CN117326811A - Wet step desulfurization method for manganese slag - Google Patents
Wet step desulfurization method for manganese slag Download PDFInfo
- Publication number
- CN117326811A CN117326811A CN202311313996.7A CN202311313996A CN117326811A CN 117326811 A CN117326811 A CN 117326811A CN 202311313996 A CN202311313996 A CN 202311313996A CN 117326811 A CN117326811 A CN 117326811A
- Authority
- CN
- China
- Prior art keywords
- manganese
- slag
- manganese slag
- leaching
- ore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 323
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 322
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 320
- 239000002893 slag Substances 0.000 title claims abstract description 285
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 17
- 230000023556 desulfurization Effects 0.000 title claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 78
- 239000011593 sulfur Substances 0.000 claims abstract description 77
- 238000002386 leaching Methods 0.000 claims abstract description 71
- 239000004568 cement Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 28
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 41
- 239000011702 manganese sulphate Substances 0.000 claims description 41
- 235000007079 manganese sulphate Nutrition 0.000 claims description 41
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 238000005188 flotation Methods 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 238000004073 vulcanization Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 239000011656 manganese carbonate Substances 0.000 claims description 12
- 235000006748 manganese carbonate Nutrition 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 12
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 12
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 11
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 11
- 239000004571 lime Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 230000019635 sulfation Effects 0.000 claims description 2
- 238000005670 sulfation reaction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 17
- 235000011132 calcium sulphate Nutrition 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011362 coarse particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 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 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- -1 manganese residue compound Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- JBMRMLLHFBHFDV-UHFFFAOYSA-N [Ni].[Mn].[Zn] Chemical compound [Ni].[Mn].[Zn] JBMRMLLHFBHFDV-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- MVLUSZAKUKCTFJ-UHFFFAOYSA-N [S-2].[Zn+2].[Ni+2].[Co+2].[S-2].[S-2] Chemical compound [S-2].[Zn+2].[Ni+2].[Co+2].[S-2].[S-2] MVLUSZAKUKCTFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/0006—Waste inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
Abstract
The invention discloses a manganese slag wet step desulfurization method, which comprises the steps of carrying out particle size classification on manganese ores, carrying out treatments such as leaching, solution purification and filtering, carrying out particle size classification on obtained manganese slag to obtain coarse-grain manganese slag and fine-grain manganese slag, carrying out calcium sulfate part phase conversion fine-grain floc floatation on the fine-grain manganese slag to obtain low-sulfur tailings and high-sulfur manganese slag, and then mixing the coarse-grain manganese slag and the low-sulfur tailings to obtain the low-sulfur manganese slag. The low-sulfur manganese slag prepared by the method can be used as a raw material for preparing cement clinker, and the high-sulfur manganese slag can be used as a cement retarder.
Description
Technical Field
The invention relates to the technical field of manganese slag treatment and resource utilization, in particular to a wet-process cascade desulfurization method for manganese slag.
Background
Manganese and its compounds are important basic raw materials for supporting national economic development, and are widely applied to the fields of steel, batteries, electronic information, chemical industry, medicine and the like. China is the largest global electrolytic manganese producing country, consuming country and export country. In the electrolytic manganese production process, 6-10 t of manganese slag can be produced every 1t of electrolytic manganese, and the new manganese slag per year in China exceeds 1000 ten thousand tons. In addition, the amount of manganese slag generated during the production of electrolytic manganese dioxide and manganese sulfate is not so small. The manganese slag has the characteristics of large yield, high content of soluble pollutants, fine particles and the like, and has become the biggest ecological environment risk source in the manganese industry.
The method is formally implemented in the national ecological environment standard of manganese slag pollution control technical Specification (HJ 1241-2022) on the 10 th month 1 st 2022. The standard comprehensively prescribes pollution control standards of the manganese slag in the processes of collection, storage, transportation, pretreatment, utilization, filling, backfilling and landfill, and specific requirements are provided for strengthening the pollution control of the whole process of the manganese slag. Therefore, measures are taken to treat or utilize the manganese slag, and the manganese slag is a problem to be solved in the manganese industry. The main component in the manganese slag is gypsum (CaSO) 4 ·2H 2 O) and quartz, and soluble manganese, magnesium and ammonium salts, and also contains small amounts of heavy metals such as cobalt, nickel, etc. At present, the treatment of manganese slag is mainly divided into two modes of harmless treatment and resource utilization.
The innocent treatment of the manganese slag mainly utilizes a water washing, leaching or solidification stabilization mode to extract or solidify harmful elements such as manganese, ammonia nitrogen, cobalt, nickel and the like in the manganese slag. Chinese patent CN115747518A discloses a method for recovering nickel-cobalt-manganese slag, which comprises acid leaching manganese slag with sulfuric acid and formic acid, filtering, adding oxidant and alkali into the filtrate, adjusting pH to 5-6, and filtering again to obtain nickel-cobalt-manganese sulfate solution. Chinese patent CN103320621a discloses a method for solidifying heavy metals in electrolytic manganese slag and co-producing sulfur, mixing and roasting raw materials containing calcium sulfite and/or calcium sulfate with a carbon-based reducing agent to obtain calcine containing calcium sulfide, mixing the calcine containing calcium sulfide with manganese slag, adding water, stirring at room temperature for reaction, filtering to obtain filtrate and filter residue, standing the filtrate to precipitate sulfur, and obtaining filter residue which is the solidified manganese slag.
The recycling of the manganese slag is usually to further process the manganese slag to prepare a usable product. Chinese patent CN102674965A discloses a manganese residue compound fertilizer and a preparation method thereof, wherein a carbonate-containing fertilizer is added into manganese residue to convert calcium sulfate in the manganese residue into calcium carbonate, and then the calcium carbonate is mixed with a lignin-containing additive and one or more element fertilizers selected from nitrogen fertilizer, phosphate fertilizer and potash fertilizer to prepare the manganese residue compound fertilizer. Chinese patent CN102584316a discloses a method for preparing electrolytic manganese slag porous ceramics, which comprises mixing manganese slag, pore-forming agent, binder and fluxing agent, adding water, stirring uniformly, pressing and forming with steel mould to obtain green compact, drying, and sintering in high temperature electric furnace at controlled temperature. Chinese patent CN111644269B discloses a method for comprehensively utilizing manganese slag, wherein a cationic collector is used for carrying out flotation on the manganese slag to obtain concentrate foam and tailing pulp, the concentrate foam is further processed to obtain white gypsum products, and the tailing pulp is further processed to be used for manufacturing baking-free bricks or cement clinker.
In conclusion, the method has great progress in the technical fields of innocent treatment and resource utilization of the manganese slag in China, and provides a good thought for the treatment and utilization of the manganese slag. However, there is still a great room for improvement in the prior art in terms of technical economy, industrial chain engagement, technical advancement, stability, etc. Particularly, the utilization rate of manganese slag resources in China is extremely low and is only about 5%, most of manganese slag is still treated in a landfill mode, and breakthrough is still needed in the aspect of the utilization technology of the resources.
Disclosure of Invention
In view of the defects existing at present, the invention provides a manganese slag wet step desulfurization method, which can divide manganese slag into high-sulfur manganese slag and low-sulfur manganese slag which are respectively used as cement retarder and cement clinker through a manganese ore and manganese slag granularity grading and fine-grain manganese slag flotation process, and organically links the manganese slag with a cement industry chain, thereby realizing the efficient utilization of the manganese slag, avoiding the generation of new pollutants and being beneficial to the clean production of the manganese industry.
In order to achieve the purpose, the invention provides a wet-process cascade desulfurization method for manganese slag, which comprises the following steps:
step 1: crushing, grinding and grading the granularity of manganese ore, leaching the manganese ore by sulfuric acid, and obtaining manganese sulfate solution and manganese slag after pH adjustment, purification treatment and filtration; wherein coarse manganese ores with the granularity of-2 mm are obtained after the granularity classification, and the coarse manganese ores with the granularity of-2 to +0.15 mm account for more than 70 percent;
step 2: washing manganese slag with water, filtering to obtain manganese slag washing liquid and washing manganese slag, wherein the manganese slag washing liquid is purified and recycled; carrying out particle size classification on the water-washed manganese slag to obtain coarse-grain manganese slag with the particle size of plus 0.074mm and fine-grain manganese slag with the particle size of minus 0.074 mm;
step 3: dispersing fine-grained manganese slag with the diameter of-0.074 mm in water to form ore pulp, converting part of calcium sulfate in the manganese slag into calcium carbonate phase by using sodium carbonate, adjusting the pH value of the ore pulp to 7.5, stirring for 1-3 minutes, adding an anionic flocculant into the ore pulp, stirring for 1-5 minutes, then adding sodium oleate, stirring for 3-5 minutes, performing flotation to obtain high-sulfur manganese slag and low-sulfur tailings, and recycling flotation wastewater after treatment;
step 4: mixing the low-sulfur tailings with coarse-grain manganese slag with the granularity of plus 0.074mm to obtain low-sulfur manganese slag serving as a raw material for preparing cement clinker, wherein the high-sulfur manganese slag is used as a cement retarder; wherein the low isSO in sulfur-manganese slag 3 The content is lower than 5%; SO in the high-sulfur manganese slag 3 The content of (2) is more than 15%.
According to one aspect of the invention, the manganese ore comprises any one of manganese carbonate ore and manganese oxide ore.
According to one aspect of the invention, the manganese slag has a main mineral component of CaSO 4 And SiO 2 SO in the manganese slag 3 The content of the manganese slag is 10-30%, and the granularity of the manganese slag is minus 2mm.
According to one aspect of the invention, when electrolytic manganese or manganese sulfate is produced by using manganese carbonate ore as a raw material, the step 1 specifically comprises the following steps:
step A1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step A2: leaching coarse-grained manganese ore by sulfuric acid, leaching for 1-3 hours at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermi as a vulcanization precipitant to purify the leaching solution, and filtering to obtain a manganese sulfate solution and manganese slag, wherein the manganese sulfate solution is a raw material in an electrolytic manganese production process or a manganese sulfate production process;
when manganese oxide ore is used as a raw material to produce electrolytic manganese or manganese sulfate, the step 1 specifically comprises the following steps:
step B1: crushing, grinding and grading manganese oxide ores to obtain coarse-grained manganese ores with granularity of-2 mm, wherein the coarse-grained manganese ores with granularity of-2 to minus 0.15mm account for more than 70 percent;
step B2: leaching coarse-grained manganese ore with sulfuric acid under the assistance of a reducing agent, leaching for 1-4 hours at 70-100 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermet as a vulcanization precipitant to purify the leaching solution, and filtering to obtain a manganese sulfate solution and manganese slag, wherein the manganese sulfate solution is a raw material in an electrolytic manganese production process or a manganese sulfate production process;
wherein the reducing agent comprises at least one of pyrite, sulfur dioxide and manganese sulfide.
According to one aspect of the invention, the manganese slag is leaching slag obtained by leaching, neutralizing precipitation and vulcanizing precipitation, and mixed slag of neutralizing precipitation slag and vulcanizing precipitation slag; or the mixed slag of the leached slag and the neutral precipitate slag obtained by leaching and neutral precipitation;
when the obtained manganese slag is the mixed slag of leaching slag, neutralizing precipitation slag and vulcanizing precipitation slag, the step 1 specifically comprises the following steps:
step C1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step C2: leaching coarse-grained manganese ore by sulfuric acid, leaching for 1-3 hours at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermet as a vulcanization precipitant to purify the leaching solution, and filtering to obtain manganese sulfate solution and leaching residues, and neutralizing mixed residues of the precipitation residues and the vulcanization precipitation residues;
when the obtained manganese slag is the mixed slag of leaching slag and neutral precipitation slag, the step 1 specifically comprises the following steps:
step D1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step D2: leaching coarse manganese ore with sulfuric acid, leaching for 1-3 h at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, and filtering to obtain a coarse manganese sulfate solution and mixed slag of leaching slag and neutral precipitation slag;
step D3: adding sodium fermi as a vulcanization precipitator to carry out purification treatment on the crude manganese sulfate solution, and filtering to obtain manganese sulfate solution and sulfation slag.
According to one aspect of the invention, the anionic flocculant comprises one or both of polyacrylamide and sodium polyacrylate.
In accordance with one aspect of the invention, in step 3, the pulp concentration is 15% to 30%; the dosage of the sodium oleate is 1-6 kg/t; the dosage of the sodium carbonate is 2-80 kg/t.
In accordance with one aspect of the present invention, in step 4, when the low sulfur manganese slag is used to prepare cement clinker, limestone and silica sand are also added; wherein the mass ratio of the limestone to the low-sulfur manganese slag is 5:1-4; the sintering temperature for preparing the cement clinker is 1250-1400 ℃.
According to one aspect of the invention, step 1 further comprises a step-wise purification, step 1 comprising a step-wise purification being in particular:
step E1: crushing, grinding and grading the manganese ore, leaching with sulfuric acid, adjusting the pH value to 3-4, and filtering to obtain a crude manganese sulfate solution and manganese slag;
step E2: purifying the crude manganese sulfate solution by using sodium fermet as a vulcanization precipitator, and filtering to obtain the manganese sulfate solution and nickel-cobalt-containing sulfide slag.
According to one aspect of the invention, the sodium carbonate dosage in the step 3 is 2-20 kg/t; the low-sulfur manganese slag obtained in the step (4) is converted into deep phase conversion low-sulfur manganese slag; the process for converting the low-sulfur manganese slag into the deep phase-conversion low-sulfur manganese slag comprises the following steps: putting the low-sulfur manganese slag obtained in the step 3 and sodium carbonate into water, reacting for 5-30 minutes at the temperature of 10-60 ℃ to further convert calcium sulfate in the low-sulfur manganese slag into calcium carbonate, and filtering to obtain deep phase-conversion low-sulfur manganese slag; wherein the dosage of sodium carbonate is 20-60 kg/t, the liquid-solid volume mass ratio is 2-5:1, and the SO of the low-sulfur manganese slag is deeply phase-converted 3 The content is lower than 0.5%.
The invention has the beneficial effects that:
(1) The invention can make manganese slag harmless and divide the manganese slag into CaSO through the flow of manganese ore particle size classification, leaching, leachate purification, manganese slag particle size classification and calcium sulfate part phase conversion fine-grain floc floatation 4 Content of>15% high sulfur manganese slag and CaSO 4 Content of<5% of low-sulfur manganese slag is respectively used as a cement retarder and cement clinker, and the manganese slag is organically connected with a cement industry chain, so that the high-efficiency utilization of the manganese slag is realized, no new pollutants are generated, and the clean production of the manganese industry is facilitated;
(2) The manganese slag treatment method based on the physical separation of manganese ore and manganese slag provided by the invention is mainly based on a physical method, does not need heating in the process, does not introduce new harmful impurities, has simple process and lower cost, and has better technical economy and technical stability;
(3) The invention is based on calcium sulphate (CaSO 4 ) The difference of distribution in coarse and fine particle size manganese slag, namely, the rule that calcium sulfate is more distributed in fine particle manganese slag and the coarse particle manganese slag contains less calcium sulfate, creatively proposes a method for controlling the particle size of manganese ore and classifying the manganese slag, compared with the existing manganese ore with particle size of-0.15 mm which is obtained by crushing and grinding and to be leached, the manganese ore is subjected to particle size classification, the obtained coarse particle manganese ore has large particle size, coarse particles with particle size of-2 to-0.15 mm account for 70%, so that the coarse particle manganese slag is easier to obtain during the subsequent particle size classification of manganese slag, the coarse particle manganese slag accounts for a large proportion, the calcium sulfate in the manganese slag can be separated simply and conveniently, and the fine particle floc flotation technology is further utilized by adding excessive Na (sodium sulfate) part phase conversion, namely 2 CO 3 So that a part of Na 2 CO 3 With CaSO in fine-grained manganese slag 4 Reaction to produce CaCO 3 ，CaCO 3 Wrapping CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the Another part of Na 2 CO 3 Combining with anionic flocculant and sodium oleate to make CaCO 3 Wrapping CaSO 4 The floating up method strengthens the separation effect of calcium sulfate, and further performs phase transformation on the low-sulfur manganese slag to obtain deep phase-transformed SO of the low-sulfur manganese slag 3 The content is lower than 0.5%. The method not only comprises a manganese slag treatment process, but also improves the manganese ore treatment process, and provides a solution for recycling manganese slag of the system.
Drawings
FIG. 1 is a process flow diagram of preparing low-sulfur manganese slag and high-sulfur manganese slag by the wet step desulfurization method of manganese slag in the embodiment 1 of the invention;
FIG. 2 is a flow chart of the process for preparing cement according to example 2 of the present invention;
FIG. 3 is a flow chart of the process of size classification, leaching and fractional precipitation of comparative example 4 manganese ore;
FIG. 4 is a flow chart of a flotation process for fine-grained manganese slag according to examples 4-5 of the invention;
FIG. 5 is a closed circuit flotation process flow diagram of comparative example 3 fine grained manganese slag of the invention;
FIG. 6 is an XRD pattern of cement clinker prepared in example 2 of the present invention;
FIG. 7 is an XRD pattern of manganese slag before and after reaction with sodium carbonate as described in example 6 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the invention and not to limit the scope of the invention, and that the described embodiments are merely some, but not all, of the embodiments of the invention. 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, the terms of art used hereinafter are consistent with the meanings understood by those skilled in the art; unless otherwise indicated, all the materials and reagents referred to herein are commercially available or may be prepared by well-known methods.
It should be noted that the SO described in this application 3 Is in the form of sulfate, but the expressed content is often calculated as sulfur trioxide.
It should be noted that the unit "kg/t" in the present application means that a certain substance is added in a few kilograms per ton of manganese slag, for example, that "the dosage of sodium oleate is 1kg/t" means that 1 kilogram of sodium oleate is added in a ton of manganese slag.
Example 1
The manganese ore used in this example was manganese carbonate ore from Guizhou, which had a Mn grade of 16.74%.
The manganese ore is processed by adopting the process flow shown in fig. 1, and the specific steps are as follows:
s1: crushing manganese ore, grinding, screening coarse-grain manganese ore with the granularity of-2 mm, wherein the coarse-grain manganese ore with the granularity of-2 to minus 0.15mm accounts for more than 70%, the manganese ore with the granularity of-2 to minus 1mm accounts for 43.21%, sulfuric acid is used as a leaching agent, the manganese ore with the granularity of-2 to minus 1mm is leached under the conditions that the mineral acid mass ratio is 1:1 and the liquid-solid volume mass ratio is 4:1, ferrous ions in the air oxidation leaching solution are introduced after leaching for 1h at 55 ℃, sodium ferox is used as a vulcanization precipitant, the leaching solution is purified, lime is used as a pH regulator, the pH value of the solution is regulated to be 4, manganese sulfate solution and manganese slag are obtained by filtering, the manganese slag is washed by water, the manganese sulfate solution can be used as qualified electrolytic manganese solution, the manganese content in the solution is 34.56g/L, the magnesium content is 3.10g/L, and the manganese content of Ni, co, fe and the like are lower than 1mg/L;
s2: classifying the water-washed manganese slag to obtain coarse-grain manganese slag with granularity of minus 0.074mm and fine-grain manganese slag with granularity of minus 0.074mm, wherein the coarse-grain manganese slag with granularity of minus 0.074mm accounts for 44.12 percent of the mass of the manganese slag, and SO thereof 3 The content of (2) is 6.24%;
s3: dispersing fine-grained manganese slag with water, adjusting the pH of the ore pulp to 7.5 with 8.0kg/t sodium carbonate, stirring for 1-3 minutes, adding 15g/t anionic polyacrylamide into the ore pulp, stirring for 1-5 minutes, then adding 2.4kg/t sodium oleate, stirring for 3-5 minutes, performing flotation to obtain high-sulfur manganese slag and low-sulfur tailings, and recycling flotation wastewater after treatment;
s4: the low-sulfur tailings are mixed with coarse-grain manganese slag to obtain low-sulfur manganese slag which is used as a raw material for preparing cement clinker and SO thereof 3 The content is 4.60 percent, the high-sulfur manganese slag is used as a cement retarder, and SO is adopted as the retarder 3 The content is 42.35%;
example 2
The low-sulfur manganese slag and the high-sulfur manganese slag used in the present example are from example 1, and the cement is prepared by adopting the process flow shown in fig. 2, and the specific steps are as follows:
s1: grinding the low-sulfur manganese slag, and according to the low-sulfur manganese slag: limestone is added in a ratio of 2:3, the ratio of Ca, si and Al in the cement raw material is adjusted by adding limestone and silica sand, the adjusted cement raw material is calcined at 1300 ℃ to obtain cement clinker, XRD characterization is carried out on the cement clinker, and the result is shown in figure 6; as can be seen from FIG. 6, XRD peaks and C of the calcined product 2 S and C 3 The characteristic peaks of S are identical, which indicates that the product is cement clinker;
s2: mixing cement clinker and high-sulfur manganese slag according to a mass ratio of 30:1, grinding the mixture to-0.074 mm to obtain cement, and detecting SO in the cement 3 The content is 3.29 percent, accords with the SO in slag silicate cement of national standard general Portland Cement (GB 175-2007) 3 The content is less than or equal to 4.0 percent.
Example 3
The manganese ore used in this example was from Guizhou and had the same composition as the manganese ore used in example 1. The flow as shown in fig. 1 is adopted to carry out the particle size classification-leaching treatment on manganese ores, and the specific steps are as follows:
s1: crushing manganese ore, grinding and grading the granularity to obtain coarse-grain manganese ore with granularity of-2 mm, wherein manganese ore particles with granularity of-2 to +/-1 mm account for 47.12%;
s2: taking sulfuric acid as a leaching agent, leaching manganese ore particles of which the diameter is minus 2 to minus 1mm in the condition that the mass ratio of ore acid is 1:1, the liquid-solid volume ratio is 2:1, and the leaching temperature is 70 ℃, introducing air after leaching for 3 hours, adding lime to adjust the pH value to 3.5, then adding sodium fermi as a vulcanization precipitant to purify the leaching solution, and filtering to obtain a manganese sulfate solution and cobalt-containing nickel-zinc-manganese slag, wherein the Mn content in the manganese sulfate solution is 34.5g/L, the Mg content is 2.4g/L, and the Fe, ni, co, zn content is less than 1Mg/L, so that the manganese sulfate solution can be used as a qualified solution for producing electrolytic manganese;
s3: classifying the granularity of the manganese slag, and classifying SO of the manganese slag with each granularity 3 Analysis was performed and the results are shown in table 1.
TABLE 1 SO after leaching of coarse manganese ore-purification slag size classification 3 Content analysis
Example 4
The manganese slag used in this example was obtained from an electrolytic manganese plant in Guizhou, and was a mixed slag of leached slag, neutralized precipitate slag and sulfidized precipitate slag obtained from manganese carbonate ore as a raw material, and had a particle size of-0.15 mm, SO 3 The content was 12.82%. After the manganese slag was sized (see table 4 of comparative example 1), the fine-grained manganese slag was subjected to flotation using the procedure as in fig. 4, specifically:
dispersing fine-grain manganese slag with the concentration of-0.074 mm in water, regulating the pH value of the ore pulp to 7.5 by using 8.0kg/t sodium carbonate, stirring for 3 minutes, adding 15g/t anionic flocculant into the ore pulp, stirring for 5 minutes, adding 2.4kg/t sodium oleate, stirring for 5 minutes, performing flotation to obtain high-sulfur manganese slag and low-sulfur tailings, and recycling the flotation wastewater after treatment. Wherein the anionic flocculant is one of sodium polyacrylate or anionic polyacrylamide, and the flotation result is shown in table 2.
Table 2 results of fine-grained manganese slag flotation
Example 5
The manganese slag used in this example was the same as in example 4. After the manganese slag was classified in particle size, fine-grained manganese slag (-0.074 mm) was subjected to flotation using the procedure shown in fig. 4, and the difference between this example and example 5 is that the anionic flocculant used in this example was anionic polyacrylamide, dextrin was used in an amount of 0.6kg/t, sodium carbonate was used in an amount of 8.0kg/t, and sodium oleate was used in an amount of 1.2 to 6.0kg/t, and the results are shown in table 3.
TABLE 3 results of fine-grained manganese slag flotation
Example 6
The manganese slag used in this example was the same as in example 4. To prove Na 2 CO 3 The presence of (2) may enable part of the CaSO 4 In this example, under the conditions of pulp concentration of 20%, sodium carbonate dosage of 80kg/t, anionic flocculant dosage of 15g/t, sodium oleate dosage of 2kg/t and pH value of 8, stirring for 10 min, solid-liquid separation, collection of solid product and drying, and the likeThe product was XRD-characterized and the results are shown in figure 7. FIG. 7 shows Na 2 CO 3 Under the flotation condition, part of CaSO in the manganese slag can be made 4 The product is CaCO after phase inversion 3 . Na in solution 2 SO 4 And (3) recycling the flotation wastewater, and after the concentration reaches a certain degree, collecting the flotation wastewater in an open circuit mode, and recovering sodium sulfate crystals in an evaporation crystallization mode.
Example 7
The low sulfur manganese slag used in this example was from example 1. To further reduce SO in low sulfur manganese slag 3 Content by Na 2 CO 3 CaSO in low-sulfur manganese slag 4 Phase transformation into CaCO 3 . At room temperature, the low-sulfur manganese slag and 20kg/t Na 2 CO 3 Uniformly mixing, reacting for 10 minutes under the conditions that the liquid-solid volume mass ratio is 4:1, the temperature is 25 ℃ and the pH value is 8, separating solid from liquid to obtain deep phase-conversion low-sulfur manganese slag, and analyzing the deep phase-conversion low-sulfur manganese slag to obtain SO (sulfur-oxygen) thereof 3 The content is 0.4%, and compared with 4.60% before reaction, the content is obviously reduced.
Comparative example 1
The manganese slag of this comparative example was the same as in example 4. The electrolytic manganese slag was subjected to particle size classification, and specific components are shown in Table 4.
TABLE 4 SO after classification of manganese slag particle size 3 Content analysis
Comparative example 2
The manganese slag used in this comparative example was the same as in example 4. The manganese slag is subjected to particle size classification-flotation by adopting the process flow shown in figure 1, and the method specifically comprises the following steps:
s1: washing the manganese slag with water at the liquid-solid volume mass ratio of 4:1 and the temperature of 25 ℃, filtering to obtain manganese slag washing liquid and washing manganese slag, and treating the manganese slag washing liquid for recycling;
s2: classifying the water-washed manganese slag to obtain coarse manganese slag with granularity of plus 0.074mm and fine manganese slag with granularity of minus 0.074mmA coarse-grain manganese slag with a 5.13% SO ratio 3 The content of the manganese slag is 1.71%, the proportion of the fine-grain manganese slag is 94.87%, and the SO of the manganese slag is 3 The content is 12.85 percent;
s3: dispersing fine-grained manganese slag in water, regulating the pH of the ore pulp to 7.5 by adding 8.0kg/t sodium carbonate, stirring for 3 minutes, adding 15g/t anionic flocculant into the ore pulp, stirring for 5 minutes, then adding 2.4kg/t sodium oleate, stirring for 5 minutes for flotation to obtain high-sulfur manganese slag and low-sulfur tailings, recycling after flotation wastewater treatment, and measuring and analyzing to obtain the yield of the low-sulfur tailings of 46.13 percent and SO (sulfur-doped oxide) of the low-sulfur tailings 3 The content is 5.42 percent, the yield of the high-sulfur manganese slag is 49.92 percent, and the SO thereof 3 The content of (2) is 19.01%;
s4: the low-sulfur tailings are mixed with coarse-grain manganese slag to obtain low-sulfur manganese slag which is used as raw material for preparing cement clinker, and SO thereof 3 The content is 3.24%, the high-sulfur manganese slag is used as a cement retarder, and SO is used as a retarder 3 The content is 19.01%.
Comparative example 3
The manganese slag used in this comparative example was the same as in example 4, and after classification of the particle size of the manganese slag, a closed-circuit test for flotation was performed on fine-grained manganese slag using the procedure shown in fig. 5, specifically:
step 1: dispersing fine-grained manganese slag with water, adjusting the concentration of ore pulp to 20%, adding 8kg/t sodium carbonate to adjust the pH of the ore pulp to 7.5, stirring for 3 minutes, adding 15g/t anionic flocculant into the ore pulp, stirring for 5 minutes, then adding 2.4kg/t sodium oleate, stirring for 5 minutes, and carrying out roughing to obtain roughing tailings and high-sulfur manganese slag;
step 2: adding 1.0kg/t sodium oleate into the roughing tailings obtained by roughing to perform one-time scavenging to obtain middling and low-sulfur tailings, wherein the middling returns to the roughing process.
As shown by measurement and analysis of high-sulfur manganese slag and low-sulfur tailings, the yield of the high-sulfur manganese slag is 58.15 percent, and the SO thereof 3 The content is 22.41%; the yield of the low-sulfur tailings is 41.85 percent, and the SO thereof 3 The content was 1.31%.
Comparative example 4
The manganese ore used in this comparative example was the same as in example 1. The manganese ore is subjected to particle size classification, leaching and step precipitation treatment by adopting the flow chart shown in fig. 3, and the method is specifically as follows:
s1: crushing manganese ore, grinding and grading the granularity to obtain coarse-grain manganese ore with granularity of-2 mm, wherein manganese ore particles with granularity of-0.6 to minus 0.355mm account for 21.35 percent;
s2: taking sulfuric acid as a leaching agent, leaching manganese ore particles of which the concentration is minus 0.6 to minus 0.355mm in S1 by sulfuric acid under the conditions that the mass ratio of ore acid is 1:1, the liquid-solid volume ratio is 2:1 and the leaching temperature is 70 ℃, introducing air after leaching for 3 hours, adding lime to adjust the pH value to 4, and filtering to obtain a crude manganese sulfate solution and mixed slag of leaching slag and neutral precipitation slag, wherein the Mn content in the solution is 30.47g/L, the Mg content is 3.47g/L, the Zn content is 25Mg/L, the Co content is 35Mg/L, the Fe and Ni content is lower than 1Mg/L, and the crude manganese sulfate solution is further vulcanized, precipitated and purified to obtain manganese sulfate solution and nickel cobalt zinc sulfide slag;
s3: classifying the manganese slag in the step S2 in particle size, and classifying the SO of the manganese slag in each particle size 3 Analysis was performed and the results are shown in table 5.
TABLE 5 leaching of coarse manganese ore-SO after classification of manganese slag particle size 3 Content analysis
Analysis of results:
from table 1 of example 3 and table 4 of comparative example 1, it is evident that the coarse-grained manganese slag of example 3 has a much larger ratio (42.08%) than that of comparative example 1 (5.02%), indicating that the size-graded leaching of manganese ore using the present invention is advantageous for increasing the ratio of coarse-grained manganese slag.
As can be seen from table 5 of comparative example 4, table 4 of comparative example 1 and table 1 of example 3, the ratio of coarse manganese slag of comparative example 4 (20.12%) is greater than that of comparative example 1 (5.02%) and less than that of example 3 (42.08%), indicating that increasing the particle size of leached manganese ore is advantageous for increasing the ratio of coarse manganese slag.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The wet step desulfurization method for the manganese slag is characterized by comprising the following steps of:
step 1: crushing, grinding and grading the granularity of manganese ore, leaching the manganese ore by sulfuric acid, and obtaining manganese sulfate solution and manganese slag after pH adjustment, purification treatment and filtration; wherein coarse manganese ores with the granularity of-2 mm are obtained after the granularity classification, and the coarse manganese ores with the granularity of-2 to +0.15 mm account for more than 70 percent;
step 2: washing manganese slag with water, filtering to obtain manganese slag washing liquid and washing manganese slag, wherein the manganese slag washing liquid is purified and recycled; carrying out particle size classification on the water-washed manganese slag to obtain coarse-grain manganese slag with the particle size of plus 0.074mm and fine-grain manganese slag with the particle size of minus 0.074 mm;
step 3: dispersing fine-grained manganese slag with the diameter of-0.074 mm in water to form ore pulp, converting part of calcium sulfate in the manganese slag into calcium carbonate phase by using sodium carbonate, adjusting the pH value of the ore pulp to 7.5, stirring for 1-3 minutes, adding an anionic flocculant into the ore pulp, stirring for 1-5 minutes, then adding sodium oleate, stirring for 3-5 minutes, performing fine-grained floc flotation, obtaining high-sulfur manganese slag and low-sulfur tailings, and recycling flotation wastewater after treatment;
step 4: mixing the low-sulfur tailings with coarse-grain manganese slag with the granularity of plus 0.074mm to obtain low-sulfur manganese slag serving as a raw material for preparing cement clinker, wherein the high-sulfur manganese slag is used as a cement retarder; wherein SO in the low-sulfur manganese slag 3 The content is lower than 5%; SO in the high-sulfur manganese slag 3 The content of (2) is more than 15%.
2. The method for wet cascade desulfurization of manganese slag according to claim 1, wherein the manganese ore comprises any one of manganese carbonate ore and manganese oxide ore.
3. The method for wet step desulfurization of manganese slag according to claim 1, wherein the main mineral component of the manganese slag is CaSO 4 And SiO 2 SO in the manganese slag 3 The content of the manganese slag is 10-30%, and the granularity of the manganese slag is minus 2mm.
4. The method for wet step desulfurization of manganese slag according to claim 2, wherein when electrolytic manganese or manganese sulfate is produced by using manganese carbonate ore as a raw material, the step 1 is specifically as follows:
step A1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step A2: leaching coarse-grained manganese ore by sulfuric acid, leaching for 1-3 hours at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermi as a vulcanization precipitant to purify the leaching solution, and filtering to obtain a manganese sulfate solution and manganese slag, wherein the manganese sulfate solution is a raw material in an electrolytic manganese production process or a manganese sulfate production process;
when manganese oxide ore is used as a raw material to produce electrolytic manganese or manganese sulfate, the step 1 specifically comprises the following steps:
step B1: crushing, grinding and grading manganese oxide ores to obtain coarse-grained manganese ores with granularity of-2 mm, wherein the coarse-grained manganese ores with granularity of-2 to minus 0.15mm account for more than 70 percent;
step B2: leaching coarse-grained manganese ore with sulfuric acid under the assistance of a reducing agent, leaching for 1-4 hours at 70-100 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermet as a vulcanization precipitant to purify the leaching solution, and filtering to obtain a manganese sulfate solution and manganese slag, wherein the manganese sulfate solution is a raw material in an electrolytic manganese production process or a manganese sulfate production process;
wherein the reducing agent comprises at least one of pyrite, sulfur dioxide and manganese sulfide.
5. The method for wet cascade desulfurization of manganese slag according to claim 1, wherein the manganese slag is leached slag obtained by leaching, neutralization precipitation and vulcanization precipitation, and mixed slag of neutralization precipitation slag and vulcanization precipitation slag; or the mixed slag of the leached slag and the neutral precipitate slag obtained by leaching and neutral precipitation;
when the obtained manganese slag is the mixed slag of leaching slag, neutralizing precipitation slag and vulcanizing precipitation slag, the step 1 specifically comprises the following steps:
step C1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step C2: leaching coarse-grained manganese ore by sulfuric acid, leaching for 1-3 hours at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, adding sodium fermet as a vulcanization precipitant to purify the leaching solution, and filtering to obtain manganese sulfate solution and leaching residues, and neutralizing mixed residues of the precipitation residues and the vulcanization precipitation residues;
when the obtained manganese slag is the mixed slag of leaching slag and neutral precipitation slag, the step 1 specifically comprises the following steps:
step D1: crushing, grinding and grading manganese carbonate ore to obtain coarse manganese ore with granularity of-2 mm; wherein, the coarse-grain manganese ore with the granularity of minus 2 to minus 0.15mm accounts for more than 70 percent;
step D2: leaching coarse manganese ore with sulfuric acid, leaching for 1-3 h at 40-70 ℃, introducing air after leaching, adding lime to adjust pH, and filtering to obtain a coarse manganese sulfate solution and mixed slag of leaching slag and neutral precipitation slag;
step D3: adding sodium fermi as a vulcanization precipitator to carry out purification treatment on the crude manganese sulfate solution, and filtering to obtain manganese sulfate solution and sulfation slag.
6. The method for wet step desulfurization of manganese slag according to claim 1, wherein the anionic flocculant comprises one or two of polyacrylamide and sodium polyacrylate.
7. The method for wet step desulfurization of manganese slag according to claim 1, wherein in the step 3, the concentration of ore pulp is 15% -30%; the dosage of the sodium oleate is 1-6 kg/t; the dosage of the sodium carbonate is 2-80 kg/t.
8. The method for wet step desulfurization of manganese slag according to claim 1, wherein in step 4, limestone and silica sand are further added when preparing cement clinker from the low-sulfur manganese slag; wherein the mass ratio of the limestone to the low-sulfur manganese slag is 5:1-4; the sintering temperature for preparing the cement clinker is 1250-1400 ℃.
9. The method for wet step desulfurization of manganese slag according to claim 1, wherein step 1 further comprises step-by-step purification, and step 1 comprising step-by-step purification specifically comprises:
step E1: crushing, grinding and grading the manganese ore, leaching with sulfuric acid, adjusting the pH value to 3-4, and filtering to obtain a crude manganese sulfate solution and manganese slag;
step E2: purifying the crude manganese sulfate solution by using sodium fermet as a vulcanization precipitator, and filtering to obtain the manganese sulfate solution and nickel-cobalt-containing sulfide slag.
10. The method for wet step desulfurization of manganese slag according to claim 1 or 7, wherein the dosage of sodium carbonate in the step 3 is 2-20 kg/t; the low-sulfur manganese slag obtained in the step (4) is converted into deep phase conversion low-sulfur manganese slag; the process for converting the low-sulfur manganese slag into the deep phase-conversion low-sulfur manganese slag comprises the following steps: putting the low-sulfur manganese slag obtained in the step 3 and sodium carbonate into water, reacting for 5-30 minutes at the temperature of 10-60 ℃ to further convert calcium sulfate in the low-sulfur manganese slag into calcium carbonate, and filtering to obtain deep phase-conversion low-sulfur manganese slag; wherein the dosage of sodium carbonate is 20-60 kg/t, the liquid-solid volume mass ratio is 2-5:1, and the SO of the low-sulfur manganese slag is deeply phase-converted 3 The content is lower than 0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311313996.7A CN117326811A (en) | 2023-10-11 | 2023-10-11 | Wet step desulfurization method for manganese slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311313996.7A CN117326811A (en) | 2023-10-11 | 2023-10-11 | Wet step desulfurization method for manganese slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117326811A true CN117326811A (en) | 2024-01-02 |
Family
ID=89282651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311313996.7A Pending CN117326811A (en) | 2023-10-11 | 2023-10-11 | Wet step desulfurization method for manganese slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117326811A (en) |
-
2023
- 2023-10-11 CN CN202311313996.7A patent/CN117326811A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104689913B (en) | A kind of method that polycrystalline series troilite mixing is reclaimed | |
| CN103274471B (en) | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN105567976B (en) | A kind of vanadium extraction industrial acidic wastewater processing and the method for valuable metal synthetical recovery | |
| CN104445431A (en) | Method for preparing high-purity iron oxide red from pyrites slag | |
| CN114804177B (en) | Mineralized CO of industrial solid waste electrolytic manganese slag 2 Resource utilization method | |
| CN101760632A (en) | Method for recovering zinc from zinc sulfate solution | |
| CN110284004A (en) | A kind of method that copper ashes cooperates with recycling with sodium sulphate waste residue | |
| AU2022402780A1 (en) | Method for comprehensively recovering lithium, tantalum-niobium, silicon-aluminum micro-powder, iron ore concentrate and gypsum from lithium slag | |
| CN109734105A (en) | A kind of method that titanium gypsum conversion and cycle metal self enrichment and whole amount utilize | |
| CN110255689B (en) | Sulfur and sulfite hydrothermal disproportionation and sulfuration arsenic fixation method | |
| CN114737066A (en) | Method for extracting lithium from lithium ore leaching slag | |
| CN104843750A (en) | Method for converting aluminium in Bayer red mud from hydrate garnet phase to alumina phase | |
| CN112090576A (en) | Method and device for purifying quartz in non-ferrous metal tailings | |
| CN114192274B (en) | Manganese ore resource utilization method combining smelting and selecting materials | |
| CN101759233A (en) | Method for recovering cobalt from cobalt sulfate solution | |
| CN117326811A (en) | Wet step desulfurization method for manganese slag | |
| CN114014578B (en) | Expanding agent based on industrial waste and preparation method thereof | |
| CN113215388B (en) | Method for converting niobium minerals in niobium rough concentrate into niobium-calcium ore and producing niobium concentrate | |
| CN109319896A (en) | The method for preparing flocculant with flyash and vanadium titano-magnetite | |
| CN101760630A (en) | Method for recovering copper from copper sulfate solution | |
| CN112191666B (en) | Method for recycling industrial waste | |
| CN117361563A (en) | Manganese slag gradient generation and classification resource utilization method | |
| CN102115813A (en) | Comprehensive utilization method for low-grade magnesite | |
| CN101760635A (en) | Method for recovering nickel from nickel sulfate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |