CN107828965B - 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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- 239000010941 cobalt Substances 0.000 title claims abstract description 91
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 91
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000011572 manganese Substances 0.000 title claims abstract description 66
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 62
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- WRWZNPYXEXPBAY-UHFFFAOYSA-N azane cobalt Chemical compound N.[Co] WRWZNPYXEXPBAY-UHFFFAOYSA-N 0.000 claims abstract description 33
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 30
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 43
- 230000029087 digestion Effects 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 8
- 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 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 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
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 28
- 229940039790 sodium oxalate Drugs 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical group [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004176 ammonification Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction 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
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005303 weighing 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
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 and physics Substances 0.000 description 1
- 238000009835 boiling Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000284 extract Substances 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
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 238000001179 sorption measurement 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
-
- 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
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth 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, introducing ozone after reacting for a certain time, oxidizing bivalent manganese ions in the solution to generate more stable manganese dioxide, filtering, and recovering manganese in a manganese dioxide form; 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%. When the cobalt-ammonia complex is treated by the method to recover cobalt, the cobalt-ammonia complex is reduced firstly, the addition of the reducing agent can destroy the stability of the trivalent cobalt-ammonia complex, and the reduced cobalt-ammonia complex can react with sodium hydroxide or oxalate more easily, so that the recovery rate of cobalt is improved, and the purity of the prepared cobalt product is high.
Description
The application is application No. is 201510839442.X, and the applying date is on November 27th, 2015, and invention and created name is
The divisional application of the application for a patent for invention of " method of cobalt and manganese in separating and recovering cobalt manganese waste material ".
Technical field
The present invention relates to a kind of methods of cobalt and manganese in separating and recovering cobalt manganese waste material.
Background technique
Containing a large amount of cobalt, manganese element in the useless cobalt-manganese catalyst generated in PTA production, wherein cobalt content is about 10 %,
Manganese content is about 20 %.Cobalt is a kind of important strategy metal, and physics, chemical property are excellent, is production heat-resisting alloy, hard
The important source material of alloy, anti-corrosion alloy, magnetic alloy and various cobalt salts；And there is a serious shortage of but years of cobalt for China's cobalt ore resource
Consumption figure increases year by year, and domestic cobalt resource has been unable to 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.
Currently, both at home and abroad the method for common separation and recovery cobalt-manganese catalyst mainly have chemical precipitation method, solvent extraction,
Electrolysis method and ion-exchange etc..Chemical precipitation method is easy to operate, process flow is simple, but is easy to cause to corrode to equipment,
It needs to optimize.Solvent extraction can efficiently separate out cobalt, cheap, but organic solvent easily causes to endanger to environment
Evil, and the condition control requirement reacted is also relatively high.Electrolysis method can recycle to obtain the electrolytic cobalt of purity is high, but have electricity
Solve the unstable defect of liquid.Ion-exchange can achieve the purpose that rich product and purification, storng-acid cation exchange resin tool simultaneously
There is absorption to hold maximum, the fast feature of adsorption rate, but ion exchange resin needs regular regeneration, generates a large amount of alkaline waste waters,
It pollutes the environment.
About 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 will first be added vulcanized sodium and be co-precipitated cobalt manganese after mixture acidolysis, then pass 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 recycled, but acid dissolution consumes a large amount of acid solutions three times, and the discharge of acid solution can cause environment greatly to pollute.
Chinese patent literature CN 1059241C(application number 98111506.3) disclose one kind height from leftover bits and pieces containing cobalt
Effect extracts the new process of 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 that leftover bits and pieces is preprocessed or is directly dissolved in sulfuric acid or hydrochloric acid, sour
Solution ph is maintained at 2~3；Ammonification separation be by acid it is molten come clear mixed acid solution excessive ammonia is added, keep pH value 8~
9, iron and manganese are separated from reaction solution in this step in the form that hydroxide precipitates；Adding alkali heat sink is in cobalt ammonia complexing
Caustic soda is added in solution based on object to be heated to boiling, obtains cobalt oxide.Actual treatment cobalt manganese is useless according to the method described above by inventor
When material, it is found that the rate of recovery of cobalt is only 70%.
Summary of the invention
That technical problem to be solved by the invention is to provide 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 solution for realizing the object of the invention is a kind of method of cobalt and manganese in separating and recovering cobalt manganese waste material, including following
Step:
1. pre-processing, by cobalt manganese waste material acid dissolution to be processed, the pH value of material is less than or equal to 3.5 after control acid is molten,
After the acid material that pH value is less than or equal to 3. 5 after molten is heated in 70 DEG C~85 DEG C of water-bath, filter, obtained filtrate conduct
Digestion solution is to be processed.
2. cobalt is complexed, ammonium hydroxide is added in the digestion solution obtained after 1. filtering to step, so that the pH value of digestion solution is greater than
7.5, the ratio between amount of substance of ammonia and cobalt is 2: 1~50: 1, is stirred to react 20~60min, the cobalt ions in digestion solution with
Complex reaction occurs for ammonium root.
3. heavy manganese, is passed through ozone into the digestion solution after step 2. complex reaction under stirring, the ozone and manganese being passed through
The ratio between the amount of substance=1:1~5:1, stopping is passed through after ozone that the reaction was continued 5h~15h, the divalent manganesetion in digestion solution
By ozone oxidation.
After reaction, it filters, filtrate is cobalt ammonia complexing liquid, and filter residue is manganese dioxide precipitate, is completed in cobalt manganese waste material
The separation of cobalt and manganese, and manganese is recycled in the form of manganese dioxide.
4. the cobalt ammonia complex solution being obtained by filtration after step 3. heavy manganese is heated to 70 DEG C~185 DEG C by Call Provision, to
Reducing agent is wherein added, the ratio between amount of substance of cobalt is 0.8:1~5:1, reaction in reducing agent and cobalt ammonia complex solution
15min~60min；Then lower dropwise addition sodium hydroxide solution or oxalate solution are stirred into the material after reduction reaction,
20min~60min is reacted after being added dropwise；It filters after reaction, obtains hydroxide after the washing of precipitate filtered is dry
Cobalt or cobalt oxalate complete the recycling of cobalt.
Above-mentioned steps 1. used in acid be nitric acid, hydrochloric acid or sulfuric acid, the pH value of acid used less than 1, sour dosage with
The ratio between amount of substance of cobalt, manganese is n (H in cobalt manganese waste material+): [n (Mn)+n (Co)]=2:1~4:1.
Above-mentioned steps 1. in front of heating water bath, if the pH value of material is less than or equal to 3.5 and refers to liquid after acid is molten after control acid is molten
The pH value of body is greater than 3.5, and acid used makes its pH value lower than 3.5 when sour molten waste material being added thereto；The pH of liquid after if acid is molten
Value then directly carries out heating water bath less than 3.5.
Above-mentioned steps 3. sink manganese when, be passed through ozone into the digestion solution after step 2. complex reaction under stirring, be passed through
Maintenance fluid temperature is 20 DEG C~80 DEG C when ozone, mixing speed is the r/min of 100 r/min~1000；After 0.5 h~8h
Stopping is passed through ozone, then proceedes to 5~15 h of reaction.
4. reducing agent that above-mentioned steps add is one of hydrazine hydrate, sodium borohydride, ethylene glycol or paraformaldehyde.
Further, step 4. in 3. cobalt ammonia complex solution that step is obtained by filtration be placed in water-bath be heated to 70
DEG C~85 DEG C, reducing agent is then added, the reducing agent being added is hydrazine hydrate, sodium borohydride or paraformaldehyde；Or step is 4.
3. cobalt ammonia complex solution that step is obtained by filtration is placed in oil bath pan and is heated to 170 DEG C~185 DEG C, reduction is then added
Agent, the reducing agent being added are ethylene glycol.
Further, step adds in 70 DEG C~85 DEG C water-baths after 4. sodium hydroxide solution or oxalate solution are added dropwise
20min~60min is reacted under conditions of heat.
Further, when step be 4. added dropwise be sodium hydroxide solution when, n(NaOH): n(Co)=8.5:1~15:1；
When dropwise addition be oxalates when, n(C2O4 2-): n(Co)=8:1~20:1.
Step 1. in cobalt in cobalt manganese waste material to be processed, manganese mass ratio be 1:1~1:4.
The present invention has the effect of positive:
(1) separation and recovery method of the invention is suitble to the high manganese waste material of all cobalt manganese waste materials, especially low cobalt, such as petroleum row
Industry produces the useless cobalt-manganese catalyst that PTA is generated, 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 95% or more, the rate of recovery of manganese can achieve 99% or more.
(2) present invention pretreatment Shi Xianyong pH value is molten by cobalt manganese waste material acid less than 1 strong acid, and 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 filtrate after removal organic matter
Add ammonium hydroxide that system pH is adjusted to alkalinity, complex reaction occurs for cobalt ions and ammonium ion under alkaline condition, so that cobalt ions is steady
Determine in the solution；Complex reaction is passed through ozone into the liquid after reaction after terminating, ozone is by the divalent manganesetion oxygen in liquid
Metaplasia is at manganese dioxide precipitate；It is filtered after oxidation reaction, cobalt is in filtrate, and for manganese in filter residue, cobalt and manganese complete separation；Into
One step, the manganese in cobalt manganese waste material is recycled in the form of manganese dioxide, and cobalt is stayed in a liquid in the form of cobalt ammonia complex,
Recycling is completed in the form of cobalt hydroxide or cobalt oxalate after being further processed.It is increased during separation and recovery of the invention
The step of except organic matter, to guarantee 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 restored, trivalent cobalt is reduced to two
Then sodium hydroxide or sodium oxalate or ammonium oxalate are added into the cobalt ammonia complex of divalent, obtains cobalt sediment for valence cobalt.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 reaction, to improve the rate of recovery of cobalt, cobalt product purity obtained is high.
Specific embodiment
(embodiment 1)
Cobalt manganese waste material handled by the present embodiment is the useless cobalt-manganese catalyst generated in PTA production, and wherein the content of cobalt is
9.872wt %, the content of manganese are 17.12 wt %.
The method of cobalt and manganese in the separating and recovering cobalt manganese waste material of the present embodiment the following steps are included:
1. pre-processing.13 grams of cobalt manganese waste materials are taken, the nitric acid solution of 40 % is added in the reaction vessel of Xiang Shengyou 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 substance be n (H+): [n (Mn)+n (Co)]=2: 1~4: 1.
By molten rear material of the pH value less than 3.5 30 min of heating water bath in 80 DEG C of water-bath of acid, filters, go to deacidify
Organic matter after molten in material.Filtrate is digestion solution, and cobalt content is 50.25 g/L in digestion solution, and manganese content is 95.75 g/L.
Need to control before heating water bath acid it is molten after liquid pH value, if acid it is molten after liquid pH value be greater than 3.5, thereto plus
Acid i.e. nitric acid used makes its pH value lower than 3.5 when entering sour molten waste material, since the pH value of the molten rear liquid of acid is in the present embodiment
1.5, therefore can directly heat.
2. cobalt is complexed.The ammonium hydroxide of the g/L of 50 g/L~250 is added in the digestion solution obtained after 1. filtering to step, so that
The pH value of digestion solution is greater than 7, and the ratio between ammonia and the amount of substance of cobalt are 2: 1~50: 1, disappears after ammonium hydroxide is added in the present embodiment
The pH value for solving liquid is 8.79；It then is 20 DEG C~60 DEG C (being 30 DEG C in the present embodiment), mixing speeds 100 in reaction temperature
Be 500 r/min in~1000 r/min(the present embodiment) under conditions of to be stirred to react be 30 in 20~60min(the present embodiment
Min), complex reaction occurs for the cobalt ions in digestion solution and ammonium root in this step.
3. heavy manganese.Ozone is passed through under stirring into the digestion solution after step 2. complex reaction, ozone output speed is 3
G/h, maintenance fluid temperature is 50 DEG C when being passed through ozone, mixing speed is 500 r/min；Stop being passed through ozone after 1 h, 50
DEG C, mixing speed be the reaction was continued 10 h under 500 r/min, the divalent manganesetion in digestion solution is by ozone oxidation.What is be passed through is smelly
The ratio between amount of substance of oxygen and manganese=1:1~5:1 is 1.54:1 in the present embodiment.
After reaction, it filters, filtrate is cobalt ammonia complexing liquid, and filter residue is manganese dioxide precipitate, is completed in cobalt manganese waste material
The separation of cobalt and manganese, and manganese is recycled in the form of manganese dioxide, manganese dioxide precipitate is through weighing after washing is dry
3.5201g, the rate of recovery for being computed manganese in cobalt manganese waste material is 99.99 %, and the purity of manganese dioxide is 99.9%.
4. Call Provision.The cobalt ammonia complex solution being obtained by filtration after step 3. heavy manganese is placed in water-bath and is heated to 80
℃.It is added into 80 DEG C of cobalt ammonia complex solution in 20%~80%(of reducing agent the present embodiment as hydrazine hydrate 1.00 80%)
ML maintains to be 20min in 80 DEG C of reaction 15min~60min(the present embodiment of water-bath), the cobalt ammonia complex of trivalent is reduced to two
The cobalt ammonia complex of valence.
The reducing agent can also be sodium borohydride, ethylene glycol or paraformaldehyde other than above-mentioned hydrazine hydrate used, also
The ratio between amount of substance of former agent and cobalt is 0.8:1~5:1.The reducing agent being wherein added is hydrazine hydrate, sodium borohydride or more
When polyformaldehyde, 3. cobalt ammonia complex solution that step is obtained by filtration is placed in water-bath and is heated to 70 DEG C~85 DEG C, then plus
Enter reducing agent；When the reducing agent being added is ethylene glycol, 3. cobalt ammonia complex solution that step is obtained by filtration is placed in oil bath pan
In be heated to 170 DEG C~185 DEG C, reducing agent is then added.
Stirring is lower to be added dropwise sodium hydroxide solution, n(NaOH): n(Co)=8.5:1~15:1.
The lower concentration that is added dropwise is stirred in the present embodiment as 15 mL of sodium hydroxide solution, rate of addition 1mL/ of 500 g/L
Min, mixing speed are 200 r/min；It after maintaining 80 DEG C of water-bath 30 min of reaction after being added dropwise, filters, what is filtered is heavy
It forms sediment and first uses ethanol wash, then after being washed with distilled water, be placed in baking oven and dried at 70 DEG C~90 DEG C.It is ground after drying with mortar
Mill, sieves with 100 mesh sieve son, obtains cobalt hydroxide product 1.9568g, and the rate of recovery for being computed cobalt is 96.73 %.Cobalt hydroxide it is pure
Degree is 99.8%.
(embodiment 2)
The content of cobalt is 8.82 wt % in cobalt manganese waste material handled by the present embodiment, and the content of manganese is 25.64wt %.
Remaining is same as Example 1 for the method for cobalt and manganese in the separating and recovering cobalt manganese waste material of the present embodiment, and difference exists
In:
When step pre-processes 1., 15 grams of cobalt manganese waste materials are taken, the nitre of 40 % is added in the reaction vessel of Xiang Shengyou cobalt manganese waste material
50 mL of acid solution, after the resolution completely of cobalt manganese waste material, the pH value of liquid is 0.7 after measurement acid is molten.
By molten rear material of the pH value less than 3.5 30 min of heating water bath in 80 DEG C of water-bath of acid, filters, go to deacidify
Organic matter after molten in material.Filtrate is digestion solution, and cobalt content is 40.21 g/L in digestion solution, and manganese content is 125.85 g/L.
The ammonium hydroxide 80mL of 100 g/L is added when 2. cobalt is complexed in step in the digestion solution that obtains after 1. filtering to step, so that
The pH value of digestion solution is 9.86；Then 60 are stirred to react under conditions of reaction temperature is 32 DEG C, mixing speed is 800 r/min
Min, complex reaction occurs for the cobalt ions in digestion solution and ammonium root in this step.
Step 3. in, ozone, ozone output speed are passed through under stirring into the digestion solution after step 2. complex reaction
For 2 g/h, maintenance fluid temperature is 50 DEG C when being passed through ozone, mixing speed is 1000 r/min；Stop being passed through after 3 h smelly
Oxygen, the reaction was continued 5h under being 1000 r/min in 50 DEG C, mixing speed, divalent manganesetion in digestion solution by ozone oxidation, this
It is 1.79:1 in embodiment.
After reaction, it filters, filtrate is cobalt ammonia complexing liquid, and filter residue is manganese dioxide precipitate, is completed in cobalt manganese waste material
The separation of cobalt and manganese, and manganese is recycled in the form of manganese dioxide, manganese dioxide precipitate is through weighing after washing is dry
6.0825 g, the rate of recovery for being computed manganese in cobalt manganese waste material is 99.98 %, and the purity of manganese dioxide is 99.7 %.
4. step obtains cobalt hydroxide product 2.0610g, the rate of recovery for being computed cobalt is 98.83 %.Cobalt hydroxide it is pure
Degree is 99.2%.
(embodiment 3)
Cobalt manganese waste material handled by the present embodiment is same as Example 1, the method for cobalt and manganese in separating and recovering cobalt manganese waste material
Remaining is same as Example 1, the difference is that:
Step 4. in trivalent cobalt ammonia complex be reduced to the cobalt ammonia complex of divalent after, stir that lower that sodium oxalate is added dropwise is molten
Liquid adds 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
Degree is 500 r/min.
In addition to sodium oxalate solution described in the present embodiment, ammonium oxalate can also be used to substitute sodium oxalate.
Cobalt oxalate 3.1602g is obtained after washing and drying, the rate of recovery of cobalt is 98.9%, and the purity of cobalt oxalate is 97.3%.Cobalt
Cobalt in manganese waste material is recycled in the form of cobalt oxalate.
(embodiment 4)
Cobalt manganese waste material handled by the present embodiment is same as Example 1, the method for cobalt and manganese in separating and recovering cobalt manganese waste material
Remaining is same as Example 1, the difference is that:
When step pre-processes 1., the hydrochloric acid solution 44mL of 10 % is added in the reaction vessel of Xiang Shengyou cobalt manganese waste material, to 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 3.5 hereinafter, be then transferred to 30 min of heating water bath in 80 DEG C of water-bath, filter, go to deacidify it is molten after in material
Organic matter.
The rate of recovery of cobalt is 96.3% in the present embodiment, and the rate of recovery of manganese is 99.6%.
(embodiment 5)
Cobalt manganese waste material handled by the present embodiment is same as Example 1, the method for cobalt and manganese in separating and recovering cobalt manganese waste material
Remaining is same as Example 1, the difference is that:
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., the sulfuric acid solution 25mL of 30 % is added in the reaction vessel of Xiang Shengyou cobalt manganese waste material, to 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
Middle 30 min of heating water bath is filtered, go to deacidify it is molten after organic matter in material.
The rate of recovery of cobalt is 95.7% in the present embodiment, and the rate of recovery of manganese is 99.8%.
(embodiment 6)
Cobalt manganese waste material handled by the present embodiment is same as Example 1, the method for cobalt and manganese in separating and recovering cobalt manganese waste material
Remaining is same as Example 1, the difference is that:
Step 3. in, ozone, ozone output speed are passed through under stirring into the digestion solution after step 2. complex reaction
For 3g/h, maintenance fluid temperature is 20 DEG C when being passed through ozone, mixing speed is 200 r/min；Stop being passed through ozone after 3 h,
The reaction was continued 15h under being 200 r/min in 20 DEG C, mixing speed, the divalent manganesetion in digestion solution is by ozone oxidation, this reality
It applies in example as 4.62:1.
The rate of recovery of cobalt is 99.8% in the present embodiment, and the rate of recovery of manganese is 99.9%.
Claims (5)
1. a kind of method of cobalt and manganese in separating and recovering cobalt manganese waste material, it is characterised in that the following steps are included:
1. pre-processing, by cobalt manganese waste material acid dissolution to be processed, acid used is nitric acid, hydrochloric acid or sulfuric acid, acid used
PH value is less than 1, and the ratio between amount of substance of cobalt, manganese is n (H in sour dosage and cobalt manganese waste material+):[n (Mn) + n(Co) ]=
2:1~4:1；The pH value for controlling the molten rear material of acid is less than or equal to 3.5, by molten rear material of the pH value less than or equal to 3.5 of acid at 70 DEG C
It after being heated in~85 DEG C of water-bath, filters, obtained filtrate is to be processed as digestion solution；
2. cobalt is complexed, ammonium hydroxide is added in the digestion solution obtained after 1. filtering to step, so that the pH value of digestion solution is greater than 7.5, ammonia
It is 2:1~50:1 with the ratio between the amount of substance of cobalt, is stirred to react 20~60min, network occurs for the cobalt ions in digestion solution and ammonium root
Close reaction；
3. heavy manganese, is passed through ozone into the digestion solution after step 2. complex reaction under stirring, the object of the ozone and manganese that are passed through
The ratio between amount of matter=1:1~5:1, when being passed through ozone maintain fluid temperature be 20 DEG C~80 DEG C, mixing speed be 100 r/min~
1000 r/min；Stop being passed through ozone after 0.5h~8h, stopping is passed through after ozone that the reaction was continued 5h~15h, two in digestion solution
Valence manganese ion is by ozone oxidation；
After reaction, filter, filtrate is cobalt ammonia complexing liquid, and filter residue is manganese dioxide precipitate, complete in cobalt manganese waste material cobalt and
The separation of manganese, and manganese is recycled in the form of manganese dioxide；
4. the cobalt ammonia complex solution being obtained by filtration after step 3. heavy manganese is placed in water-bath and is heated to 70 DEG C~85 by Call Provision
DEG C, reducing agent is added thereto, and the reducing agent added is one of hydrazine hydrate, sodium borohydride or paraformaldehyde, or will be walked
Suddenly the cobalt ammonia complex solution being 3. obtained by filtration, which is placed in oil bath pan, is heated to 170 DEG C~185 DEG C, reducing agent is then added, institute
The reducing agent of addition is ethylene glycol；The ratio between amount of substance of cobalt is 0.8:1~5:1 in reducing agent and cobalt ammonia complex solution, instead
Answer 15min~60min；
Then lower dropwise addition sodium hydroxide solution or oxalate solution are stirred into the material after reduction reaction, after being added dropwise
React 20min~60min；It filters after reaction, obtains cobalt hydroxide or cobalt oxalate after the washing of precipitate filtered is dry,
Complete the recycling of cobalt.
2. the method for cobalt and manganese in separating and recovering cobalt manganese waste material according to claim 1, it is characterised in that: step 1. in water
Before bath heating, if the pH value for controlling the molten rear material of acid, which is less than or equal to 3.5, refers to that the pH value of the molten rear liquid of acid is greater than 3.5, thereto
Acid used makes its pH value lower than 3.5 when sour molten waste material is added；If the pH value of liquid is less than 3.5 after acid is molten, water is directly carried out
Bath heating.
3. the method for cobalt and manganese in separating and recovering cobalt manganese waste material according to claim 1, it is characterised in that: step 4. hydrogen-oxygen
After change sodium solution or oxalate solution are added dropwise, 20min~60min is reacted under conditions of 70 DEG C~85 DEG C of heating water baths.
4. the method for cobalt and manganese in separating and recovering cobalt manganese waste material according to claim 3, it is characterised in that: when 4. 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. according to claim 1 into separating and recovering cobalt manganese waste material described in one of 4 cobalt and manganese method, it is characterised in that: step
Suddenly 1. in cobalt in cobalt manganese waste material to be processed, manganese mass ratio be 1:1~1:4.
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| CN107732351B (en) * | 2017-10-11 | 2019-12-03 | 上海应用技术大学 | The separation of nickel and cobalt and method of resource in a kind of waste and old ni-mh positive electrode |
| CN109148995B (en) * | 2018-07-26 | 2020-10-30 | 江苏理工学院 | Common treatment method for low-cobalt high-manganese waste and waste lithium battery cathode material |
| CN110563044B (en) * | 2019-09-30 | 2022-04-01 | 深圳市德方纳米科技股份有限公司 | Method for recycling positive electrode material of waste ternary battery and recycled material |
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| CN1059241C (en) * | 1998-09-25 | 2000-12-06 | 孔令树 | Process for efficiently extracting cobalt compound from leftover containing cobalt |
| CN102503813A (en) * | 2011-09-22 | 2012-06-20 | 曹善文 | Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue |
| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
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| CN104058514A (en) * | 2013-08-28 | 2014-09-24 | 无锡市兴盛环保设备有限公司 | PTA wastewater sectionalizing separating and cobalt-manganese recycling method |
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| CN1059241C (en) * | 1998-09-25 | 2000-12-06 | 孔令树 | Process for efficiently extracting cobalt compound from leftover containing cobalt |
| CN102503813A (en) * | 2011-09-22 | 2012-06-20 | 曹善文 | Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue |
| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
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