CN116426976A - Method and equipment for resource utilization and innocent treatment of manganese slag - Google Patents
Method and equipment for resource utilization and innocent treatment of manganese slag Download PDFInfo
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- CN116426976A CN116426976A CN202310386122.8A CN202310386122A CN116426976A CN 116426976 A CN116426976 A CN 116426976A CN 202310386122 A CN202310386122 A CN 202310386122A CN 116426976 A CN116426976 A CN 116426976A
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- manganese
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000011572 manganese Substances 0.000 title claims abstract description 144
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 142
- 239000002893 slag Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 36
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 36
- 238000003825 pressing Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 30
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000011449 brick Substances 0.000 claims abstract description 12
- 239000004568 cement Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims description 71
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 40
- 238000000855 fermentation Methods 0.000 claims description 39
- 230000004151 fermentation Effects 0.000 claims description 39
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000004458 analytical method Methods 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 241000894006 Bacteria Species 0.000 claims description 16
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004567 concrete Substances 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000012629 purifying agent Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 5
- 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 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 2
- 241000235342 Saccharomycetes Species 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 abstract description 22
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 22
- 239000011702 manganese sulphate Substances 0.000 abstract description 17
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 17
- 238000004064 recycling Methods 0.000 abstract description 12
- 239000004566 building material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 19
- 238000002386 leaching Methods 0.000 description 13
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/144—Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
-
- 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
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/36—Means for collection or storage of gas; Gas holders
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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Abstract
The invention discloses a method and equipment for resource utilization and innocent treatment of manganese slag, wherein the method comprises the steps of washing the manganese slag by utilizing a water washing method to separate ammonium sulfate from manganese sulfate, electrolyzing the manganese sulfate to obtain electrolytic manganese, washing and filter-pressing the slag by using slag washing water to perform innocent treatment, and recycling divalent manganese and ammonium sulfate in the manganese slag and performing innocent treatment on the slag to finish the recycling of divalent manganese and ammonium sulfate in the manganese slag, wherein the slag after the innocent treatment can be used for producing environment-friendly bricks or used as cement mixture to realize recycling of resources and economic circulation. The method has low production cost, the recovery rate of the separated and recovered soluble manganese and ammonium sulfate can reach more than 80%, the treated manganese slag reaches the national building material quality standard, the method is environment-friendly and safe, the comprehensive utilization value of the manganese slag is improved, and the sustainable development is realized.
Description
Technical Field
The invention relates to the technical field of manganese slag waste residue treatment, in particular to a method and equipment for resource utilization and innocent treatment of manganese slag.
Background
The electrolytic manganese slag is an industrial waste slag produced by filter pressing in the process of producing metal manganese by an electrolytic method, and most of the manganese slag of enterprises at one time is discharged in an open-air piling mode, but heavy metal elements contained in the manganese slag can continuously enter ecological environments such as surface water, groundwater, soil and the like around the manganese slag through long-term feeding and weathering in the piling process, so that the ecological environment of a mining area is seriously influenced, and according to the requirements of the latest policy, the manganese slag produced by the electrolytic manganese industry can only be subjected to harmless treatment and is not allowed to be piled for a long time.
Harmless treatment of electrolytic manganese slag aims at reducing or removing Mn in manganese slag 2+ NH and NH 4 + Under the conditions of the like, the manganese metal and other metal substances are recovered, and the recycling of resources is realized. At present, most of manganese slag produced in the domestic manganese industry is generally treated by methods such as high-temperature roasting, dry ammonium removal and the like, lime powder is used for alkalizing ammonium sulfate and manganese sulfate in the manganese slag, a large amount of ammonia gas is volatilized and manganese hydroxide is formed, so that the ammonium sulfate and the manganese sulfate in a free state are solidified and are used for processing cement bricks or serving as cement mixtures, but the cost produced in the process is high, the cost consumption is high, and the maximum reasonable resource utilization is not realized. Therefore, how to realize the harmless treatment of the electrolytic manganese slag and to carry out the resource utilization topic of the electrolytic manganese slag becomes an urgent difficult problem in the electrolytic manganese industry.
The documents related to the resource utilization and innocent treatment of the manganese slag are searched as follows:
1. chinese patent: "method for treating electrolytic manganese slag harmless", application number: 201710916632.6; summary: the invention discloses a harmless method for treating electrolytic slag, which comprises the following steps: (1) The manganese slag is heated to 450-900 ℃ and the oxygen partial pressure is 10 -2 Pa~10 4 Roasting under Pa condition of 0.5-0.5%4 hours; (2) Soaking the manganese slag obtained in the step (1) for 0.5-2 hours by using an aqueous solution containing a chelating agent or dilute sulfuric acid; (3) And (3) carrying out filter pressing on the product obtained in the step (2), and drying a filter cake to obtain harmless manganese slag. The method can lead the color of the innocuous manganese slag to be the same as the color of the local clay, and the concentration of harmful substances including heavy metals to reach the national agricultural soil standard. The harmless manganese slag can be used as soil for improving farmland and can also be used for secondary tillage of local desertification land.
2. Chinese patent: "a pretreatment of electrolytic manganese slag and a composite admixture combination and resource utilization technology for preparing concrete"; application number: 201811354272.6; summary: the invention belongs to the technical field of industrial waste treatment, and provides a harmless and recycling technology combining pretreatment of electrolytic manganese slag and preparation of composite admixture for concrete. The technology comprises the following steps: (1) pretreatment; (2) preparing the composite admixture for concrete. The technology can solve the pollution problems that ammonia nitrogen, soluble heavy metal manganese Mn and the like in electrolytic manganese slag cannot be removed in the prior art, and can also carry out thorough hazard treatment and comprehensive recycling on the electrolytic manganese slag; the technology is not only suitable for the problems of innocent treatment and recycling comprehensive utilization of the electrolytic manganese slag with large scale and the electrolytic manganese enterprise, but also solves the industrial problems that the single electrolytic manganese enterprise has small scale and is difficult to achieve the economic treatment scale and the like in the electrolytic manganese industrialization concentration area by combining the dispersion innocent pretreatment and the centralized preparation of the composite admixture for concrete.
3. Chinese patent: "harmless treatment method of electrolytic manganese slag"; application number: 201810589477.6; summary: the invention discloses a harmless treatment method of electrolytic manganese slag, which comprises the following steps: (1) Drying and crushing electrolytic manganese slag, and then roasting at low temperature to obtain roasted material and produce the product containing NH 3 And SO 2 Is a flue gas of (1); (2) Soaking the obtained roasting material in water, and then carrying out solid-liquid separation to obtain filter residues and manganese-containing filtrate; (3) Drying the separated filter residues to obtain harmless manganese residues, adding a precipitator into the manganese-containing filtrate to precipitate manganese, and waiting for the manganese precipitationAnd (5) carrying out solid-liquid separation after the manganese precipitation is completed, and obtaining a manganese-precipitated liquid and a manganese-containing product. The method disclosed by the invention is simple in process, mild in process condition, short in time required by the process and low in cost, can effectively realize harmless recycling treatment of electrolytic manganese slag, is environment-friendly, and reduces the environment-friendly pressure and production cost of related enterprises.
4. Chinese patent: "an electrolytic manganese slag harmless and recycling disposal system"; application number: 201910934265.1; summary: the invention discloses an electrolytic manganese slag harmless and recycling treatment system, which relates to the technical field of solid waste treatment and comprises a hopper, a conveyor belt, a crusher, a slurry melting tank, thickeners, stirring leaching tanks, a filter press, a clean water tank and a dosing barrel, wherein n number of thickeners is greater than or equal to 3, and one stirring leaching tank is arranged between every two adjacent thickeners; the bottom discharge port of the nth thickener is connected to the filter press through a sludge pump; the water outlet of the clean water tank is connected with the feed inlet of the n-1 stirring leaching tank through a centrifugal pump, the top overflow water outlets of the 3 rd to n-th thickeners are respectively connected with the feed inlet of the 1 st to n-2 stirring leaching tank in one-to-one correspondence through the centrifugal pump, and the top overflow water outlet of the 2 nd thickener is connected with the slurry melting tank through the centrifugal pump. The invention has reasonable structure, simple operation and good effect, and effectively reduces the investment cost of enterprises.
5. Chinese patent: "a method for innocent treatment and resource utilization of electrolytic manganese slag"; application number: 201811241670.7; summary: the invention discloses a method for innocent treatment and resource utilization of electrolytic manganese slag. The method comprises the following steps: firstly, adding calcium oxide and calcium carbonate additives into the leaching solution to effectively remove impurities such as iron, magnesium, calcium and the like in the leaching solution; secondly, regulating the pH value of the leaching solution by using sodium hydroxide, and adding sodium carbonate to react to obtain a product manganese carbonate; and finally, removing high-concentration ammonia nitrogen in the filtrate by adding calcium oxide and air stripping, and absorbing the escaped gas by adopting clear water, so that the filtrate is recycled. The method effectively reduces the contents of heavy metals and ammonia nitrogen in the electrolytic manganese slag, shortens the leaching time of manganese and ammonia nitrogen, and improves the leaching rate of manganese and ammonia nitrogen in the electrolytic manganese slag; manganese in the leaching solution is mainly recycled by manganese carbonate, the product can be directly used as an electrolytic manganese metal raw material, and in addition, the leaching solution after the stripping reaction can be recycled.
The roasting methods adopted in the documents 1 to 3 all have the technical problems of high energy consumption, high cost and the like caused by high temperature conditions, secondary pollution is caused by directly evacuating the gas generated by the high temperature in the documents 1 to 2 if the gas is subjected to desorption treatment, and the concentrated sulfuric acid is added to leach out the gas in the document 3, and the sulfuric acid and waste residues generate harmful gases such as sulfur dioxide, hydrogen sulfide and the like, so that the environmental pollution is caused; the equipment of document 4 is large and complex, resulting in expensive equipment and increased production cost; in document 5, ph is required to be adjusted multiple times for innocent treatment of manganese slag, which results in complicated and complicated process steps.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method and a method for resource utilization and innocent treatment of manganese slag, the method can effectively recycle soluble manganese and ammonium sulfate in the manganese slag, the recovery rate can reach more than 80 percent, the waste slag obtained by filter pressing can be used for producing environment-friendly bricks or used as fine sand for concrete stirring and the like after the innocent treatment, the method is low in production cost, safe and environment-friendly, the current situation of long-term storage of electrolytic manganese slag can be solved, waste materials are changed into valuable materials, and reasonable utilization of resources is achieved.
In order to achieve the above object, the present invention adopts the following technical method;
(1) Putting the manganese slag into a pulverizer to pulverize, and sieving with a 60-mesh sieve;
(2) Adding clear water or slag washing water into the crushed manganese slag, heating to 40-60 ℃, stirring and slurrying for 2 hours; the heating method can be a mode of introducing hot air into the manganese slag or heating the manganese slag in another way;
(3) After stirring completely, carrying out filter pressing on the mixture to obtain filter residues and filtrate, adding clear water into the filter residues or washing the residues for multiple times and filter pressing to obtain cleaned filter residues without manganese, and combining the filtrate for multiple times to obtain filtrate 1;
(4) The filtrate 1 was sulfidized: adding 0.1g/L sodium fermi to remove nickel in the filtrate 1, adding 0.2ml/L impurity removing agent after the reaction is completed, removing calcium, magnesium and other double salts, and performing filter pressing to obtain filtrate 2;
(5) Adding 0.15ml/L hydrogen peroxide to the filtrate 2 to remove iron, and after the reaction is completed, performing filter pressing to obtain filtrate 3;
(6) Adding 1.2ml/L purifying agent into the filtrate 3 for purification treatment, standing, and press-filtering to obtain filtrate 4; wherein the filtrate 4 contains 70-80g/L ammonium sulfate and 30-40g/L manganese sulfate;
(7) Adding selenium dioxide into the filtrate 4, delivering the filtrate into an electrolytic tank for electrolysis for 24 hours, discharging the filtrate, passivating, desulfurizing, drying and stripping to obtain an electrolytic manganese product; during the electrolysis, adding ammonium sulfate into the continuously consumed solution to ensure that the solution can contain 80-100g/L of ammonium sulfate;
(8) Carrying out mass analysis on the filter residue in the step (3) to obtain the contents of soluble manganese, ammonium sulfate, pH value, total iron, calcium, silicon and the like; adding calcium oxide powder and a free radical curing agent according to the analysis result of the soluble manganese, uniformly mixing, and crushing filter residues again to obtain powder;
(9) Conveying the crushed filter residues to a fermentation recovery tank, adding compound bacteria to ferment for 12-24 hours, and conveying a large amount of ammonia generated during fermentation to an ammonia collector to prepare ammonia water;
(10) After the fermentation time is reached, discharging, sampling and analyzing; according to the analysis result, the filter residue reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for stirring concrete; the filter residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
The slag washing water in the step (2) is water after the first or nth filter pressing; the continuously added manganese slag can be washed with slag washing water obtained after the previous press filtration or several times; generally, when the machine is started, the manganese slag is cleaned by using clear water, and the manganese slag can be subjected to gradient cleaning by using slag cleaning water with a thinner concentration, so that the concentration of the filtrate 1 is ensured.
The impurity removing agent in the step (4) is prepared by mixing ammonium bicarbonate, potassium permanganate and acetic acid according to a ratio of 0.5-1:2:0.1; the impurity removing agent is added to precipitate calcium and magnesium and remove other double salts.
The purifying agent in the step (6) is prepared by mixing polymeric ferric chloride, polyacrylamide and high-purity ammonium sulfate in a ratio of 5:0.1:1.
The addition amount of the selenium dioxide in the step (7) is 10mg/l.
The composite bacteria in the step (9) are yeast, bacillus and EM bacteria, which are mixed according to the proportion of 1-3:1:1, and the adding amount is 0.5-1% of the mass of the filter residue; the purpose of fermentation is to remove organic matters in the manganese slag.
The equipment comprises a wet crusher, a stirring barrel, a vulcanization stirring barrel, a Roots blower, a filter press, an electrolytic tank, a fermentation tank, an ammonia collector and parts matched with the wet crusher, the stirring barrel, the vulcanization stirring barrel, the Roots blower, the filter press, the electrolytic tank and the fermentation tank; the stirring barrel is internally provided with a stirring motor, a Roots blower and a temperature sensor.
The top of the fermentation tank is provided with a pulse dust collection device and an extraction opening, the tank body is airtight, and a gas outlet pipe at the top is connected with an ammonia collector to recover the generated ammonia.
The slag washing water obtained after the filter pressing for several times contains manganese sulfate and 3-5 g/L ammonium sulfate, and a proper amount of ammonium sulfate is needed to be added to ensure that the ammonium sulfate content is 80-100g/L, so that the electrolysis can be performed, and the electrolyte after the electrolysis can return to the slag washing water.
In the electrolytic tank, a lead plate is used as an anode, stainless steel is used as a cathode, the voltage of the electrolytic tank is 4.2-4.5V, and the current is 180-200A/m 2 Effective area of small electrolytic manganese plate 0.036m 2 The yield of electrolytic manganese produced in 24 hours is more than 200g, and the yield of cathode plates and single plates of a conversion production line can be more than 3.3 kg; the current is the average current per square meter flowing through the active area of the cathode.
The device of the invention comprises: the functions and the working principles of the filter press, the stirring barrel, the electrolytic tank, the fermentation tank and the ammonia water collector are respectively introduced as follows:
1. the stirring barrel comprises a stirring barrel for washing waste residues in the earlier stage and a vulcanizing stirring barrel in the later stage; the method comprises the steps of starting a Roots blower, controlling the temperature of the stirring barrel to be 40-60 ℃ by hot air, reacting the crushed manganese slag with slag washing water, stirring to enable the reaction to occur faster, reacting to obtain dissolved metal sulfate, including manganese sulfate, ammonium sulfate and other metal salts, filtering after the reaction is completed, adding slag washing water into the obtained waste slag in a filter press to wash, wherein the mass ratio of the waste slag to the slag washing water is 0.3:1, repeatedly cleaning for a plurality of times, filtering and separating to obtain the cleaned waste slag and metal sulfate solution containing manganese sulfate and the like, and carrying out further harmless treatment on the waste slag; the vulcanizing agent and the impurity removing agent are added into the vulcanizing stirring barrel, so that manganese sulfate can be primarily purified, insoluble metal salt generated by the reaction can be removed, and most of impurities are removed.
2. The invention adopts a filter press for multiple times, mainly separates the completely reacted precipitate from the solution, presses the filter press until no water drops, separates out waste residue, manganese sulfate and other metal sulfate salts, and then separates out the completely reacted precipitate from the solution to obtain the purified manganese sulfate solution.
3. The electrolytic tank is used for electrolyzing manganese in manganese sulfate to obtain electrolytic manganese, after selenium dioxide is added into the manganese sulfate, a lead plate is used as an anode, stainless steel is used as a cathode, and specific current and voltage are passed through the electrolytic tank (the voltage of the electrolytic tank is 4.2-4.5V, and the current is 180-200A/m) 2 ) And (3) electrolyzing to obtain an electrolytic manganese crude product, and then passivating, desulfurizing, drying and stripping to obtain a high-purity electrolytic manganese product.
4. The fermentation tank is a sealed tank body, the tank body is ventilated, pulse dust collection equipment is arranged at the top of the tank body, an air extraction opening is arranged at the top of the tank body, the tank body is airtight, waste residues obtained by washing slag are added with calcium oxide and a free ion curing agent and are conveyed into the fermentation tank for fermentation, the temperature is continuously increased in the fermentation process, the water content is reduced, the fermentation product gradually tends to be stable in the fermentation process, ammonium salt is decomposed to generate ammonia gas during the period, the ammonia gas is recycled into an ammonia gas collector through the air extraction opening, after the fermentation is finished, the fermentation product is inspected, and the waste residues reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for concrete stirring; the waste residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
5. The ammonia collector is communicated with the top of the fermentation tank, after ammonia is generated by the fermentation tank, the ammonia collector is pumped into the ammonia collector from an extraction opening at the top of the fermentation tank, clear water is injected into the ammonia collector in advance, the ammonia is introduced into the clear water, ammonia water is formed by dissolution, and an exhaust opening is further formed in the ammonia collector, so that air is conveniently discharged.
The beneficial effects of the invention are as follows:
1. the normal waste manganese slag contains 1-2% of soluble manganese and 3-5% of ammonium sulfate, the soluble manganese and the ammonium are in a free form, and the water washing method can be used for washing out manganese and ammonium, and part of impurities can be simultaneously washed out. The method can recover manganese, ammonium sulfate and other substances in free state by using a small amount of harmless treatment agent, so that the soluble manganese and ammonium sulfate in free state in manganese slag are reduced; the method separates the waste residue from soluble metal sulfate such as manganese sulfate, ammonium sulfate and the like, then carries out impurity removal and filter pressing on the filtrate for a plurality of times, adds a vulcanizing agent, an impurity removing agent, an oxidizing agent and a purifying agent to purify the filtrate, removes heavy metals such as nickel, calcium and the like, and has the recovery rate of the soluble manganese and the ammonium sulfate up to more than 80 percent, wherein the manganese sulfate is electrolyzed to obtain a high-purity electrolytic manganese product, so that the recycling and sustainable development of resources are realized.
2. The invention carries on innocent treatment to the waste residue after washing and filter pressing, carries the waste residue to ferment in the fermenter, the effect of the waste residue ferment is to use calcium oxide and ferment reagent to fully react with ammonium sulfate, form ammonia, reduce ammonia nitrogen content in the waste residue, reach the quality standard of building materials, and add compound bacteria to carry on auxiliary ferment, can remove stink (organic matter) in the waste residue, accelerate the fermentation speed of the waste residue, the ammonia produced during the period can be transported to ammonia collector to recycle, achieve the rational utilization of resources, the waste residue after ferment reaches the national standard, can directly produce environment-friendly brick or be used as fine sand for concrete agitation, the invention can make waste residue change into valuables, realize the utilization of diversified resources, the treatment process of the invention is safe and environment-friendly, has no harmful gas generation, reduces the harm of manganese residue to the environment of China, and improves the problem of manganese residue piling.
3. According to the invention, the recovered manganese sulfate solution is electrolyzed to produce electrolytic manganese, the purity of the electrolytic manganese product is high, the sulfur content in the product is less than or equal to 0.02%, other impurities are less than the national standard, the manganese content in the product is more than or equal to 99.8%, the grade A product in DJMN99.7% grade is reached in the national standard, the heavy metal content is qualified, and the product quality is good.
4. In the method, the harmless waste residues are subjected to mass analysis after natural air drying, the pH value is less than or equal to 8, the manganese content is less than or equal to 1. 1mg/L, the ammonia nitrogen content is less than or equal to 1.0 mg/L, and the fermented waste residues which are not up to standard are heated and dried, and the mass analysis data of the waste residues are as follows: the pH value is less than or equal to 9, the manganese content is less than or equal to 0.1mg/L, the ammonia nitrogen content is less than or equal to 0.7mg/L, and the ammonia nitrogen content is smaller than the limit value of the national standard of the horizontal oscillation method of solid waste leaching toxicity leaching method (HJ 557-2010), the obtained waste residue accords with the national standard, can be used in the building material industry, and improves the recycling rate of manganese residue.
5. Compared with the methods of stacking waste residues, roasting at high temperature and the like, the method can treat the manganese residues at lower production cost, changes the manganese residues into valuable, improves the profit and the value of the manganese residues, has low cost, can realize industrial production, and solves the technical problems of high energy consumption and high cost caused by the requirement of high temperature; taking 3 ten thousand tons of electrolytic manganese products in production year as an example, calculated by using 13 percent manganese ore, the annual consumption ore can reach more than 30 ten thousand tons, the weight of the generated wet slag exceeds 40 ten thousand tons, the stacking cost of the average ton slag reaches 230 yuan (the early investment is calculated without interest), compared with the stacking slag, the economic benefit of more than 165 yuan per ton of slag (the production cost of each ton of slag is reduced) can be directly generated, the gap of about 400 yuan can be reached, compared with the stacking slag, the economic benefit of 12000 ten thousand yuan can be generated for 30 ten thousand tons of manganese slag per year, the investment is saved by 60 percent, and the economic benefit of manganese slag is improved (the investment of a slag warehouse is not needed by adopting the method).
6. The invention can recycle low-grade manganese ore and can also produce electrolytic manganese by a high-sulfur and high-iron ore three-ore process; and can utilize the waste gas recovery equipment, remove sulfuric acid mist, ammonia, hydrogen sulfide and dust pollution, the waste water treatment can reach good effect, and some new technologies have been tested and produced, reduce pollutant emission for a great deal of electrolytic manganese enterprises, be favorable to the nation to the improvement of manganese slag environmental pollution, have great significance to the reduction of burden for the manganese industry enterprise, benefit the country and people, increase economic benefits simultaneously.
Drawings
FIG. 1 is a process flow diagram of a method and apparatus for resource utilization and innocent treatment of manganese slag in accordance with the present invention.
Detailed Description
The present invention will be further described with reference to examples for more detailed description of the invention.
Example 1
A method and equipment for resource utilization and innocent treatment of manganese slag comprise the following steps:
(1) Putting the manganese slag into a pulverizer to pulverize, and sieving with a 60-mesh sieve;
(2) Adding clear water or slag washing water into the crushed manganese slag, introducing hot air, heating to 40 ℃, stirring and slurrying for 2 hours; the slag washing water is water after the first time or the nth time of filter pressing;
(3) After stirring completely, carrying out filter pressing on the mixture to obtain filter residues and filtrate, adding clear water into the filter residues or washing the residues for multiple times and filter pressing to obtain cleaned filter residues without manganese, and combining the filtrate for multiple times to obtain filtrate 1;
(4) The filtrate 1 was sulfidized: adding 0.1g/L sodium fermi to remove nickel in the filtrate 1, adding 0.2ml/L impurity removing agent after the reaction is completed, removing calcium, magnesium and other double salts, and performing filter pressing to obtain filtrate 2; the impurity removing agent is prepared by mixing ammonium bicarbonate, potassium permanganate and acetic acid according to a ratio of 0.5:2:0.1;
(5) Adding 0.15ml/L hydrogen peroxide to the filtrate 2 to remove iron, and after the reaction is completed, performing filter pressing to obtain filtrate 3;
(6) Adding 1.2ml/L purifying agent into the filtrate 3 for purification treatment, standing, and press-filtering to obtain filtrate 4; the purifying agent is prepared by mixing polymeric ferric chloride, polyacrylamide and high-purity ammonium sulfate in a ratio of 5:0.1:1;
(7) Adding 10mg/l of selenium dioxide into the filtrate 4, delivering the filtrate into an electrolytic tank for electrolysis for 24 hours, discharging the filtrate, passivating, desulfurizing, drying and stripping to obtain an electrolytic manganese product; during the electrolysis, adding ammonium sulfate into the continuously consumed solution to ensure that the solution can contain 80-100g/L of ammonium sulfate; in the electrolytic tank, a lead plate is used as an anode, stainless steel is used as a cathode, the voltage of the electrolytic tank is 4.3V, and the current is 200A/m 2 Effective area of small electrolytic manganese plate 0.036m 2 The yield of electrolytic manganese produced in 24 hours is more than 200g, and the yield of cathode plates and single plates of a conversion production line can be more than 3.3 kg;
(8) Carrying out mass analysis on the filter residue in the step (3) to obtain the contents of soluble manganese, ammonium sulfate, pH value, total iron, calcium, silicon and the like; adding calcium oxide powder and a free radical curing agent according to the analysis result of the soluble manganese, uniformly mixing, and crushing filter residues again to obtain powder;
(9) Conveying the crushed filter residues to a fermentation recovery tank, adding compound bacteria for fermentation for 24 hours, and conveying a large amount of ammonia generated during fermentation to an ammonia collector to prepare ammonia water; the composite bacteria are yeast, bacillus and EM bacteria, which are mixed according to the proportion of 1:1:1, and the adding amount is 1% of the mass of the filter residue;
(10) After the fermentation time is reached, discharging, sampling and analyzing; according to the analysis result, the filter residue reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for stirring concrete; the filter residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
Example 2
A method and equipment for resource utilization and innocent treatment of manganese slag comprise the following steps:
(1) Putting the manganese slag into a pulverizer to pulverize, and sieving with a 60-mesh sieve;
(2) Adding clear water or slag washing water into the crushed manganese slag, heating to 60 ℃, stirring and slurrying for 2 hours; the slag washing water is water after the first time or the nth time of filter pressing;
(3) After stirring completely, carrying out filter pressing on the mixture to obtain filter residues and filtrate, adding clear water into the filter residues or washing the residues for multiple times and filter pressing to obtain cleaned filter residues without manganese, and combining the filtrate for multiple times to obtain filtrate 1;
(4) The filtrate 1 was sulfidized: adding 0.1g/L sodium fermi to remove nickel in the filtrate 1, adding 0.2ml/L impurity removing agent after the reaction is completed, removing calcium, magnesium and other double salts, and performing filter pressing to obtain filtrate 2; the impurity removing agent is prepared by mixing ammonium bicarbonate, potassium permanganate and acetic acid according to a ratio of 1:2:0.1;
(5) Adding 0.15ml/L hydrogen peroxide to the filtrate 2 to remove iron, and after the reaction is completed, performing filter pressing to obtain filtrate 3;
(6) Adding 1.2ml/L purifying agent into the filtrate 3 for purification treatment, standing, and press-filtering to obtain filtrate 4; the purifying agent is prepared by mixing polymeric ferric chloride, polyacrylamide and high-purity ammonium sulfate in a ratio of 5:0.1:1;
(7) Adding 10mg/l selenium dioxide into the filtrate 4, delivering the filtrate into an electrolytic tank for electrolysis for 24 hours, discharging, passivating, desulfurizing, drying and stripping to obtain an electrolytic manganese product; during the electrolysis, adding ammonium sulfate into the continuously consumed solution to ensure that the solution can contain 80-100g/L of ammonium sulfate; in the electrolytic tank, a lead plate is used as an anode, stainless steel is used as a cathode, the voltage of the electrolytic tank is 4.3V, and the current is 200A/m 2 Effective area of small electrolytic manganese plate 0.036m 2 The yield of electrolytic manganese produced in 24 hours is more than 200g, and the yield of cathode plates and single plates of a conversion production line can be more than 3.3 kg;
(8) Carrying out mass analysis on the filter residue in the step (3) to obtain the contents of soluble manganese, ammonium sulfate, pH value, total iron, calcium, silicon and the like; adding calcium oxide powder and a free radical curing agent according to the analysis result of the soluble manganese, uniformly mixing, and crushing filter residues again to obtain powder;
(9) Conveying the crushed filter residues to a fermentation recovery tank, adding compound bacteria for fermentation for 18 hours, and conveying a large amount of ammonia generated during fermentation to an ammonia collector to prepare ammonia water; the composite bacteria are yeast, bacillus and EM bacteria, which are mixed according to the proportion of 3:1:1, and the addition amount is 0.5% of the mass of the filter residue;
(10) After the fermentation time is reached, discharging, sampling and analyzing; according to the analysis result, the filter residue reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for stirring concrete; the filter residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
Example 3
A method and equipment for resource utilization and innocent treatment of manganese slag comprise the following steps:
(1) Putting the manganese slag into a pulverizer to pulverize, and sieving with a 60-mesh sieve;
(2) Adding clear water or slag washing water into the crushed manganese slag, introducing hot air, heating to 50 ℃, stirring and slurrying for 2 hours; the slag washing water is water after the first time or the nth time of filter pressing;
(3) After stirring completely, carrying out filter pressing on the mixture to obtain filter residues and filtrate, adding clear water into the filter residues or washing the residues for multiple times and filter pressing to obtain cleaned filter residues without manganese, and combining the filtrate for multiple times to obtain filtrate 1;
(4) The filtrate 1 was sulfidized: adding 0.1g/L sodium fermi to remove nickel in the filtrate 1, adding 0.2ml/L impurity removing agent after the reaction is completed, removing calcium, magnesium and other double salts, and performing filter pressing to obtain filtrate 2; the impurity removing agent is prepared by mixing ammonium bicarbonate, potassium permanganate and acetic acid according to a ratio of 0.8:2:0.1;
(5) Adding 0.15ml/L hydrogen peroxide to the filtrate 2 to remove iron, and after the reaction is completed, performing filter pressing to obtain filtrate 3;
(6) Adding 1.2ml/L purifying agent into the filtrate 3 for purification treatment, standing, and press-filtering to obtain filtrate 4; the purifying agent is prepared by mixing polymeric ferric chloride, polyacrylamide and high-purity ammonium sulfate in a ratio of 5:0.1:1;
(7) Adding 10mg/l selenium dioxide into the filtrate 4, delivering the filtrate into an electrolytic tank for electrolysis for 24 hours, discharging, passivating, desulfurizing, drying and stripping to obtain an electrolytic manganese product; during the course of the electrolysis,adding ammonium sulfate into the continuously consumed solution to ensure that the solution can contain 80-100g/L of ammonium sulfate; in the electrolytic tank, a lead plate is used as an anode, stainless steel is used as a cathode, the voltage of the electrolytic tank is 4.3V, and the current is 200A/m 2 Effective area of small electrolytic manganese plate 0.036m 2 The yield of electrolytic manganese produced in 24 hours is more than 200g, and the yield of cathode plates and single plates of a conversion production line can be more than 3.3 kg;
(8) Carrying out mass analysis on the filter residue in the step (3) to obtain the contents of soluble manganese, ammonium sulfate, pH value, total iron, calcium, silicon and the like; adding calcium oxide powder and a free radical curing agent according to the analysis result of the soluble manganese, uniformly mixing, and crushing filter residues again to obtain powder;
(9) Conveying the crushed filter residues to a fermentation recovery tank, adding compound bacteria for fermentation for 12 hours, and conveying a large amount of ammonia generated during fermentation to an ammonia collector to prepare ammonia water; the composite bacteria are yeast, bacillus and EM bacteria, which are mixed according to the proportion of 2:1:1, and the adding amount is 1% of the mass of the filter residue;
(10) After the fermentation time is reached, discharging, sampling and analyzing; according to the analysis result, the filter residue reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for stirring concrete; the filter residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
Electrolytic manganese product quality analysis
The electrolytic manganese products obtained by electrolytic production of the manganese sulfate solution in the embodiments 1-3 of the present invention were subjected to quality detection according to the national standard YB/T051-2015 electrolytic manganese metal industry standard, and the detection results are shown in Table 1.
As can be seen from the product quality data in Table 1, the impurity data in the electrolytic manganese product produced by the method is lower than the corresponding impurity indexes in the national standard, and reaches the grade A product in DJMN99.7% grade in the standard, so that the electrolytic manganese product produced by the method has good quality and high quality.
Manganese slag (innocuous) mass analysis:
the fermented waste residue in the embodiment 1 of the present invention was subjected to mass analysis, and the mass analysis results are shown in table 2:
as can be seen from the table, the waste residue which does not reach the standard in the fermentation tank is heated and dried, and the pH value, the manganese content and the ammonia nitrogen content are all within the limit value range of the national standard, so that the waste residue can be used for cement mixture; and the indexes of the fermented waste residues reaching the standards are in the limit value range of the national standard after natural air drying, so that the fermented waste residues can be used for producing environment-friendly bricks, and the environment-friendly bricks have good overall quality.
Claims (9)
1. A method and equipment for resource utilization and innocent treatment of manganese slag are characterized by comprising the following steps:
(1) Putting the manganese slag into a pulverizer to pulverize, and sieving with a 60-mesh sieve;
(2) Adding clear water or slag washing water into the crushed manganese slag, heating to 40-60 ℃, stirring and slurrying for 2 hours;
(3) After stirring completely, carrying out filter pressing on the mixture to obtain filter residues and filtrate, adding clear water into the filter residues or washing the residues for multiple times and filter pressing to obtain cleaned filter residues without manganese, and combining the filtrate for multiple times to obtain filtrate 1;
(4) The filtrate 1 was sulfidized: adding 0.1g/L sodium fermi to remove nickel in the filtrate 1, adding 0.2ml/L impurity removing agent after the reaction is completed, removing calcium, magnesium and other double salts, and performing filter pressing to obtain filtrate 2;
(5) Adding 0.15ml/L hydrogen peroxide to the filtrate 2 to remove iron, and after the reaction is completed, performing filter pressing to obtain filtrate 3;
(6) Adding 1.2ml/L purifying agent into the filtrate 3 for purification treatment, standing, and press-filtering to obtain filtrate 4;
(7) Adding an electrolysis additive selenium dioxide into the filtrate 4, delivering the filtrate into an electrolytic tank for electrolysis for 24 hours, discharging the filtrate, passivating, desulfurizing, drying and stripping to obtain an electrolytic manganese product;
(8) Carrying out mass analysis on the filter residue in the step (3) to obtain the contents of soluble manganese, ammonium sulfate, pH value, total iron, calcium, silicon and the like; adding calcium oxide powder and a free radical curing agent according to the analysis result of the soluble manganese, uniformly mixing, and crushing filter residues again to obtain powder;
(9) Conveying the crushed filter residues to a fermentation recovery tank, adding compound bacteria to ferment for 12-24 hours, and conveying a large amount of ammonia generated during fermentation to an ammonia collector to prepare ammonia water;
(10) After the fermentation time is reached, discharging, sampling and analyzing; according to the analysis result, the filter residue reaching or approaching the standard can be directly used for producing environment-friendly bricks or used as fine sand for stirring concrete; the filter residue which does not reach the standard can be heated to 300 ℃ by a dryer and baked for 2 hours until the quality of the filter residue reaches the standard, and can be used as a cement mixture.
2. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the slag washing water in the step (2) is water after the first or n-th filter pressing.
3. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the impurity removing agent in the step (4) is a mixture of ammonium bicarbonate, potassium permanganate and acetic acid.
4. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the purifying agent in the step (6) is a mixture of polymeric ferric chloride, potassium permanganate and high-purity ammonium sulfate.
5. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the adding amount of selenium dioxide in the step (7) is 10mg/l.
6. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the composite bacteria in the step (9) are mixed by saccharomycetes, bacillus and EM bacteria according to the ratio of 1-3:1:1, and the addition amount is 0.5-1% of the mass of the filter slag.
7. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the adopted equipment comprises a wet crusher, a stirring barrel, a vulcanization stirring barrel, a Roots blower, a filter press, an electrolytic tank, a fermentation tank, an ammonia collector and parts matched with the wet crusher, the stirring barrel, the vulcanization stirring barrel, the Roots blower, the filter press, the electrolytic tank and the fermentation tank; the stirring barrel is internally provided with a stirring motor, a Roots blower and a temperature sensor.
8. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the fermentation tank is provided with a pulse dust collection device and an extraction opening at the top, the tank body is airtight, and a gas outlet pipe at the top is connected with an ammonia collector to recover the generated ammonia.
9. The method for resource utilization and innocent treatment of manganese slag according to claim 1, wherein the electrolytic bath is characterized in that a lead plate is used as an anode, stainless steel is used as a cathode, the voltage of the electrolytic bath is 4.2-4.5V, and the current is 180-200A/m 2 Effective area of small electrolytic manganese plate 0.036m 2 The yield of electrolytic manganese produced in 24 hours is more than 200g, and the yield of cathode plates and single plates of a conversion production line can be more than 3.3 kg.
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| CN117024098A (en) * | 2023-08-14 | 2023-11-10 | 北京建工环境修复股份有限公司 | Electrolytic manganese slag hydrothermal self-curing building material and preparation method thereof |
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| CN117024098A (en) * | 2023-08-14 | 2023-11-10 | 北京建工环境修复股份有限公司 | Electrolytic manganese slag hydrothermal self-curing building material and preparation method thereof |
| CN117024098B (en) * | 2023-08-14 | 2024-04-02 | 北京建工环境修复股份有限公司 | Electrolytic manganese slag hydrothermal self-curing building material and preparation method thereof |
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