pollute to environment.
Chinese patent literature CN 1059241C（Application number 98111506.3）It is high from leftover bits and pieces containing cobalt to disclose one kind
The new technology of effect extraction cobalt/cobalt oxide, including acid is molten, ammonification separation plus alkali are heat sink, absorbs, separating, washing step；It is described to contain cobalt
Leftover bits and pieces includes cobalt, iron, manganese element；The molten processing of acid is leftover bits and pieces is preprocessed or be directly dissolved in sulfuric acid or hydrochloric acid, acid
Solution ph is maintained at 2~3；Ammonification separation be by acid it is molten come clear mixed acid solution add excessive ammonia, keep pH value 8~
9, iron and manganese are separated in the form of hydroxide precipitates from reaction solution in this step；It is in cobalt ammonia complexing to add alkali heat sink
Caustic soda is added in solution based on thing to be heated to seething with excitement, and obtains cobalt oxide.Actual treatment cobalt manganese gives up inventor according to the method described above
During material, the rate of recovery for finding cobalt is only 70%.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of separation of cobalt from manganese is thorough, the rate of recovery is high, recovery product purity
The separation and recovery method of cobalt and manganese in high cobalt manganese waste material.
The technical scheme for realizing the object of the invention is the separation and recovery method of cobalt and manganese in a kind of cobalt manganese waste material, including following
Step：
1. pre-processing, pending cobalt manganese waste material acid is dissolved, the pH value of material is less than or equal to 3.5 after control acid is molten,
After molten rear material of the pH value less than or equal to 3. 5 of acid is heated in 70 DEG C~85 DEG C of water-bath, filter；Hydrogen is added into filtrate
Sodium hydroxide solution makes its pH value rise to 4~5, is filtered after standing, and obtained filtrate is pending as digestion solution.
2. cobalt is complexed, ammoniacal liquor is added in the digestion solution obtained after 1. being filtered to step so that the pH value of digestion solution is more than
9.5, the ratio between amount of material of ammonia and cobalt is 6:1~50:1,20~40min of stirring reaction, cobalt ions in digestion solution with
Complex reaction occurs for ammonium root.
3. once sinking manganese, 5%~30% hydrogen peroxide is added dropwise into material of the step after 2. complex reaction terminates, it is double after addition
The ratio between amount of material of oxygen water and manganese is 1:1~5:1；5~15h of stirring reaction at 20 DEG C~60 DEG C, reaction terminate
Afterwards, filter, filter residue is manganese dioxide, and manganese dioxide reclaims.
4. secondary heavy manganese, adds sodium carbonate liquor in the filtrate being 3. filtrated to get to step, sodium carbonate with it is remaining in filtrate
The ratio between amount of material of manganese is 1:1~10:1, more than the min of stirring reaction 30 at 20 DEG C~40 DEG C, after reaction terminates,
Filtering, respectively obtain cobalt ammonia complex solution and manganese carbonate, manganese carbonate recovery.
5. Call Provision, the cobalt ammonia complex solution being filtrated to get after step 4. secondary heavy manganese is placed in water-bath and is heated to
70 DEG C~85 DEG C, add reducing agent thereto, the ratio between reducing agent and amount of material of cobalt in cobalt ammonia complex solution are 0.8:1
~5:1, react 15min~60min；Then lower dropwise addition sodium hydroxide solution or grass are stirred in the material after terminating to reduction reaction
Acid salt solution, 20min~60min is reacted after being added dropwise；Reaction filters after terminating, and the washing of precipitate for filtering to obtain obtains after drying
To cobalt hydroxide or cobalt oxalate, the recovery of cobalt is completed.
Above-mentioned steps 1. in used acid be nitric acid, hydrochloric acid or sulfuric acid, preferably nitric acid, in sour dosage and cobalt manganese waste material
Cobalt, the ratio between the amount of material of manganese are n (H+) : [ n ( Mn ) + n ( Co ) ] = 2 :1~4: 1.
Above-mentioned steps 1. it is middle with sour dissolved cobalt manganese waste material when, sour pH value used be less than 1.
As preferable, 5. step adds reducing agent after, 15min is reacted under conditions of 70 DEG C~85 DEG C heating water baths
~60min.
5. reducing agent that above-mentioned steps add is one kind in hydrazine hydrate, sodium borohydride, ethylene glycol or paraformaldehyde.
It is specific optional, step 5. in 4. cobalt ammonia complex solution that step is filtrated to get be placed in water-bath be heated to
70 DEG C~85 DEG C, reducing agent is then added, the reducing agent added is hydrazine hydrate, sodium borohydride or paraformaldehyde；Or step
4. 3. cobalt ammonia complex solution that step is filtrated to get is placed in oil bath pan and is heated to 170 DEG C~185 DEG C, then add also
Former agent, the reducing agent added are ethylene glycol.
As preferable, step is after 5. sodium hydroxide solution or oxalate solution are added dropwise, in 70 DEG C~85 DEG C water-baths
20min~60min is reacted under conditions of heating.
When what 5. step was added dropwise is sodium hydroxide solution, n（NaOH）:n（Co）=8.5:1~15:1；What it is when dropwise addition is grass
During hydrochlorate, n（C2O4 2-）:n（Co）=8:1~20:1.
Step 1. in pending cobalt manganese waste material cobalt, the mass ratio of manganese be 1:1~1:4.
The present invention has positive effect：
（1）The separation and recovery method of the present invention is adapted to the high manganese waste material of all cobalt manganese waste materials, particularly low cobalt, such as oil row
Give up cobalt-manganese catalyst caused by industry production PTA, and present invention process is simple, and the rate of recovery of cobalt and manganese is all very high, and the rate of recovery of cobalt can
To be up to more than 95%, the rate of recovery of manganese can reach more than 99%.
（2）First less than 1 strong acid that cobalt manganese waste material acid is molten with pH value during present invention pretreatment, acid, which is dissolved, finishes control liquid
PH value is less than or equal to 3.5, heats and filters off the organic matter in the molten rear material that deacidifies, then into the material after organics removal
Hydrogenation sodium oxide molybdena makes the pH value of liquid rise to 4~5, and the purpose of this regulation pH value is to remove impurity iron, if containing in cobalt manganese waste material
There is impurity iron, the iron ion after acid is molten can precipitate with hydroxyl from generation, is removed after filtering.Removal of the invention by impurity iron
It is placed on before ammonification step, ensure that the cobalt of separation and recovery and the purity of manganese；And the step of adding organics removal, enter one
Step ensures the cobalt of separation and recovery and the purity of manganese.
（3）When present invention processing cobalt ammonia complex is with Call Provision, first cobalt ammonia complex is reduced, trivalent cobalt is reduced to two
Valency cobalt, sodium hydroxide or sodium oxalate or ammonium oxalate are then added into the cobalt ammonia complex of divalence, obtains cobalt sediment.Reducing agent
Addition can destroy the stability of trivalent cobalt ammonia complex, the cobalt ammonia complex after reduction is easier and sodium hydroxide or oxalic acid
Root reacts, and so as to improve the rate of recovery of cobalt, obtained cobalt product purity is high.
Brief description of the drawings
Fig. 1 reclaims the XRD spectrum of obtained cobalt hydroxide for embodiment 1, and abscissa is scanning angle in figure（°）, indulge and sit
It is designated as intensity（cps）.
Fig. 2 reclaims the infrared spectrogram of obtained cobalt oxalate for embodiment 2, and abscissa is wavenumber in figure, Chinese
Look like for wave number, ordinate Transmittance, the Chinese meaning is light transmittance（%）.
Embodiment
（Embodiment 1）
Cobalt manganese waste material handled by the present embodiment is caused useless cobalt-manganese catalyst in PTA productions, and the content of wherein cobalt is
9.872wt %, the content of manganese is 17.12 wt %.
The separation and recovery method of cobalt and manganese comprises the following steps in the cobalt manganese waste material of the present embodiment：
1. pre-process.13 grams of cobalt manganese waste materials are taken, 40 % salpeter solution is added into the reaction vessel for filling cobalt manganese waste material
30 mL, after the resolution completely of cobalt manganese waste material, the pH value of liquid is 1.5 after measurement acid is molten.Cobalt manganese in the dosage and dead catalyst of acid
The ratio between the amount of material be n (H+) : [ n ( Mn ) + n ( Co ) ] = 2 :1~4: 1.By the molten rear pH of acid
The value min of heating water bath 30 in 80 DEG C of water-bath of the material less than 3.5, is filtered, go to deacidify it is molten after organic matter in material.
The pH value of liquid after needing control acid molten before heating water bath, if the pH value of liquid is more than 3.5 after acid is molten, it is molten useless to add acid thereto
Acid used is that nitric acid makes its pH value less than 3.5 during material, because the pH value of the molten rear liquid of acid is 1.5 in the present embodiment, therefore can
To directly heat.
5mol/L sodium hydroxide solution is added into the material for eliminate organic matter makes its pH value rise to 4~5（This reality
Apply in example is 4.5）；Filtered after standing 20min, obtained filtrate i.e. digestion solution is pending.Measuring cobalt content in digestion solution is
50.25 g/L, manganese content are 95.75 g/L.If having iron ion in material after acid is molten, iron ion generates hydroxide in this step
Iron precipitates, and is removed after suction filtration from digestion solution.
2. cobalt is complexed.The g/L of 100 g/L~250 ammoniacal liquor is added in the digestion solution obtained after 1. being filtered to step, is made
The pH value of digestion solution is obtained more than 9.5, the ratio between amount of material of ammonia and cobalt is 6:1~50:1, ammoniacal liquor is added in the present embodiment
Afterwards the pH value of digestion solution be 9.79, under conditions of reaction temperature is 30 DEG C, mixing speed is 300 r/min stirring reaction 20~
40min（It is 30 min in the present embodiment）, the cobalt ions in digestion solution and ammonium root generation complex reaction in this step.
3. once heavy manganese.5%~30% hydrogen peroxide is added dropwise into material of the step after 2. complex reaction terminates, it is double after addition
The ratio between amount of material of oxygen water and manganese is 1:1~5:1；In the present embodiment into material of the step after 2. complex reaction terminates plus
Enter 30% mL of hydrogen peroxide 5, at 20 DEG C~60 DEG C（It is 35 DEG C in the present embodiment）, mixing speed be 100~600 r/
min （It is 300 r/min in the present embodiment）Under conditions of 5~15h of stirring reaction（It is 10 h in the present embodiment）, in digestion solution
Most of divalent manganesetion by hydrogen peroxide oxidation；After oxidation reaction terminates, filtering, filtrate cobalt ammonia complexing liquid and filter are respectively obtained
Slag manganese dioxide precipitate, the scrubbed drying of manganese dioxide precipitate weigh to obtain 3.4976g, and filtrate cobalt ammonia complex solution is treated further
Processing.The purity of manganese dioxide precipitate is 98.7%.
4. secondary heavy manganese.0.2~2 mol/L carbonic acid is added in the filtrate cobalt ammonia complexing liquid being 3. filtrated to get to step
The ratio between amount of material of remaining manganese is 1 in sodium solution, sodium carbonate and filtrate:1~10:1,3. filtered to step in the present embodiment
The sodium carbonate liquor that 3 mL concentration are 1 mol/L is added in obtained filtrate cobalt ammonia complexing liquid；Then it is 20 DEG C in reaction temperature
~40 DEG C（It is 30 DEG C in the present embodiment）, mixing speed be 100~600 r/min（It is 300 r/ in the present embodiment
min）Under conditions of more than the min of stirring reaction 30（It is 60min in the present embodiment）；After reaction terminates, filtering, cobalt is respectively obtained
Ammino-complex solution and manganese carbonate precipitation, manganese carbonate precipitate scrubbed drying and weigh to obtain 0.0278g.Manganese carbonate precipitation purity be
99.9%。
By step 3. with step 4., the manganese in cobalt manganese waste material is recycled in the form of manganese dioxide and manganese carbonate, meter
Calculate in cobalt manganese waste material the rate of recovery of manganese be 99.95 %.
5. Call Provision.The cobalt ammonia complex solution being filtrated to get after step 4. secondary heavy manganese is placed in water-bath and is heated to
80 ℃.The mL of reducing agent hydrazine hydrate 1.00 is added into 80 DEG C of cobalt ammonia complex solution, maintains 80 DEG C of reaction 15min of water-bath
~60min（It is 20min in the present embodiment）, the cobalt ammonia complex of trivalent is reduced to the cobalt ammonia complex of divalence.
The reducing agent can also be sodium borohydride, ethylene glycol or paraformaldehyde in addition to above-mentioned hydrazine hydrate used, also
The ratio between amount of material of former agent and cobalt is 0.8:1~5:1.
Stirring is lower to be added dropwise sodium hydroxide solution, n（NaOH）：n（Co）=8.5:1~15:1.
The mL of sodium hydroxide solution 15, rate of addition 1mL/ that lower dropwise addition concentration is 500 g/L are stirred in the present embodiment
Min, mixing speed are 200 r/min；After 80 DEG C of 30 min of reaction of water-bath are maintained after being added dropwise, filter, filter to obtain sinks
Ethanol wash is first used in shallow lake, then with after distillation water washing, is placed in baking oven and is dried at 70 DEG C~90 DEG C.Ground after drying with mortar
Mill, 100 mesh sieve are crossed, obtain cobalt hydroxide product 1.93g.The purity of cobalt hydroxide is 97.8%.
The rate of recovery for being computed cobalt is 95.19 %, and the XRD spectrum of resulting cobalt hydroxide is shown in Fig. 1, in cobalt manganese waste material
Cobalt be recycled in the form of cobalt hydroxide.
（Embodiment 2）
Remaining is same as Example 1 for the separation and recovery method of cobalt and manganese in the cobalt manganese waste material of the present embodiment, and difference exists
In：
After the cobalt ammonia complex of step 5. middle trivalent is reduced to the cobalt ammonia complex of divalence, stir that lower that sodium oxalate is added dropwise is molten
Liquid, add rear n（C2O4 2-）：n（Co）=8:1~20:1.
Sodium oxalate solution 150 mL, the rate of addition 20mL/min that concentration is 50g/L, stirring speed are added dropwise in the present embodiment
Spend for 500 r/min.
Except the sodium oxalate solution described in the present embodiment, ammonium oxalate can also be used to substitute sodium oxalate.
Cobalt oxalate 3.08g is obtained after drying, the rate of recovery of cobalt is 95.25 %, and the purity of cobalt oxalate is 98.6%.Cobalt manganese gives up
Cobalt in material is recycled in the form of cobalt oxalate.The infrared spectrogram of obtained cobalt oxalate is shown in Fig. 2.
（Embodiment 3）
Remaining is same as Example 1 for the separation and recovery method of cobalt and manganese in the cobalt manganese waste material of the present embodiment, and difference exists
In：
When step pre-processes 1., 10 % hydrochloric acid solution 44mL is added into the reaction vessel for filling cobalt manganese waste material, treats cobalt
After the resolution completely of manganese waste material, the pH value of liquid is 4.2 after measurement acid is molten.10% hydrochloric acid is added into liquid of the acid after molten to pH
Drop to less than 3.5, be then transferred to the min of heating water bath 30 in 80 DEG C of water-bath, filter, go to deacidify it is molten after in material
Organic matter.
（Embodiment 4）
Remaining is same as Example 1 for the separation and recovery method of cobalt and manganese in the cobalt manganese waste material of the present embodiment, and difference exists
In：
When step pre-processes 1., 30 % sulfuric acid solution 25mL is added into the reaction vessel for filling cobalt manganese waste material, treats cobalt
After the resolution completely of manganese waste material, the pH value of liquid is 1.7 after measurement acid is molten.Liquid of the acid after molten is transferred to 80 DEG C of water-bath
The middle min of heating water bath 30, filter, go to deacidify it is molten after organic matter in material.
Claims (5)
1. the separation and recovery method of cobalt and manganese in a kind of cobalt manganese waste material, it is characterised in that comprise the following steps：
1. pre-processing, pending cobalt manganese waste material acid is dissolved, the pH value of material is less than or equal to 3.5 after control acid is molten, by acid
After material of the pH value less than or equal to 3.5 heats in 70 DEG C~85 DEG C of water-bath after molten, filter；Sodium hydroxide is added into filtrate
Solution makes its pH value rise to 4~5, is filtered after standing, and obtained filtrate is pending as digestion solution；
2. cobalt is complexed, ammoniacal liquor is added in the digestion solution obtained after 1. being filtered to step so that the pH value of digestion solution is more than 9.5, ammonia
It is 6 with the ratio between the amount of material of cobalt:1~50:With ammonium root network occurs for 1,20~40min of stirring reaction, the cobalt ions in digestion solution
Close reaction；
3. once sinking manganese, 5%~30% hydrogen peroxide, hydrogen peroxide after addition are added dropwise into material of the step after 2. complex reaction terminates
It is 1 with the ratio between the amount of material of manganese:1~5:1；5~15h of stirring reaction at 20 DEG C~60 DEG C, after reaction terminates, filter, filter
Slag is manganese dioxide, and manganese dioxide reclaims；
4. secondary heavy manganese, sodium carbonate liquor, sodium carbonate and remaining manganese in filtrate are added in the filtrate being 3. filtrated to get to step
The ratio between amount of material is 1:1~10:1, more than the stirring reaction 30min at 20 DEG C~40 DEG C, after reaction terminates, filter, respectively
Obtain cobalt ammonia complex solution and manganese carbonate, manganese carbonate recovery；
5. Call Provision, the cobalt ammonia complex solution being filtrated to get after step 4. secondary heavy manganese is placed in water-bath and is heated to 70 DEG C
~85 DEG C, reducing agent is added thereto, and the reducing agent added is one kind in hydrazine hydrate, sodium borohydride or paraformaldehyde, is reduced
The ratio between amount of material of cobalt is 0.8 in agent and cobalt ammonia complex solution:1~5:1, react 15min~60min；
Then lower dropwise addition sodium hydroxide solution or oxalate solution are stirred in the material after terminating to reduction reaction, after being added dropwise
React 20min~60min；Reaction filters after terminating, and the washing of precipitate for filtering to obtain obtains cobalt hydroxide or cobalt oxalate after drying,
Complete the recovery of cobalt.
2. the separation and recovery method of cobalt and manganese in cobalt manganese waste material according to claim 1, it is characterised in that：Step 1. middle institute
Acid is nitric acid, hydrochloric acid or sulfuric acid, and sour dosage is n (H with the ratio between amount of material of cobalt, manganese in cobalt manganese waste material+) : [
n ( Mn ) + n ( Co ) ] = 2 :1~4: 1.
3. the separation and recovery method of cobalt and manganese in cobalt manganese waste material according to claim 2, it is characterised in that：Step 1. middle use
During sour dissolved cobalt manganese waste material, sour pH value used is less than 1.
4. the separation and recovery method of cobalt and manganese in cobalt manganese waste material according to claim 1, it is characterised in that：When 5. step is dripped
When what is added is sodium hydroxide solution, n（NaOH）：n（Co）=8.5：1~15：1；When dropwise addition be oxalates when, n（C2O4 2-）：n
（Co）=8：1~20：1.
5. the separation and recovery method of cobalt and manganese in the cobalt manganese waste material according to one of Claims 1-4, it is characterised in that：Step
Suddenly 1. in pending cobalt manganese waste material cobalt, the mass ratio of manganese be 1:1~1:4.
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| CN106290334B (en) * | 2016-08-05 | 2019-01-08 | 江苏理工学院 | The chemistry in detecting of cobalt and manganese content in cobalt manganese raw material |
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| CN110721703B (en) * | 2019-10-25 | 2022-09-09 | 南华大学 | Preparation method and application of nanoscale magnetic cobalt-manganese spinel |
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