CN105779777A - Method for separating and recycling nickel and cobalt from nickel and cobalt slag - Google Patents
Method for separating and recycling nickel and cobalt from nickel and cobalt slag Download PDFInfo
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- CN105779777A CN105779777A CN201610124842.7A CN201610124842A CN105779777A CN 105779777 A CN105779777 A CN 105779777A CN 201610124842 A CN201610124842 A CN 201610124842A CN 105779777 A CN105779777 A CN 105779777A
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- Prior art keywords
- cobalt
- nickel
- slag
- separation
- recovery
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000010941 cobalt Substances 0.000 title claims abstract description 136
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 136
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 75
- 239000002893 slag Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004064 recycling Methods 0.000 title abstract 3
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 35
- 239000007800 oxidant agent Substances 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 241001625808 Trona Species 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 45
- 230000003647 oxidation Effects 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 8
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 229950009390 symclosene Drugs 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000004886 process control Methods 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 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 40
- 239000012535 impurity Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 2
- 238000010907 mechanical stirring Methods 0.000 abstract 2
- 238000007664 blowing Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 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 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- C22B7/04—Working-up slag
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating and recycling nickel and cobalt from nickel and cobalt slag. According to the method, the nickel and cobalt slag is placed in an acidic solution at the room temperature condition to be subjected to mechanical stirring and air blowing leaching; then solid and liquid separation is performed; an oxidant composition is added into leach liquor to conduct oxidization for cobalt depositing; meanwhile, trona or sodium bicarbonate is added to adjust the pH value; the solution is heated to 50 DEG C to 80 DEG C, and mechanical stirring reaction is performed for 3-5 h; liquid and solid separation is performed; filter liquor is a nickel-containing acidic solution; the filter liquor is fed to be subjected to cyclone electro-deposition so that electro-nickel can be produced; and filter slag is fed into a cobalt extraction process to be processed. According to the method, no impurity ions are introduced in the whole process system, no influences are caused to subsequent production, the quality of electrolytic nickel can be guaranteed, the technological process is simple, the nickel and cobalt separation efficiency is high, the production cost is low, the cobalt depositing rate is not lower than 98%, the nickel recycling rate is high, and the direct recovery rate can reach 88%. By means of the method, the nickel and cobalt separation purpose can be effectively achieved, reagents in use are free of waste gas generation and can be recycled, and the operation environment is good.
Description
Technical field
The present invention relates to a kind of separation and recovery nickel, method of cobalt from nickel cobalt slag, belong to non-ferrous metal wet method smelting
Gold refining purification technique field.
Background technology
Nickel cobalt slag is the intermediate product in lateritic nickel ore (containing cobalt) hydrometallurgy flow process, mostly by nickel, cobalt,
Ferrum, calcium, magnesium, the composition such as the hydroxide of the heavy metal such as a small amount of lead, copper, zinc and silicon oxide.Due to cobalt
Price higher, the physicochemical property of cobalt and nickel closely, therefore to nickel cobalt be separately recovered, improve cobalt
The response rate, the most common method be control condition by the nickel cobalt dissolution in nickel cobalt slag, then by the leaching of nickel and cobalt containing
Go out liquid separation and recovery nickel, cobalt.The method separating nickel cobalt both at home and abroad from the acid solution of nickel and cobalt containing mainly has extraction
Take partition method, ion exchange, chlorine oxidation process, black nickel oxidizing process, sodium peroxydisulfate oxidizing process etc. multiple,
But these methods are individually present certain deficiency when Separation of nickel and cobalt produces.Chlorine oxidation sinks cobalt method and can make
Becoming the nickeliferous height of cobalt slag, the cobalt quantity of slag is big, if this method reaction condition controls bad, then the oxidation effectiveness of cobalt is the best,
Operating environment even has the danger of chlorine leakage；Organic solvent extractionprocess technological process is long, but exists organic molten
Agent consumption is big, relatively costly, can be to the problem of environment；Black nickel oxidizing process removes cobalt in nickel materials
Time do not introduce impurity, separation efficiency is high, and will not introduce impurity, but, black nickel sinks cobalt and need to use electroxidation
Method prepares black nickel, and reaction time is long, and black nickel conversion ratio is in reduced levels, averagely about 50%, and black nickel
Preparation cost is higher；When using cobalt and nickel in cation exchange resin separation solution, do not reach degree of depth separation cobalt
Purpose with nickel；In chelating resin separation solution, the method efficiency of cobalt nickel is high, but there is resin bad mechanical strength,
The defect that resin absorption capacity is little, operating cost is high；Sodium peroxydisulfate oxidizing process sinks cobalt, and reagent consumption is big, oxygen
Changing temperature high, about 80-90 DEG C, the time is long, about 5-8h, and cost is high, easily causes sodium ion in liquor accumulation etc.
The most not enough.The many deficiencies existed due to above-mentioned separation method, therefore develop a kind of low cost, safety
Environmental protection, the separation method not introducing foreign ion and good separating effect have very important significance.
Summary of the invention
The technical problem to be solved is to provide a kind of separation and recovery nickel, method of cobalt from nickel cobalt slag,
The method mainly solves oxidizing process, and to sink cobalt cost high, easily causes environmental pollution, after heavy cobalt during organic solvent extraction
Liquid also needs to carry out oil removing operation, the heavy cobalt of oxidation use in sodium carbonate and time to there will be local base concentration too high, make
Become the problem that nickel loss is high, reach higher cobalt precipitation rate simultaneously.
To achieve these goals, the technical solution adopted in the present invention is to provide a kind of separation from nickel cobalt slag
Reclaim nickel, the method for cobalt, comprise the following steps:
(1) prepare nickel cobalt slag acid leaching solution: with nickel cobalt slag as raw material, add acid solution, mechanical agitation
And blast air and leach, leach and terminate rear solid-liquid separation, obtain nickeliferous, the acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, mechanical agitation in the acid leaching solution of nickeliferous, cobalt
And heat, under the conditions of 50-80 DEG C, react 3-5h, in course of reaction, control ph is at 5.0-5.5；Reaction knot
Shu Hou, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxalate or oxygen
Change cobalt.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 4-7 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 5.8-8.2 part, monoacetylaniline 1.0-2.3 part and polyacrylamide 0.15-0.25 part,
Consumption is addition oxidation synergist to final concentration 1-5g/L.
In step (1), acid solution is sulfuric acid solution, hydrochloric acid solution or salpeter solution, and concentration is 5-20%.
In step (1), the liquid-solid ratio of acid solution and nickel cobalt slag is 3-10:1.
In step (1) and (2), churned mechanically speed is 60-120r/min.
The air capacity blasted in step (1) is needed for precipitated iron, manganese 3-6 times of theoretical amount.
The time leached in step (1) is 2-3h, and it is 2.0 that leaching process controls pH.
In step (2), the reagent used by control ph is trona or sodium bicarbonate.
Described solid-liquid separation is to use vacuum filtration machine, filter press or centrifuge to carry out solid-liquid separation.
Described nickel cobalt slag processes through ore grinding, and mog accounts for more than 90% for-74 μm.
Described ore grinding processes and uses ball mill, rod mill or jet mill to carry out ore grinding.
Nickel cobalt slag refers to the hydroxide of nickel and cobalt, oxide, carbonate, sulfate, solid alloy, gives up
Catalyst etc., containing ferrum, copper, zinc, manganese, lead, bismuth, magnesium, etc. the compound of impurity element or monomer
Metal, aluminium oxide, the mixture of the mineral such as silicon oxide.
Beneficial effects of the present invention
1, the present invention uses acid solution to leach the nickel in nickel cobalt slag, cobalt, makes nickel, cobalt enter solution
In, but will also result in other impurity element a large amount of and enter in solution, cause leachate is not only enriched nickel,
Cobalt, and containing other foreign metal.Therefore, the present invention, while acidic leaching, blasts in leachate
Air, it is possible to oxidation removes the major part metal such as ferrum, manganese in leachate, reduces follow-up heavy cobalt operation oxidant
The consumption of compositions.
2, sym-closene, monoacetylaniline and polyacrylamide are combined by the present invention, by adjusting three kinds
Proportioning between component so that it is as oxidation synergist, be applied to nickel in nickel cobalt slag acid leaching solution, cobalt
The oxidation operation of separation and recovery, it is possible to significantly improve the oxidation effectiveness of original oxidant.The oxidation of the present invention increases
Effect agent produces without waste gas, to environment, and can will not recycle, good operational environment.
3, oxidation synergist and oxidants hydrogen peroxide are combined together as oxidizing agent composition by the present invention,
Utilize the bivalence cobalt in its Strong oxdiative character oxidation precipitation nickel cobalt slag acid leaching solution, oxygen occurs in the reactor
Change reaction, nickel cobalt leachate is processed, have the advantage that (1) is organic due to oxidation synergist
Macromolecular material, hydrogen peroxide does not contains foreign ion yet, the most whole during will not introduce any impurity
Ion, it is possible to obtain the metal salt solution of cleaning, follow-up metal recovery operation, it is possible to after guarantee
The quality of continuous metal recovery；(2) price of hydrogen peroxide is relatively low, and heating-up temperature low (50-80 DEG C), the time is short
(3-5h), it is possible to saving energy resource consumption, economical, production cost is low；(3) simple to operate, separation effect
Rate is high.
4, the present invention uses trona or sodium bicarbonate to adjust pH value, can not only be cost-effective, Er Qieneng
Enough avoid local basicity too high, form basic nickel carbonate, make, except nickel content raises in cobalt slag, to cause the damage of nickel
Lose.Meanwhile, the present invention uses trona or sodium bicarbonate to adjust pH value, and control ph is at 5.0-5.5, energy
The heavy cobalt effect of enough raisings.
5, nickel cobalt slag acid leaching solution is processed by the present invention, reclaims the nickel in this leachate and cobalt, whole
Process system does not introduce any foreign ion, subsequent production is not impacted, it is possible to ensure electrolytic nickel
Quality, and technological process is simple, Separation of nickel and cobalt efficiency is high, production cost is low, cobalt precipitation rate is not less than 98%,
Nickel recovery is high, and nickel direct yield is up to more than 88%.The method using the present invention, can effectively achieve nickel
The purpose that cobalt separates, agents useful for same produces without waste gas, can recycle, good operational environment.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described in further detail.
Embodiment 1
The present embodiment separates and recovers nickel, the method for cobalt from nickel cobalt slag, comprises the following steps:
(1) nickel cobalt slag acid leaching solution is prepared: to be mainly composed of Ni 25.60%, Co 3.58%, Cu
It is raw material that the lateritic nickel ore pressurized heat acid leaching liquor of 0.73%, Fe 6.20% adds the hydroxide nickel cobalt that Caustic soda is settled out,
Adding the sulfuric acid solution of concentration 5%, liquid-solid ratio is 5:1,80r/min mechanical agitation and blasts air and leach,
The air capacity blasted is needed for precipitated iron, manganese 3 times of theoretical amount, extraction time 3h under room temperature, leaching process
Controlling pH is 2.0, obtains nickeliferous, the acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, 80r/min in the acid leaching solution of nickeliferous, cobalt
Mechanical agitation also heats, and reacts 5h under the conditions of 80 DEG C, adds trona control ph and exist in course of reaction
5.4；After reaction terminates, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxalate.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 5 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 5.8 parts, monoacetylaniline 2.0 parts and polyacrylamide 0.15 part, consumption is for adding
Oxidation synergist is to final concentration 3g/L.
Described solid-liquid separation is to use centrifuge to carry out solid-liquid separation.
The cobalt precipitation rate of the present embodiment is 99.6%, and nickel direct yield is 87.5%.
Embodiment 2
The present embodiment separates and recovers nickel, the method for cobalt from nickel cobalt slag, comprises the following steps:
(1) prepare nickel cobalt slag acid leaching solution: with certain nickel and cobalt containing oxide slag as raw material, add concentration 20%
Sulfuric acid solution, liquid-solid ratio is 5:1,60r/min mechanical agitation and blasts air and leach, the sky blasted
Tolerance is needed for precipitated iron, manganese 4 times of theoretical amount, and extraction time 2h under room temperature, leaching process controls pH
It is 2.0, obtains nickeliferous, the acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, 60r/min in the acid leaching solution of nickeliferous, cobalt
Mechanical agitation also heats, and reacts 3h under the conditions of 65 DEG C, adds trona control ph and exist in course of reaction
5.0；After reaction terminates, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxalate.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 6 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 5.8 parts, monoacetylaniline 2.0 parts and polyacrylamide 0.15 part, consumption is for adding
Oxidation synergist is to final concentration 2g/L.
Described solid-liquid separation is to use vacuum filtration machine to carry out solid-liquid separation.
The cobalt precipitation rate of the present embodiment is 99.0%, and nickel direct yield is 88.1%.
Embodiment 3
The present embodiment separates and recovers nickel, the method for cobalt from nickel cobalt slag, comprises the following steps:
(1) nickel cobalt slag acid leaching solution is prepared: to be mainly composed of Ni 25.88%, Co 2.70%, Fe
The nickel and cobalt containing carbonate of 35.06%, Cu 2.8% is raw material, adds the sulfuric acid solution of concentration 10%, and liquid-solid ratio is
8:1,100r/min mechanical agitation also blasts air and leaches, needed for the air capacity blasted is precipitated iron, manganese
5 times of theoretical amount, extraction time 3h under room temperature, it is 2.0 that leaching process controls pH, obtains nickeliferous, cobalt
Acid leaching solution；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, 100r/min in the acid leaching solution of nickeliferous, cobalt
Mechanical agitation also heats, and reacts 4h under the conditions of 50 DEG C, adds sodium bicarbonate control ph in course of reaction
5.5；After reaction terminates, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxalate.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 4 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 7.5 parts, monoacetylaniline 1.0 parts and polyacrylamide 0.2 part, consumption is for adding
Oxidation synergist is to final concentration 1g/L.
Described solid-liquid separation is to use centrifuge to carry out solid-liquid separation.
The cobalt precipitation rate of the present embodiment is 98.6%, and nickel direct yield is 88.3%.
Embodiment 4
The present embodiment separates and recovers nickel, the method for cobalt from nickel cobalt slag, comprises the following steps:
(1) nickel cobalt slag acid leaching solution is prepared: to be mainly composed of Ni 13.57%, Co 0.32%, Fe
The nickel cobalt slag of 51.86%, Cu 2.5% is raw material, uses ball mill that nickel cobalt slag is carried out ore grinding process, and ore grinding is thin
Degree accounts for more than 90% for-74 μm, adds the sulfuric acid solution of concentration 15%, and liquid-solid ratio is 3:1,100r/min machine
Tool stirs and blasts air and leaches, and the air capacity blasted is needed for precipitated iron, manganese 6 times of theoretical amount,
Extraction time 2.5h under room temperature, it is 2.0 that leaching process controls pH, obtains nickeliferous, the acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, 100r/min in the acid leaching solution of nickeliferous, cobalt
Mechanical agitation also heats, and reacts 3.5h under the conditions of 75 DEG C, adds trona control ph in course of reaction
5.3；After reaction terminates, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxide.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 7 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 8.2 parts, monoacetylaniline 2.3 parts and polyacrylamide 0.25 part, consumption is for adding
Oxidation synergist is to final concentration 5g/L.
Described solid-liquid separation is to use filter press to carry out solid-liquid separation.
The cobalt precipitation rate of the present embodiment is 98.8%, and nickel direct yield is 87.5%.
Embodiment 5
The present embodiment separates and recovers nickel, the method for cobalt from nickel cobalt slag, comprises the following steps:
(1) nickel cobalt slag acid leaching solution is prepared: to be mainly composed of Ni 3.8%, Co 5.5%, Fe 12.5%,
The petrochemical industry dead catalyst slag of Cu 1.6% is raw material, uses jet mill to petrochemical industry dead catalyst slag
Carrying out ore grinding process, mog accounts for more than 90% for-74 μm, adds the sulfuric acid solution of concentration 10%, liquid
Gu than for 10:1,120r/min mechanical agitation and blast air and leach, the air capacity blasted be precipitated iron,
Needed for manganese 3 times of theoretical amount, extraction time 3h under room temperature, it is 2.0 that leaching process controls pH, obtain nickeliferous,
The acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, 120r/min in the acid leaching solution of nickeliferous, cobalt
Mechanical agitation also heats, and reacts 5h under the conditions of 75 DEG C, adds trona control ph and exist in course of reaction
5.5；After reaction terminates, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxide.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 7 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 6.0 parts, monoacetylaniline 1.5 parts and polyacrylamide 0.2 part, consumption is for adding
Oxidation synergist is to final concentration 2.5g/L.
Described solid-liquid separation is to use vacuum filtration machine to carry out solid-liquid separation.
The cobalt precipitation rate of the present embodiment is 99.3%, and nickel direct yield is 88.5%.
Claims (10)
1. one kind separates and recovers nickel, the method for cobalt from nickel cobalt slag, it is characterised in that comprise the following steps:
(1) prepare nickel cobalt slag acid leaching solution: with nickel cobalt slag as raw material, add acid solution, mechanical agitation
And blast air and leach, leach and terminate rear solid-liquid separation, obtain nickeliferous, the acid leaching solution of cobalt；
(2) the heavy cobalt of oxidation: add oxidizing agent composition, mechanical agitation in the acid leaching solution of nickeliferous, cobalt
And heat, under the conditions of 50-80 DEG C, react 3-5h, in course of reaction, control ph is at 5.0-5.5；Reaction knot
Shu Hou, solid-liquid separation, obtain liquid and heavy cobalt slag after heavy cobalt；
(3) after heavy cobalt, liquid carries out eddy flow electrodeposition extraction nickel, and heavy cobalt slag send cobalt recovery circuit to produce cobalt oxalate or oxygen
Change cobalt.
Described oxidizing agent composition includes oxidants hydrogen peroxide and oxidation synergist, wherein, oxidant mistake
The consumption of hydrogen oxide is needed for precipitate cobalt 4-7 times of theoretical amount, and oxidation synergist includes the group of following weight portion meter
Point: sym-closene 5.8-8.2 part, monoacetylaniline 1.0-2.3 part and polyacrylamide 0.15-0.25 part,
Consumption is addition oxidation synergist to final concentration 1-5g/L.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
In step (1), acid solution is sulfuric acid solution, hydrochloric acid solution or salpeter solution, and concentration is 5-20%.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
In step (1), the liquid-solid ratio of acid solution and nickel cobalt slag is 3-10:1.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
In step (1) and (2), churned mechanically speed is 60-120r/min.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
The air capacity blasted in step (1) is needed for precipitated iron, manganese 3-6 times of theoretical amount.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
The time leached in step (1) is 2-3h, and it is 2.0 that leaching process controls pH.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
In step (2), the reagent used by control ph is trona or sodium bicarbonate.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
Described solid-liquid separation is to use vacuum filtration machine, filter press or centrifuge to carry out solid-liquid separation.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 1, it is characterised in that
Described nickel cobalt slag processes through ore grinding, and mog accounts for more than 90% for-74 μm.
Separation and recovery nickel, the method for cobalt from nickel cobalt slag the most according to claim 9, its feature exists
In, described ore grinding processes and uses ball mill, rod mill or jet mill to carry out ore grinding.
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| CN107815540A (en) * | 2017-12-13 | 2018-03-20 | 栗秀臣 | A kind of method of hydrometallurgy metal nickel cobalt and its salt product |
| CN109216817A (en) * | 2017-06-30 | 2019-01-15 | 荆门市格林美新材料有限公司 | A kind of element recovery method of waste and old nickle cobalt lithium manganate cell positive material |
| CN110438344A (en) * | 2019-08-20 | 2019-11-12 | 中国恩菲工程技术有限公司 | The method of separation of Cu and Co recycling |
| CN111534699A (en) * | 2020-06-16 | 2020-08-14 | 江西一元再生资源有限公司 | Method for recovering valuable substances from cemented carbide scrap |
| CN113512649A (en) * | 2021-05-27 | 2021-10-19 | 金川集团股份有限公司 | Production method for realizing nickel-cobalt separation by utilizing ozone under mixed acid system |
| CN114291881A (en) * | 2021-12-24 | 2022-04-08 | 湖南有色郴州氟化学有限公司 | Ammonia nitrogen wastewater treatment agent and use method and application thereof |
| CN116751965A (en) * | 2023-07-21 | 2023-09-15 | 河北地质大学 | Method for removing iron and manganese ions from laterite nickel ore acid leaching solution using pyrite |
| EP4524268A4 (en) * | 2023-07-27 | 2025-10-08 | Pt Esg New Energy Mat | METHOD FOR EXTRACTING METALS FROM SAPROLITE-LATERITIC NICKEL ORE |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109216817A (en) * | 2017-06-30 | 2019-01-15 | 荆门市格林美新材料有限公司 | A kind of element recovery method of waste and old nickle cobalt lithium manganate cell positive material |
| CN107815540A (en) * | 2017-12-13 | 2018-03-20 | 栗秀臣 | A kind of method of hydrometallurgy metal nickel cobalt and its salt product |
| CN110438344A (en) * | 2019-08-20 | 2019-11-12 | 中国恩菲工程技术有限公司 | The method of separation of Cu and Co recycling |
| CN111534699A (en) * | 2020-06-16 | 2020-08-14 | 江西一元再生资源有限公司 | Method for recovering valuable substances from cemented carbide scrap |
| CN113512649A (en) * | 2021-05-27 | 2021-10-19 | 金川集团股份有限公司 | Production method for realizing nickel-cobalt separation by utilizing ozone under mixed acid system |
| CN114291881A (en) * | 2021-12-24 | 2022-04-08 | 湖南有色郴州氟化学有限公司 | Ammonia nitrogen wastewater treatment agent and use method and application thereof |
| CN114291881B (en) * | 2021-12-24 | 2023-03-03 | 湖南有色郴州氟化学有限公司 | Ammonia nitrogen wastewater treatment agent and use method and application thereof |
| CN116751965A (en) * | 2023-07-21 | 2023-09-15 | 河北地质大学 | Method for removing iron and manganese ions from laterite nickel ore acid leaching solution using pyrite |
| EP4524268A4 (en) * | 2023-07-27 | 2025-10-08 | Pt Esg New Energy Mat | METHOD FOR EXTRACTING METALS FROM SAPROLITE-LATERITIC NICKEL ORE |
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