CN116516172A - Recovery method of sodium cobalt Fumei slag - Google Patents
Recovery method of sodium cobalt Fumei slag Download PDFInfo
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- CN116516172A CN116516172A CN202310797686.0A CN202310797686A CN116516172A CN 116516172 A CN116516172 A CN 116516172A CN 202310797686 A CN202310797686 A CN 202310797686A CN 116516172 A CN116516172 A CN 116516172A
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- roasting
- slag
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- temperature
- sodium
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- 239000002893 slag Substances 0.000 title claims abstract description 232
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 88
- 238000011084 recovery Methods 0.000 title abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000005406 washing Methods 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 88
- 238000002386 leaching Methods 0.000 claims abstract description 82
- 230000008569 process Effects 0.000 claims abstract description 50
- 230000001180 sulfating effect Effects 0.000 claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 127
- 238000007654 immersion Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 60
- 239000010941 cobalt Substances 0.000 abstract description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 60
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 229910052725 zinc Inorganic materials 0.000 description 26
- 239000011701 zinc Substances 0.000 description 26
- 150000002739 metals Chemical class 0.000 description 25
- 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 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005670 sulfation reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000019635 sulfation Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000005870 Ziram Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical compound [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000005843 Thiram Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YUHVOWXJFDOPMW-UHFFFAOYSA-N [Co].[Na].[Na] Chemical compound [Co].[Na].[Na] YUHVOWXJFDOPMW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 cobalt and zinc Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a recovery method of sodium cobalt slag, and belongs to the technical field of cobalt slag recovery and utilization. The recovery method of the sodium cobalt blepharde slag comprises the following steps: oxidizing and roasting the sodium cobalt slag with air to obtain a first roasting material; the first roasting material is subjected to a first water leaching washing treatment; after washing, obtaining a second roasting material through sulfating roasting; and carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material. The recovery method of the sodium cobalt slag realizes the efficient recovery of the cobalt slag, can treat various organic cobalt slag materials with fluctuating components, has no new solid waste such as residues and the like, and can greatly reduce the emission of sulfur-containing gas; the method has the advantages that the effective extraction of Ni, fe, mn and Cd in the cobalt slag is realized, the treatment process condition is simple, the efficient recovery is realized, the environment-friendly requirements of energy conservation and emission reduction are met, the cost of cobalt slag treatment or recovery is greatly reduced, and convenience is brought to cobalt slag recovery.
Description
Technical Field
The invention belongs to the technical field of cobalt slag recycling, and particularly relates to a method for recycling sodium cobalt slag.
Background
Sodium Fumei is a metal precipitant/chelating agent, which can react with various heavy metal ions at normal temperature (such as chromium, nickel, copper, zinc, manganese, cadmium, vanadium and tin) to remove heavy metal ions.
The sodium Fumei has a plurality of advantages, the application range of the sodium Fumei to the types and the concentration ranges of heavy metal ions is wide, a plurality of heavy metal ions can be removed at the same time, and the cost is low; moreover, the sodium thiram has the physicochemical properties of good solubility, high flocculating body formation speed, high treatment capacity and small corrosion to equipment; in addition, the metal precipitate formed by the sodium Fumerate is stable, is not easy to exude in a dilute acid solution, and is safe to handle.
In the existing treatment and recovery technology for sodium cobalt slag, as disclosed in patent CN105950875A, a method for treating purified cobalt slag of zinc and manganese hydrometallurgy is disclosed, wherein water or a mixture of water and sulfuric acid or a mixture of water and leaching liquid is firstly added into the purified cobalt slag, and the liquid-solid mass ratio is regulated to be 2-8; then reacting for 1-8 hours under the atmosphere of oxygen pressure of 1-2 MPa and temperature of 110-180 ℃ to obtain leaching solution, but the method needs high-temperature pressure leaching and has high equipment investment and production cost; the treatment process disclosed in the patent CN110358917a comprises the following steps in sequence: acid pickling dezincification, roasting, water leaching, extraction purification, ammonium oxalate precipitation and cobalt oxalate calcination are carried out, sodium persulfate is required to be introduced in the process, the leaching slag rate is still higher, and the grade of residual cobalt in leaching slag is still higher; for another example, patent CN110205482a discloses a comprehensive recovery method of cobalt-removing purification slag of zinc smelting organic matters, which comprises the following steps: adding sodium carbonate into the cobalt-removing purification slag of sodium ziram, and calcining at 600-1000 ℃ to obtain a calcined product A; adding water into the A to form slurry, adding sodium persulfate, adding concentrated sulfuric acid to enable the pH value to be 1-4, reacting for 1-2 hours, and filtering to obtain zinc sulfate solution and leaching residue C; adding water into the leaching residue C, adding hydrochloric acid to enable the pH value to be 1-3, reacting for 1-3 hours, and filtering to obtain cobalt chloride solution D and leaching residue E; adding ammonium sulfide solution into the solution D, and reacting for 0.5 to 1 hour to remove heavy metal impurities, thereby obtaining purified cobalt chloride solution F; heating to 50-60 ℃, adding oxalic acid solution into F, reacting for 15-20 minutes, filtering, washing the obtained filter material with pure water, and drying to obtain the cobalt oxalate product G. The process of the patent requires high temperature and a large amount of acid, and has high cost.
In a word, in the existing cobalt slag treatment or recovery process, the problems of harsh treatment process conditions, higher grade of residual cobalt in leaching slag and the like exist, so that the cost of cobalt slag treatment or recovery is greatly increased, and great inconvenience is brought to cobalt slag recovery.
Disclosure of Invention
In order to solve the problems, the invention provides a recovery method of sodium cobalt Fumei slag, comprising the following steps:
s1, oxidizing and roasting sodium cobalt slag with air to obtain a first roasting material;
s2, carrying out primary water immersion washing treatment on the first roasting material;
s3, after washing, obtaining a second roasting material through sulfating roasting;
s4, carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material.
Preferably, in the step of obtaining the first roasting material by oxidizing and roasting the sodium cobalt slag with air, the roasting mode is temperature-raising roasting; and the roasting temperature is 350-800 ℃;
the sodium cobalt slag amount per unit area during roasting is 0.1 g/cm 2 -1.0 g/cm 2 ；
The granularity of the sodium cobalt slag is not more than 50mm during roasting;
the temperature rising rate during roasting is not more than 100 ℃/min;
when roasting, the opening and closing degree of the furnace door is from closed to fully opened.
Preferably, in the step of obtaining the first roasting material by oxidizing and roasting the sodium cobalt slag with air, the roasting mode is temperature-raising roasting;
the roasting temperature in the heating roasting is 500 ℃;
the roasting time during the heating roasting is 1 hour;
the heating rate during heating and roasting is 10 ℃/min;
when the temperature is raised and roasting is performed, the furnace door is fully opened in the roasting process.
Preferably, in the step of performing the first water immersion washing treatment on the first roasting material, the solid-to-liquid ratio in the condition of the water immersion washing treatment is in a range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L.
Preferably, in the step of performing the first water immersion washing treatment on the first roasting material, the condition of the water immersion washing treatment is that the solid-liquid ratio is 1:10; the sulfuric acid concentration was 1g/L.
Preferably, in the step of obtaining the second baked material through sulfating baking after washing, the sulfating baking mode is constant temperature baking or heating baking;
the roasting temperature of the sulfating roasting is 100-600 ℃;
the firing time of the sulfating firing is not more than 5 hours;
the sulfuric acid excess coefficient of the sulfating roasting is 0.5-1.4.
Preferably, in the step of obtaining the second baked material through sulfating baking after washing, the baking mode of the sulfating baking is temperature raising baking; and, in addition, the processing unit,
the roasting temperature of the sulfating roasting is 350 ℃;
the roasting time of the sulfating roasting is 1 hour;
the sulfuric acid excess coefficient of the sulfating roasting is 1.4.
Preferably, in the step of performing the second water immersion washing treatment on the second baked material to obtain the recovered material, the step of performing the first water immersion washing treatment on the first baked material with the water washing solution in the step of performing the first water immersion washing treatment with the S2 is performed.
Preferably, in the step of performing a second water leaching washing treatment on the second roasting material to obtain a recovered material, the solid-to-liquid ratio in the condition of the water leaching washing treatment is in the range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L.
Preferably, in the step of performing a second water leaching washing treatment on the second roasting material to obtain the recovered material, the solid-liquid ratio is 1:10, and the sulfuric acid concentration is 1g/L.
The invention provides a recovery method of sodium cobalt slag, which comprises the following steps: s1, oxidizing and roasting sodium cobalt slag with air to obtain a first roasting material; s2, carrying out primary water immersion washing treatment on the first roasting material; s3, after washing, obtaining a second roasting material through sulfating roasting; s4, carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material. The recovery method of the sodium cobalt slag realizes the efficient recovery of the cobalt slag, can treat various organic cobalt slag materials with fluctuating components, has no new solid waste such as residues and the like, and can greatly reduce the emission of sulfur-containing gas; the recovery rate of Co and Zn respectively reaches 98.3 percent and 97.25 percent, the Ni, fe, mn, cd in the cobalt slag is effectively extracted, the treatment process condition is simple, the efficient recovery is realized, the environment-friendly requirement of energy conservation and emission reduction is met, the cost of cobalt slag treatment or recovery is greatly reduced, and convenience is brought to the recovery of the cobalt slag.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering sodium cobalt Fumei slag of the invention;
FIG. 2 is an EDS image of sodium cobalt blepharamate used in the example of the recovery method of sodium cobalt blepharamate of the present invention;
FIG. 3 is a graph showing the effect of the roasting temperature of the cobalt sodium ziram slag on the slag rate in example 3 of the recovery method of the cobalt sodium ziram slag of the present invention;
FIG. 4 is a thermogravimetric-differential heat curve of the cobalt sodium ziram slag of comparative example 2 of the recovery method of the cobalt sodium ziram slag of the present invention;
FIG. 5 is an XRD spectrum of acid-washed slag of oxidized roasting slag of sodium cobalt slag in comparative example 3 of the recovering method of sodium cobalt slag of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise hereinafter, all technical and scientific terms used in the detailed description of the invention are intended to be identical to what is commonly understood by one of ordinary skill in the art. While the following terms are believed to be well understood by those skilled in the art, the following definitions are set forth to better explain the present invention.
As used herein, the terms "comprising," "including," "having," "containing," or "involving" are inclusive or open-ended and do not exclude additional unrecited elements or method steps. The term "consisting of …" is considered to be a preferred embodiment of the term "comprising". If a certain group is defined below to contain at least a certain number of embodiments, this should also be understood to disclose a group that preferably consists of only these embodiments.
The indefinite or definite article "a" or "an" when used in reference to a singular noun includes a plural of that noun.
The term "about" in the present invention means a range of accuracy that one skilled in the art can understand while still guaranteeing the technical effect of the features in question. The term generally means a deviation of + -10%, preferably + -5%, from the indicated value.
Furthermore, the terms first, second, third, (a), (b), (c), and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
Unless defined otherwise or clearly indicated by context, all technical and scientific terms in this disclosure have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
The technical solution of the present invention is further described in detail below with reference to specific embodiments, but the present invention is not limited thereto, and any modifications made by anyone within the scope of the claims of the present invention are still within the scope of the claims of the present invention.
Referring to fig. 1, the invention provides a method for recovering sodium cobalt slag, comprising the following steps:
step S1 (one-stage roasting), roasting sodium cobalt slag of the sodium thiram by air oxidation to obtain a first roasting material;
step S2 (one-stage water immersion washing treatment), the first roasting material is subjected to a first water immersion washing treatment;
step S3 (two-stage roasting), washing, and then, obtaining a second roasting material through sulfating roasting;
and S4 (two-stage water leaching washing treatment), carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material.
In step S1, the sodium cobalt slag is air-oxidized and roasted. In the zinc hydrometallurgy production process, elements such as copper, cadmium, cobalt, nickel, arsenic, antimony, germanium and the like have influence on product quality, so sodium ziram is often adopted to remove cobalt in the purification process, and the produced sodium ziram cobalt removal slag contains valuable metals such as cobalt, zinc and the like. In order to recover these valuable metals, first, sodium cobalt Fumerate slag is subjected to air oxidation roasting treatment.
The method mainly comprises the step of reacting oxidizing gas (such as air) with sodium cobalt Fumei slag to generate oxidation reaction to obtain oxide. During the process, organic matters and some volatile matters in the sodium cobalt Fumei slag are quenched or volatilized along with the introduction of oxidizing gas.
The air oxidation roasting of the sodium cobalt slag can effectively remove organic matters and volatile matters in the sodium cobalt slag, and the sodium cobalt slag is laid for the subsequent process. Through oxidation reaction, valuable metals in the sodium cobalt Fumei slag can be converted into an oxide form, and better recovery conditions are provided for the subsequent process.
After step S1, step S2 is performed, i.e., the first water immersion washes the first baked goods (baked slag). After the air oxidation roasting of the sodium cobalt slag is completed in the first step, a first roasting material is obtained, and the roasting slag is required to be subjected to water leaching washing. The step mainly comprises the steps of removing mechanical impurities and soluble metal ions such as copper, zinc and the like which are subjected to air oxidation roasting.
Specifically, this step requires immersing the first calcined material in water, which may be sulfuric acid-containing water, and by mechanical stirring and flushing with water flow, impurities and soluble metals remaining in the calcined slag are effectively removed, and sulfate ions remaining in the slag are sufficiently dissolved.
Mechanical impurities and soluble metals in the slag can be effectively removed by washing the roasting slag with water. The sulfate ions remained in the slag can be fully dissolved while washing by water immersion, so that a mat is made for the subsequent process.
After step S2, step S3 is performed, i.e., the two-stage low-temperature sulfation roasting leaching residue performed after washing, thereby obtaining a second roasting material. After the water immersion washing roasting slag treatment is completed, a two-stage low-temperature sulfating roasting leaching slag process is needed. The principle of the step is to dissolve valuable metals (such as cobalt, zinc and the like) in the sodium cobalt Fumei slag into the immersion liquid by utilizing chelation and oxidation-reduction reaction of sulfuric acid. At the same time, the excess sulfuric acid can promote the reaction rate and avoid the formation of sulfate precipitates that are difficult to decompose.
Specifically, the step needs to perform secondary roasting on the roasting slag after water leaching and washing, and a proper amount of sulfuric acid is added in the roasting process to react, so that valuable metals such as cobalt, zinc and the like in the roasting slag are converted into a sulfate form, and thus effective dissolution and leaching are realized.
The technology of two-stage low-temperature sulfatizing roasting leaching slag can realize the efficient recovery of valuable metals such as cobalt, zinc and the like in the roasting slag. And when a proper amount of sulfuric acid is added for reaction, some impurities which are difficult to dissolve and leach in the roasting slag can be further removed.
In a word, the step S3 can effectively extract valuable metals in the sodium cobalt Fumei slag, and meanwhile, sulfate precipitation which is difficult to decompose is not generated, so that the recovery rate is improved, and meanwhile, the environmental pollution is reduced.
In step S4, after washing, the second baked material is subjected to a second water leaching washing treatment to obtain a recovered material. After the two-stage low-temperature sulfation roasting leaching slag treatment is completed, a two-stage water leaching roasting slag technology (second leaching washing) is needed. The step mainly uses water to collect and recycle the valuable metals such as cobalt, zinc and the like which are dissolved and leached.
Specifically, this step requires leaching the slag leached by two-stage low-temperature sulfatizing roasting, so that valuable metals such as cobalt and zinc remained therein are sufficiently collected and recovered.
Through the two-stage water leaching roasting slag process, the high-efficiency recovery of the dissolved and leached valuable metals such as cobalt, zinc and the like can be realized. Through the water immersion mode, sulfate ions which are remained in the slag finally can be fully washed and removed, so that the pollution to the environment is avoided.
First, the main purpose of this process is to recover valuable metals, such as cobalt and zinc, from the sodium cobalt Fumerate slag. These valuable metals are very important substances for related industries, and can be widely applied to the fields of batteries, alloys, coatings and the like. Therefore, recycling valuable metals can not only realize the reutilization of resources, but also bring economic benefits to enterprises.
Secondly, by adopting the process flow, the efficient recovery of valuable metals in the sodium cobalt Fumei slag can be effectively realized. Specifically, the process flow mainly comprises four steps: air oxidation roasting sodium cobalt slag, water leaching washing roasting slag, two-stage low-temperature sulfating roasting leaching slag and two-stage water leaching roasting slag. Each step plays a key role, so that the whole process flow can effectively realize the efficient recovery of valuable metals.
Specifically, in the whole process flow, the first step of air oxidation roasting of the sodium cobalt slag is to effectively remove organic matters and volatile matters in the sodium cobalt slag and convert sulfides into oxides, so that better recovery conditions are provided for the subsequent process; and in the second step, washing the roasting slag by water immersion. The mechanical impurities and soluble metals in the slag are effectively removed, and sulfate ions remained in the slag are fully dissolved; in the third step, the second-stage low-temperature sulfating roasting leaching slag is mainly prepared by attacking and dissolving roasting slag by sulfuric acid, so as to obtain soluble valuable metals such as cobalt, zinc and the like; and in the fourth step, the second-stage water leaching roasting slag is obtained by collecting and recycling valuable metals such as cobalt, zinc and the like which are dissolved and leached by utilizing water.
The whole process flow realizes the efficient recovery of valuable metals in the sodium cobalt slag of the sodium Fumei through various process means, and simultaneously can avoid polluting the environment. The specific advantages include:
(1) The valuable metals are efficiently recycled, so that the recycling of resources is realized, and economic benefits are brought to enterprises.
(2) The sodium cobalt slag is used as a precipitator and a chelating agent, so that the effective removal of heavy metals can be realized, and the effect of environmental protection is achieved.
(3) By adopting a plurality of process means to be combined, each step plays a key role, so that the whole process flow can be a unified target of high efficiency, economy and environmental protection.
In general, the technological process utilizes sodium fermi to carry out metal precipitation and chelation, combines various technological means such as air oxidation, water immersion washing, two-stage low-temperature sulfation roasting and the like, effectively realizes the efficient recovery of valuable metals in sodium fermi cobalt slag, and can also avoid polluting the environment. Moreover, the steps are tightly connected, and each step plays a key role, so that the whole process flow achieves the unified targets of high efficiency, economy and environmental protection.
In a word, the recovery method of the sodium cobalt slag of the invention realizes the efficient recovery of the cobalt slag, and the process can treat various organic cobalt slag materials with fluctuating components, has no new solid waste such as residues and the like, and can greatly reduce the emission of sulfur-containing gas; the recovery rate of Co and Zn respectively reaches 98.3 percent and 97.25 percent, the Ni, fe, mn, cd in the cobalt slag is effectively extracted, the treatment process condition is simple, the efficient recovery is realized, the environment-friendly requirement of energy conservation and emission reduction is met, the cost of cobalt slag treatment or recovery is greatly reduced, and convenience is brought to the recovery of the cobalt slag.
Further, in the step of obtaining the first roasting material by oxidizing and roasting the sodium cobalt slag with air, the roasting mode is temperature-raising roasting.
In the baking process, the heating can be performed by adopting a resistance furnace, a gas furnace or a reducing atmosphere furnace and other devices. Among them, the resistance furnace and the gas furnace are one of the most common firing apparatuses. The resistance furnace generates heat in the resistance wire through current, so that materials are heated; the gas furnace generates heat by burning gas or using electric arc, etc. to heat the material. The reducing atmosphere furnace realizes the purpose of reducing (or oxidizing) materials by controlling atmosphere in the heating equipment.
Further, the roasting temperature is 350-800 ℃; for example, it may be 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 500 ℃,600 ℃, 700 ℃, 800 ℃.
Further, the cobalt sodium fermi amount per unit area is 0.1 g/cm during roasting 2 -1.0 g/cm 2 . For example, it may be 0.1 g/cm 2 、0.2 g/cm 2 、0.3 g/cm 2 、0.4 g/cm 2 、0.5 g/cm 2 、0.6 g/cm 2 、0.7 g/cm 2 、0.8 g/cm 2 、0.9 g/cm 2 、1.0 g/cm 2 。
The amount of sodium cobalt sodium Fumei slag per unit area is used to control the size and depth of the roasting reaction zone during roasting. By controlling the addition and distribution of the sodium cobalt Fumei slag, the roasting reaction area can be reasonably controlled, thereby obtaining the required roasting effect.
Specifically, the amount of sodium cobalt slag per unit area refers to the mass range of sodium cobalt sodium slag added per square centimeter of surface area over the calcination reaction zone. In the present invention, the value is controlled to be between 0.1 and g/cm 2 -1.0 g/cm 2 Between them.
The amount of sodium cobalt slag per unit area is of great significance to the roasting process. When the amount of the sodium cobalt slag is too low, the roasting reaction area may be limited, so that the roasting effect is poor; when the amount of the sodium cobalt Fumei slag is too high, the roasting reaction area is excessively large, so that energy sources are wasted and the roasting efficiency is reduced. Therefore, when roasting, the addition amount and distribution of the sodium cobalt slag of the sodium thiram are required to be adjusted according to specific conditions, so as to reach the range, and the best roasting effect is obtained.
Further, the granularity of the sodium cobalt slag is not more than 50mm during roasting; for example, 1 mm, 3 mm, 5 mm, 7 mm, 8 mm, 10 mm, 20 mm, 40 mm, 50 mm.
Further, the temperature rising rate during roasting is not more than 100 ℃/min; for example, it may be 10℃per minute, 20℃per minute, 30℃per minute, 40℃per minute, 50℃per minute, 60℃per minute, 70℃per minute, 80℃per minute, 90℃per minute, 100℃per minute.
Further, during roasting, the opening and closing degree of the furnace door is from closed to fully opened.
In the roasting process, the opening and closing degree of the furnace door directly influences gas exchange and temperature distribution. If the oven door is completely closed, the gas exchange is slowed down, resulting in a decrease in oxygen concentration, thereby affecting the combustion effect; meanwhile, high pressure is easy to generate in the airtight space, so that dead angle areas are formed in the roasting furnace, and even heating of materials is further affected.
Conversely, if the furnace door is completely opened, the gas exchange speed is greatly increased, the roasting speed is increased, and the roasting result is affected; but at the same time, too large an opening of the oven door also causes heat loss, further affecting the energy consumption.
Therefore, in the roasting process, the opening and closing degree of the furnace door needs to be properly controlled according to factors such as process requirements, material characteristics and the like so as to achieve the optimal heat transfer efficiency and roasting effect.
In a preferred embodiment, the step S1, in which the sodium cobalt blephare slag is oxidized and roasted by air to obtain the first roasted material, the roasting mode is temperature raising roasting; and, still contain the following characteristics:
the roasting temperature in the heating roasting is 500 ℃;
the roasting time during the heating roasting is 1 hour;
the heating rate during heating and roasting is 10 ℃/min;
when the temperature is raised and roasting is performed, the furnace door is fully opened in the roasting process.
Further, in the step of performing the first water immersion washing treatment on the first roasting material, the solid-liquid ratio in the condition of the water immersion washing treatment is in the range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L. For example, the solid to liquid ratio may be 3:1, 2:1, 1:1, 1:10, 1:20, 1:50, 1:100, 1:200, 1:300; the sulfuric acid concentration may be 1g/L, 3 g/L, 5 g/L, 7 g/L, 9 g/L, 10 g/L, 20 g/L, 30 g/L, 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L. As another example, the sulfuric acid concentration may be 1g/L, 5 g/L, 10 g/L, 20 g/L, 30 g/L, 40 g/L, 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L.
In a preferred embodiment, in the step of S2, the first baked material is subjected to a first water immersion washing treatment, where the condition of the water immersion washing treatment is a solid-to-liquid ratio of 1:10; the sulfuric acid concentration was 1g/L.
Further, in the step of obtaining the second roasting material through sulfating roasting after washing, the roasting mode of sulfating roasting is constant temperature roasting or temperature-rising roasting;
further, the roasting temperature of the sulfating roasting is 100-600 ℃; for example, it may be 100℃at 200℃at 300℃at 400℃at 500℃at 600 ℃.
Further, the firing time of the sulfatizing firing is not more than 5 hours; for example, the time period may be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.
Further, the sulfuric acid excess coefficient of the sulfating roasting is 0.5-1.4. For example, it may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4.
The sulfuric acid excess coefficient refers to the ratio of sulfuric acid actually added to the theoretically required amount of sulfuric acid in the sulfation roasting reaction. The larger the sulfuric acid excess coefficient is, the more the added sulfuric acid exceeds the theoretically required sulfuric acid amount, and on the contrary, the insufficient sulfuric acid is.
In a preferred embodiment, in the step of obtaining the second baked material by sulfating baking after the washing, the baking mode of the sulfating baking is temperature raising baking;
in a preferred embodiment, the firing temperature of the sulfation firing is 350 ℃;
in a preferred embodiment, the firing time of the sulfatizing firing is 1 hour;
in a preferred embodiment, the sulfated firing has a sulfuric acid excess factor of 1.4.
In a preferred embodiment, the step of performing the second water immersion washing treatment on the second baked material to obtain the recovered material, the step of performing the first water immersion washing treatment on the first baked material with the water washing solution in the step of performing the second water immersion washing treatment with the S2.
Above-mentioned, the second time water logging washing in S4 can adopt the water-logging washing liquid in the first time water logging washing in S2 directly to carry out reuse, has reduced the emission of waste water, and is more environmental protection to processing cost has been reduced.
Further, in the step of performing a second water leaching washing treatment on the second roasting material to obtain a recovered material, the solid-to-liquid ratio in the condition of the water leaching washing treatment is in the range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L. For example, the solid to liquid ratio may be 3:1, 2:1, 1:1, 1:10, 1:20, 1:50, 1:100, 1:200, 1:300; the sulfuric acid concentration may be 1g/L, 3 g/L, 5 g/L, 7 g/L, 9 g/L, 10 g/L, 20 g/L, 30 g/L, 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L. As another example, the sulfuric acid concentration may be 1g/L, 5 g/L, 10 g/L, 20 g/L, 30 g/L, 40 g/L, 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L.
In a preferred embodiment, in the step of performing a second water immersion washing treatment on the second baked material to obtain a recovered material, the water immersion washing treatment is performed under the conditions that the solid-to-liquid ratio is 1:10 and the sulfuric acid concentration is 1g/L.
The invention is further illustrated by the following specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way.
The chemical composition analysis of the raw materials (sodium cobalt Fumei slag) used in the examples is shown in the following table:
table 1, table (unit%) of analysis results of main elements in sodium cobalt Fumei slag
Referring to fig. 2, an EDS diagram of sodium cobalt, sodium, and cobalt, slag was used in the examples.
Example 1
In this example, for sodium cobalt Fumei slag, one stage of air oxidation roasting and the first water leaching washing are performed, and specific process and experimental data are as follows:
(1) S1, oxidizing and roasting sodium cobalt Fumei slag by air to obtain a first roasting material:
carrying out air oxidation heating roasting on the sodium cobalt slag in the table 1, heating to 500 ℃ at a heating speed of 10 ℃/min, then roasting for 1 hour, and keeping a furnace door half open in the heating process and circulating air atmosphere;
(2) S2, carrying out primary water immersion washing treatment on the first roasting material:
washing the roasting slag with 1g/L sulfuric acid, wherein the solid-liquid ratio is 1:10.
According to the method, three 100g samples are respectively taken and put into a porcelain plate, one-stage air oxidation roasting is carried out according to the conditions, and the three samples are respectively: s500-1, S500-2 and S500-3.
TABLE 2 slag Rate of one-stage temperature-increasing roasting product
The above table shows the slag rate of the temperature-rising roasting products of three groups of comparison samples. According to the data in the table above, the hot slag rate of three parallel roasting slightly fluctuates, and is 34.23% on average, but the weight gain rate after cooling is different to some extent, which indicates that the non-uniformity of the cobalt slag sample may cause slight difference in sulfate content in the product.
TABLE 3 acid wash slag Rate of one-stage temperature-rising roasting product
The above table shows that the slag washing rate is about 23.55% after three groups of roasting products are washed by 1g/L sulfuric acid under the condition of a solid-to-liquid ratio of 1:10.
Further, in this example, two-stage low-temperature sulfation roasting and a second water leaching washing were performed, and specific process and experimental data are as follows:
(3) S3, after washing, obtaining a second roasting material through sulfating roasting:
and (2) adding 40.31 g concentrated sulfuric acid into a 29.58 g-stage leaching residue prepared in the step (S2) and roasting for 1 hour, wherein the sulfuric acid excess coefficient is 1.4, and the roasting temperature is 350 ℃.
(4) S4, carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material:
the sulfuric acid roasting slag is washed by adopting 1.0 g/L sulfuric acid under the condition of solid-liquid ratio of 1:10. After roasting with sulfuric acid at 350 ℃ for 1 hour, the roasted product was relatively loose and appeared to be uniformly pink, indicating the formation of cobalt sulfate.
TABLE 4 slag Rate after sulfation roasting
The above table shows the slag rate of the sulfation roasting process. The result shows that the slag rate in the sulfuric acid roasting process is slightly 76.35% of the total mass of the washing slag and the sulfuric acid; in addition, the sulfuric acid roasting slag is basically free of residues after being washed by 1.0 g/L sulfuric acid, which indicates that the washing slag fully reacts with the sulfuric acid, thereby realizing the efficient recovery of cobalt and zinc.
TABLE 5 Total Metal recovery Table after twice washing in full Process
The above table shows the total recovery rate calculated from the solution composition obtained by the two water washing tests and the content of the raw materials. The result shows that the recovery rates of Co and Zn are respectively 98.30% and 97.25%, wherein Ni, fe, mn, cd in cobalt slag is effectively extracted, and no new solid wastes such as residues are generated in the process.
Example 2
In this example, the change of the roasting temperature to the roasting slag rate in the temperature-raising roasting process is examined, and the following experimental test is specifically carried out:
experimental conditions:
amount of sodium cobalt Fumei slag: 100 g;
area of the porcelain plate: 468 cm 2 ；
Sodium cobalt slag amount per unit area: 0.2 g/cm 2 ；
Roasting time: 1 hour;
roasting atmosphere: an air atmosphere;
experimental group and corresponding firing temperature: as shown in the table below.
Table 6, table 2, experimental group control Table corresponding to 5 roasting temperatures
The roasting mode is as follows: and (3) adopting a heating roasting mode, firstly placing a porcelain plate which is pre-filled with sodium cobalt Fumerate into a muffle furnace under the conditions of air atmosphere and ventilation of a fume hood, then gradually heating the muffle furnace to a corresponding roasting temperature under the condition of a speed of 10 ℃/min, roasting for 1 hour at the constant temperature, and directly taking out and cooling at the high temperature.
TABLE 7 slag Rate Table for temperature-increasing roasting
Experimental results: in this example, the influence of different roasting temperatures on the roasting slag rate was examined by 5 experimental groups with sample numbers S350, S400, S450, S500 and S550, respectively, under the premise of the other conditions being identical. Referring to experimental data in the table, the slag rate condition of the temperature rising roasting test is shown. Wherein, the hot slag weight is that the hot slag is weighed after roasting, and the cold slag weight is that the cold slag is weighed after being left for 12 hours in an open state.
From the experimental data it can be concluded that: in 5 experimental groups with the same experimental conditions but different roasting temperatures, the hot slag rate can be kept at about 33%, the influence of the roasting temperature is small, and the whole roasting process does not generate fire combustion. The slag cooling rate of 5 experimental groups can be basically kept at about 43%, and the change of the slag cooling rate is not obvious. In contrast, cold slag is much heavier in weight average than hot slag, mainly due to the fact that the phases contained in the roasting slag readily absorb moisture in the air.
Example 3
In this example, the effect of sulfatizing roasting of the leaching residue at different temperatures was examined. The experimental conditions were as follows:
raw materials: roasting slag obtained by acid leaching at 500 ℃;
slag leaching amount: 2g;
amount of sulfuric acid: 2.94 g; (the excess coefficient thereof is calculated as the metal element is about 1.4)
Roasting time: 1 hour;
roasting temperature: 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃;
TABLE 8 slag Rate Table after sulfation roasting at different temperatures
The above table shows the slag rate after sulfation roasting at different temperatures. Experimental results show that the slag rate obtained at the roasting temperature of 250 ℃ is about 90.34%, and the water-washed slag is possibly insufficient in conversion and residual sulfuric acid; when the roasting temperature is increased to 300 ℃, the slag rate is reduced to about 76%; and the slag rate can be reduced to about 74.5% after the roasting temperature is higher than 400 ℃, because the boiling point temperature of sulfuric acid is about 340 ℃, and the residual sulfuric acid volatilizes when the temperature is increased. The cobalt oxide phase in the water leaching slag of the sulfuric acid roasting slag is converted into sulfate at 400 ℃.
TABLE 9 Water logging data sheet after sulfation roasting at different temperatures
The above table shows the water leaching data after sulfation roasting at different temperatures, to avoid precipitate formation, 1g/L sulfuric acid solution leaching (ph=1.75) was used. The data show that the leaching rates of Co and Zn are obviously increased along with the temperature rise, and the leaching rates can reach more than 98% after the temperature is higher than 350 ℃, which shows that the leaching slag can be effectively converted into water-soluble sulfate by low-temperature sulfuric acid roasting, thereby realizing the total recovery of valuable metals in the cobalt slag.
By controlling the roasting conditions, the comprehensive slag rate in the air roasting and water leaching process can be controlled to be 5-15%, so that direct water leaching recovery of Co with the concentration of more than 58% and Zn with the concentration of more than 70% is realized; and then the second stage of low-temperature sulfating roasting can realize the complete recovery of valuable metals in the cobalt slag of the sodium Fumi.
As can be seen from the pH change of the pickling solution, sulfuric acid may remain after calcination at 250 ℃, resulting in a decrease in pH from 1.75 to 1.4; as the temperature increases, the pH of the leachate gradually increases to around 2.0, presumably due to the formation of white particulate zinc oxide during calcination, which dissolves the spent acid, ultimately leading to an increase in pH.
Comparative example 1
The comparative example adopts two roasting modes of constant temperature roasting and temperature rising roasting to examine the sodium cobalt slag of the air oxidation roasting.
Uniformly spreading 100g cobalt slag on a porcelain plate (468 cm) 2 ) Upper partAbout 0.2. 0.2 g cobalt slag per square centimeter was laid. Wherein, the roasting time is 1 hour. The firing temperatures were 350 ℃, 400 ℃, 500 ℃,600 ℃, 700 ℃ and 800 ℃, respectively.
Referring to fig. 3, the effect of the firing temperature on the slag rate is shown. As can be seen from fig. 3, the slag rate change rule in the temperature-rising roasting and the constant-temperature roasting tests is different. In the temperature-rising roasting test, the slag rate gradually increases from 25.83% to 29.96% as the temperature increases from 350 ℃ to 600 ℃, which is consistent with the phenomenon observed by thermogravimetric analysis results, indicating that part of Co or S reacts with oxygen as the temperature increases. When the temperature is continuously increased to 800 ℃, the slag rate is obviously reduced, which is probably that sulfate in the roasting slag is decomposed. In the constant temperature roasting test, the slag rate always tends to decrease as the temperature increases from 350 ℃ to 800 ℃.
Compared with the method, the slag rate of constant temperature roasting at 350 ℃ is slightly higher than that of temperature rising roasting, when the temperature is raised to above 400 ℃ and the constant temperature roasting is carried out, the organic slag in the sodium cobalt Fumei slag is easy to burn, the fire in the furnace is rapid, the temperature is rapidly raised, the combustion can be completed within 3-5 minutes, the slag rate of constant temperature roasting is obviously lower than that of temperature rising roasting, and the final slag rate is only about 20%.
In conclusion, the result shows that the roasting and decomposing behavior of the sodium cobalt slag is greatly influenced by the roasting temperature and the roasting mode, when the heating roasting mode is adopted, a large amount of smoke is emitted in a low-temperature section (320-350 ℃), open fire does not appear, and the cobalt slag is decomposed in advance in the stage; the fire phenomenon does not occur even if the temperature is continuously increased. Therefore, the temperature-rising oxidizing roasting method used in the present invention is preferable.
Comparative example 2
In this comparative example, the thermal decomposition state of sodium cobalt Fumi salt slag at the time of oxidizing roasting at different temperatures was compared.
As shown in fig. 4, since the cobalt-sodium zizanate slag was dried and dehydrated before the test, there was no significant weight loss peak before 200 ℃, indicating that the cobalt-sodium zizanate slag was not decomposed;
as the temperature is further increased, the cobalt slag starts to decompose and lose weight, particularly, the rapid weight loss occurs at 300-350 ℃, which shows that the organic matters in the cobalt slag can be effectively decomposed in the temperature range, and the weight loss rate is 57.38% at 346 ℃.
However, when the temperature exceeds 346 ℃, the weight of the roasting slag is slightly increased, and when the temperature is raised to 700 ℃, the weight of the slag is increased from 42.62% to 49.55%, which shows that after organic matters in the cobalt Fumi-ner slag are roasted and decomposed in an air atmosphere, co or S components in the cobalt Fumi-ner slag further react with oxygen to form cobalt oxide or sulfate, and the quality of the slag is increased.
From the differential thermal curve, a sharp exothermic peak appears at 346 ℃, which indicates that organic matters in the cobalt-sodium blepharde slag can be rapidly decomposed at the temperature, and a large amount of heat is released.
A slight exothermic peak appears at about 450 ℃, which is probably that the decomposition products of the cobalt slag of the sodium and the sodium are further reacted with oxygen; meanwhile, the exothermic peak at 600-800 ℃ corresponds to the conversion process of cobalt oxide.
In conclusion, when the temperature is lower than 300 ℃, the cobalt slag is not decomposed and the roasting is ineffective; and when the roasting temperature is controlled within the range of 300-800 ℃, the cobalt slag can be decomposed efficiently.
Comparative example 3
In this comparative example 3, a comparative investigation of oxidation baking-water leaching washing and oxidation baking-one-stage water leaching washing-sulfation baking-two-stage water leaching washing was performed.
The specific process and experimental data of the oxidizing roasting-one-stage water leaching washing-sulfating roasting-two-stage water leaching washing are as follows:
(1) S1, oxidizing and roasting sodium cobalt Fumei slag by air to obtain a first roasting material:
carrying out air oxidation heating roasting on the sodium cobalt slag in the table 1, heating to 500 ℃ at a heating speed of 10 ℃ per minute, then roasting for 1 hour, and keeping a furnace door half open in the heating process and circulating air atmosphere;
(2) S2, carrying out primary water immersion washing treatment on the first roasting material:
washing the roasting slag with 1g/L sulfuric acid, wherein the solid-liquid ratio is 1:10.
(3) S3, after washing, obtaining a second roasting material through sulfating roasting:
a29.58-g-stage leaching residue prepared in example 1 is added with 40.31-g concentrated sulfuric acid and then roasted for 1 hour, wherein the sulfuric acid excess coefficient is 1.4, and the roasting temperature is 350 ℃.
(4) S4, carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material: the sulfuric acid roasting slag is washed by adopting 1.0 g/L sulfuric acid under the condition of solid-liquid ratio of 1:10. After roasting with sulfuric acid at 350 ℃ for 1 hour, the roasted product was relatively loose and appeared to be uniformly pink, indicating the formation of cobalt sulfate.
After the oxidation roasting-water leaching washing, the comprehensive slag rate (converted into the cobalt-fermat slag) is about 5-15%. Referring to FIG. 5, XRD spectrum of acid-washed slag obtained by acid leaching of roasting slag, data further prove that insoluble substance is Co 3 O 4 And ZnO. Due to higher slag rate and higher cobalt-zinc slag loss, the leaching slag needs to be further roasted and leached.
The whole recovery of Co and Zn can be realized by adopting the processes of oxidizing roasting, primary water leaching washing, sulfating roasting and secondary water leaching washing. When the sulfating roasting temperature is higher than 350 ℃, the roasting temperature has little influence on sulfate conversion of the water leaching slag, and the water leaching recovery rate of Co and Zn can reach more than 98 percent; when the sulfuric acid excess coefficient is larger than 1.2, the sulfuric acid excess coefficient has little influence on sulfate conversion of the water leaching slag, and the water leaching recovery rate of Co and Zn can reach more than 98 percent. The reaction time has little influence on the sulfate conversion of the water washing slag, and the sulfate conversion process has quicker reaction.
As can be seen from this comparative example, it is necessary to perform the recovery of cobalt-forti slag by the oxidative calcination-primary water leaching washing-sulfatizing calcination-secondary water leaching washing process. The efficient recovery of cobalt and zinc cannot be realized only by adopting an oxidizing roasting-water leaching washing process.
In a word, the recovery method of the sodium cobalt slag of the invention realizes the efficient recovery of the cobalt slag, and the process can treat various organic cobalt slag materials with fluctuating components, has no new solid waste such as residues and the like, and can greatly reduce the emission of sulfur-containing gas; the recovery rate of Co and Zn respectively reaches 98.3 percent and 97.25 percent, the Ni, fe, mn, cd in the cobalt slag is effectively extracted, the treatment process condition is simple, the efficient recovery is realized, the environment-friendly requirement of energy conservation and emission reduction is met, the cost of cobalt slag treatment or recovery is greatly reduced, and convenience is brought to the recovery of the cobalt slag.
While the preferred embodiments and examples of the present invention have been described, it should be noted that those skilled in the art may make various modifications and improvements without departing from the inventive concept, including but not limited to, adjustments of proportions, procedures, and amounts, which fall within the scope of the present invention. While the preferred embodiments and examples of the present invention have been described, it should be noted that those skilled in the art may make various modifications and improvements without departing from the inventive concept, including but not limited to, adjustments of proportions, procedures, and amounts, which fall within the scope of the present invention.
Claims (10)
1. The method for recycling the sodium cobalt Fumei slag is characterized by comprising the following steps of:
s1, oxidizing and roasting sodium cobalt slag with air to obtain a first roasting material;
s2, carrying out primary water immersion washing treatment on the first roasting material;
s3, after washing, obtaining a second roasting material through sulfating roasting;
s4, carrying out water leaching washing treatment on the second roasting material for the second time to obtain a recovered material.
2. The method for recycling sodium cobalt blepharde slag of claim 1, wherein, in the step of roasting sodium cobalt blepharde slag by air oxidation to obtain the first roasting material, the roasting mode is temperature rising roasting; and, in addition, the processing unit,
the roasting temperature is 350-800 ℃;
the sodium cobalt slag amount per unit area during roasting is 0.1 g/cm 2 -1.0 g/cm 2 ；
The granularity of the sodium cobalt slag is not more than 50mm during roasting;
the temperature rising rate during roasting is not more than 100 ℃/min;
when roasting, the opening and closing degree of the furnace door is from closed to fully opened.
3. The method for recycling sodium cobalt blepharde slag of claim 1, wherein, in the step of roasting sodium cobalt blepharde slag by air oxidation to obtain the first roasting material, the roasting mode is temperature rising roasting; and, in addition, the processing unit,
the roasting temperature in the heating roasting is 500 ℃;
the roasting time during the heating roasting is 1 hour;
the heating rate during heating and roasting is 10 ℃/min;
when the temperature is raised and roasting is performed, the furnace door is fully opened in the roasting process.
4. The method for recycling sodium cobalt Fumei slag according to claim 1, wherein in the step of S2, the first roasting material is subjected to a first water leaching washing treatment, and the solid-liquid ratio in the water leaching washing treatment condition is in the range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L.
5. The method for recycling sodium cobalt Fumei slag according to claim 1, wherein in the step of S2, the first roasting material is subjected to a first water leaching washing treatment, and the condition of the water leaching washing treatment is that the solid-liquid ratio is 1:10; the sulfuric acid concentration was 1g/L.
6. The method for recycling sodium cobalt Fumei slag according to claim 1, wherein in the step of obtaining the second roasting material through sulfating roasting after the step of S3, the roasting mode of sulfating roasting is constant temperature roasting or temperature rising roasting;
the roasting temperature of the sulfating roasting is 100-600 ℃;
the firing time of the sulfating firing is not more than 5 hours;
the sulfuric acid excess coefficient of the sulfating roasting is 0.5-1.4.
7. The method for recycling sodium cobalt Fumei slag according to claim 1, wherein in the step of obtaining the second roasting material through sulfating roasting after the step of S3 is washed, the roasting mode of the sulfating roasting is temperature rising roasting;
the roasting temperature of the sulfating roasting is 350 ℃;
the roasting time of the sulfating roasting is 1 hour;
the sulfuric acid excess coefficient of the sulfating roasting is 1.4.
8. The method according to claim 1, wherein the step of S4, in which the second roasting material is subjected to a second water leaching washing treatment, is performed by using the water washing solution in the step of S2, in which the first roasting material is subjected to a first water leaching washing treatment.
9. The method for recycling sodium cobalt Fumei slag according to claim 1, wherein S4, in the step of carrying out water leaching washing treatment on the second roasting material for the second time to obtain recycled material, the solid-liquid ratio in the condition of the water leaching washing treatment is in the range of 3:1 to 1:300; the sulfuric acid concentration is not more than 100 g/L.
10. The method for recovering sodium cobalt Fumei slag according to claim 1, wherein S4, in the step of carrying out a second water leaching washing treatment on the second roasting material to obtain recovered material, the solid-liquid ratio is 1:10 and the sulfuric acid concentration is 1g/L.
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