CN107739828B - Method for separating and recovering cobalt and manganese in low-cobalt high-manganese waste by using ammonia-ammonium carbonate - Google Patents
Method for separating and recovering cobalt and manganese in low-cobalt high-manganese waste by using ammonia-ammonium carbonate Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 100
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 100
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011572 manganese Substances 0.000 title claims abstract description 82
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 78
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- FWABRVJYGBOLEM-UHFFFAOYSA-N diazanium;azane;carbonate Chemical compound N.[NH4+].[NH4+].[O-]C([O-])=O FWABRVJYGBOLEM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 68
- 238000011084 recovery Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- WRWZNPYXEXPBAY-UHFFFAOYSA-N azane cobalt Chemical compound N.[Co] WRWZNPYXEXPBAY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 11
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 11
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 11
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 36
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- 230000029087 digestion Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 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
- 229910021529 ammonia Inorganic materials 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
- 238000004090 dissolution Methods 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000001376 precipitating effect 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
- 238000005406 washing Methods 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
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 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
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 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 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 75
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004519 manufacturing process Methods 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
- -1 and physics Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000008236 heating water Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003756 stirring 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
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 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
- 239000000203 mixture Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006555 catalytic reaction 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
- 230000000536 complexating effect Effects 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
- 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
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
- C22B23/0446—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
- C22B47/0009—Obtaining manganese from spent catalysts
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal 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
- 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
- C22B7/009—General processes for recovering metals or metallic compounds 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)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (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 low-cobalt high-manganese waste by using ammonia-ammonium carbonate, which comprises the steps of pretreating the low-cobalt high-manganese waste to be treated, adding ammonia-ammonium carbonate mixed solution, filtering after the reaction is finished to respectively obtain cobalt-ammonia complex solution and manganese carbonate precipitate, and recovering manganese in the low-cobalt high-manganese waste in the form of manganese carbonate; finally, cobalt is recovered 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%, high recovery rate of manganese up to more than 99%, and high-valued recovery of non-ferrous metal resources.
Description
The application is application No. is 201510839476.9, 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 " with the method for cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt ".
Technical field
The present invention relates to a kind of separation and recovery methods of cobalt manganese waste material, and in particular to a kind of ammonia-ammonium carbonate separation and recovery
The method of cobalt and manganese in the high manganese waste material of low cobalt.
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 high method with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt.
The technical solution for realizing the object of the invention is a kind of cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt
Method, comprising the following steps:
1. pre-processing, by the high manganese waste material acid dissolution of low cobalt to be processed, the pH value of material is less than or equal to after control acid is molten
3.5, 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；Add into filtrate
Entering sodium hydroxide solution makes its pH value rise to 4~5, filters after standing, obtained filtrate is to be processed as digestion solution.
2. preparing ammonia-ammonium carbonate mixed solution, the concentration range of ammonium carbonate is 40~100 g/L, ammonium hydroxide in mixed solution
Concentration range is 50~100 g/L, and the pH value of mixed solution is 9~11.
3. cobalt, manganese separate, 2. ammonia-ammonium carbonate mixing that step is prepared is added in the digestion solution obtained after 1. filtering to step
Solution obtains reaction solution, and the pH value of reaction solution is 7.5~10.0, and the ratio between amount of substance of ammonium carbonate and manganese is 0.9 after addition:
1~2: 1, the ratio between ammonium hydroxide and the amount of substance of cobalt are 10: 1~50: 1；Reaction solution reaction 6~15 after addition
Hour.
After reaction, filter, respectively obtain cobalt ammonia complex solution and manganese carbonate precipitating, in the high manganese waste material of low cobalt manganese with
The form of manganese carbonate recycles.
4. 3. cobalt ammonia complex solution that step is obtained by filtration is heated to 70 DEG C~185 DEG C, thrown thereto by Call Provision
Adding reducing agent, the ratio between amount of substance of cobalt is 0.8:1~5:1 in reducing agent and cobalt ammonia complex solution, reaction 15min~
60min；Then lower dropwise addition sodium hydroxide solution or oxalate solution are stirred into the material after reduction reaction, are added dropwise
20min~60min is reacted afterwards；It filters after reaction, obtains cobalt hydroxide or oxalic acid after the washing of precipitate filtered is dry
Cobalt completes the recycling of cobalt.
Appeal step 1. used in acid be nitric acid, hydrochloric acid or sulfuric acid, the substance of cobalt, manganese in sour dosage and cobalt manganese waste material
The ratio between amount be n (H+): [n (Mn)+n (Co)]=2: 1~4: 1.
Further, step 1. in acid dissolution cobalt manganese waste material when, the pH value of acid used is less than 1.
Above-mentioned steps 3. in 1. filtered to step after 2. ammonia-ammonium carbonate mixing that step is prepared is added in obtained digestion solution
After solution obtains reaction solution, reaction 6~15 is small under reaction solution is 150~500 r/min in 20~40 DEG C, mixing speed
When.
4. middle reducing agent is one of hydrazine hydrate, sodium borohydride, ethylene glycol or paraformaldehyde to above-mentioned steps.
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, 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.
Above-mentioned steps 1. in cobalt in the high manganese waste material of low cobalt 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 all cobalt manganese waste materials, especially cobalt
Low cobalt high manganese waste material of the manganese ratio 1: 1~4, such as the useless cobalt-manganese catalyst that petroleum industry production PTA is generated, present invention process letter
Single, cost recovery is low, and the rate of recovery of cobalt and manganese is all very high, and the rate of recovery of cobalt can be up to 95% or more, and the rate of recovery of manganese can reach
To 99% or more.
(2) present invention pretreatment Shi Xianyong pH value is molten by the high manganese waste material acid of low cobalt less than 1 strong acid, and acid, which is dissolved, finishes control liquid
The pH value of body is less than or equal to 3.5, heats and filters off the organic matter in the molten rear material that deacidifies, then to the object after removal organic matter
Adding sodium hydroxide makes the pH value of liquid rise to 4~5 in material, this purpose for adjusting pH value is removal impurity iron, if cobalt manganese waste material
In contain impurity iron, iron ion meeting and hydroxyl after acid is molten are removed after filtering from precipitating is generated.The present invention is by impurity iron
Removal is placed on before ammonification step, ensure that the cobalt of separation and recovery and the purity of manganese；And the step of increasing removal organic matter,
It is further ensured that 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.
(4) 2. ammonia that step of the invention is prepared-ammonium carbonate mixed solution is buffer solution, so that anti-when step is reacted 3.
It answers the pH value of system in stable range, guarantees that reaction is gone on smoothly, the rate of recovery of final products is high；In addition buffering used is molten
Liquid is at low cost, reduces the cost recovery of cobalt manganese waste material.
Specific embodiment
Cobalt content, which is lower than, in the high manganese waste material of heretofore described low cobalt is equal to manganese content.
(embodiment 1)
The high manganese waste material of low cobalt handled by the present embodiment is the useless cobalt-manganese catalyst that generates in PTA production, and wherein cobalt contains
Amount is 9.872wt %, and the content of manganese is 17.12 wt %.
The present embodiment with the method for cobalt and manganese in the ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt the following steps are included:
1. pre-processing.The high manganese waste material of 13 grams of low cobalts is taken, is added 40% in the reaction vessel of the high manganese waste material of Xiang Shengyou low cobalt
30 mL of nitric acid solution, after the resolution completely of cobalt manganese waste material, the pH value of liquid is 1.5 after measurement acid is molten.The dosage of acid and useless catalysis
The ratio between amount of substance of cobalt manganese is n (H in agent+): [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.The pH value for needing to control the molten rear liquid of acid before heating water bath, if the pH value of liquid is greater than after acid is molten
3.5, acid, that is, nitric acid used makes its pH value lower than 3.5 when sour molten waste material being added thereto, due to the molten rear liquid of acid in the present embodiment
The pH value of body is 1.2, therefore can be directly heated.
The sodium hydroxide solution that 5mol/L is added into the material for eliminate organic matter makes its pH value rise to this reality of 4~5(
It applies in example as 4.5)；It is filtered after standing 20min, obtained filtrate i.e. digestion solution is to be processed.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 removes from digestion solution after suction filtration.
2. preparing ammonia-ammonium carbonate mixed solution.
Ammonium carbonate is dissolved in ammonium hydroxide, it is stand-by to obtain ammonia-ammonium carbonate mixed solution, the concentration of ammonium carbonate in mixed solution
Range is 40~100 g/L, and ammonia concn range is 50~100 g/L, and the pH value of mixed solution is 9~11.The present embodiment
The concentration of ammonium carbonate is 50 g/L in the mixed solution of preparation, and ammonia concn is 60 g/L.
3. cobalt, manganese separate.2. ammonia-ammonium carbonate that step is prepared is slowly added in the digestion solution obtained after 1. filtering to step
Mixed solution obtains reaction solution, and the pH value of reaction solution is 7.5~10.0, and the ratio between ammonium carbonate and the amount of substance of manganese are after addition
0.9: 1~2: 1, the ratio between ammonium hydroxide and the amount of substance of cobalt are 10: 1~50: 1.Reaction solution exists after addition
30 DEG C, mixing speed be 200 r/min under conditions of react 12 hours.
It is mixed that 2. ammonia-ammonium carbonate that step is prepared is slowly added in the digestion solution obtained after 1. filtering in the present embodiment to step
Close solution (wherein the concentration of ammonium carbonate is 50 g/L, and ammonia concn is 60 g/L) 60 mL, the substance of ammonium carbonate and manganese after addition
The ratio between amount be 1.3: 1, the ratio between ammonium hydroxide and the amount of substance of cobalt are 10.4: 1.
After reaction, it filters, respectively obtains cobalt ammonia complex solution and manganese carbonate precipitating, manganese carbonate washing of precipitate is dry
It weighs afterwards and obtains 4.6442g, the rate of recovery of manganese is 99.8% in the high manganese waste material of low cobalt, and the purity of the manganese carbonate recycled is
99.4%。
4. Call Provision.3. cobalt ammonia complex solution that step is obtained by filtration is placed in water-bath and is heated to 80 DEG C.To 80
DEG C cobalt ammonia complex solution in be added in 20%~80%(of reducing agent the present embodiment as 1.00 mL of hydrazine hydrate 80%), maintain water
It bathes for 20min) in 80 DEG C of reaction 15min~60min(the present embodiment, the cobalt ammonia complex of trivalent is reduced to the cobalt ammonia of divalent
Complex compound.
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 after addition): 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 2.0189g.The purity of cobalt hydroxide is 99.9%.
The rate of recovery for being computed cobalt is 99.8%.
(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:
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 3.1794g is obtained after drying, the rate of recovery of cobalt is 99.5 %, and the purity of cobalt oxalate is 99.2%.Cobalt manganese is useless
Cobalt in material is recycled in the form of cobalt oxalate.
(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., 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.
(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., 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.
(embodiment 5)
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:
Step 3. in 1. filtered to step after be slowly added to 2. ammonia-ammonium carbonate mixing that step is prepared in obtained digestion solution
Solution obtains reaction solution, and the ratio between amount of substance of ammonium carbonate and manganese is 2: 1 after addition, the ratio between ammonium hydroxide and the amount of substance of cobalt
It is 50: 1.After addition reaction solution 40 DEG C, mixing speed be 500 r/min under conditions of react 6 hours.
After reaction, it filters, respectively obtains cobalt ammonia complex solution and manganese carbonate precipitating, manganese carbonate washing of precipitate is dry
It weighs afterwards and obtains 4.6676g, the rate of recovery of manganese is 99.9% in the high manganese waste material of low cobalt, and the purity of the manganese carbonate recycled is
98.5%。
4. step obtains cobalt hydroxide product 1.9926g.The purity of cobalt hydroxide is 99.7%.
The rate of recovery for being computed cobalt is 98.3 %.
Claims (4)
1. a kind of method with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt, it is characterised in that including following step
It is rapid:
1. pre-processing, by the high manganese waste material acid dissolution of low cobalt 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；Hydrogen is added into filtrate
Sodium hydroxide solution makes its pH value rise to 4~5, filters after standing, and obtained filtrate is to be processed as digestion solution；
2. preparing ammonia-ammonium carbonate mixed solution, the concentration range of ammonium carbonate is 40~100 g/L, ammonia concn in mixed solution
Range is 50~100 g/L, and the pH value of mixed solution is 9~11；
3. cobalt, manganese separate, 2. ammonia-ammonium carbonate mixed solution that step is prepared is added in the digestion solution obtained after 1. filtering to step
Reaction solution is obtained, the pH value of reaction solution is 7.5~10.0, and the ratio between amount of substance of ammonium carbonate and manganese is 0.9: 1 after addition
~2: 1, the ratio between ammonium hydroxide and the amount of substance of cobalt are 10: 1~50: 1；Reaction solution is 20~40 after addition
DEG C, mixing speed be 150~500 r/min under react 6~15 hours；
After reaction, it filters, respectively obtains cobalt ammonia complex solution and manganese carbonate precipitating, manganese is in the high manganese waste material of low cobalt with carbonic acid
The form of manganese recycles；
4. 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 by Call Provision, to
Reducing agent is wherein added, the reducing agent added is one of hydrazine hydrate, sodium borohydride or paraformaldehyde, or by step 3. mistake
The cobalt ammonia complex solution that filter obtains, which is placed in oil bath pan, is heated to 170 DEG C~185 DEG C, and reducing agent is then added, is added
Reducing agent is ethylene glycol；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, what it is when dropwise addition is
When 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；20min~60min is reacted after being added dropwise；It filters after reaction, the washing of precipitate filtered is dry
After obtain cobalt hydroxide or cobalt oxalate, complete the recycling of cobalt.
2. the method according to claim 1 with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt, feature
Be: step 1. used in acid be nitric acid, hydrochloric acid or sulfuric acid, cobalt in sour dosage and cobalt manganese waste material, manganese substance amount it
Than for n (H+): [n (Mn)+n (Co)]=2: 1~4: 1.
3. the method according to claim 1 with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt, feature
Be: step 1. in acid dissolution cobalt manganese waste material when, the pH value of acid used is less than 1.
4. according to claim 1 to the side for separating and recovering cobalt and manganese in the high manganese waste material of low cobalt described in one of 3 with ammonia-ammonium carbonate
Method, it is characterised in that: step 1. in cobalt in the high manganese waste material of low cobalt to be processed, manganese mass ratio be 1:1~1:4.
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| GB1348031A (en) * | 1971-05-13 | 1974-03-13 | Roy T K | Process for recovery of nickel and cobalt |
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| GB751866A (en) * | 1953-12-21 | 1956-07-04 | Chemical Construction Corp | Improvements in or relating to method of recovering metals |
| GB1348031A (en) * | 1971-05-13 | 1974-03-13 | Roy T K | Process for recovery of nickel and cobalt |
| CN1651584A (en) * | 2005-02-06 | 2005-08-10 | 金川集团有限公司 | Production method of dentritic morphology nickel powder |
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