CN110467365A - The sulfur method of electrolytic manganese press filtration residues and method using the desulfurization manganese slag cement - Google Patents
The sulfur method of electrolytic manganese press filtration residues and method using the desulfurization manganese slag cement Download PDFInfo
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- CN110467365A CN110467365A CN201910829401.0A CN201910829401A CN110467365A CN 110467365 A CN110467365 A CN 110467365A CN 201910829401 A CN201910829401 A CN 201910829401A CN 110467365 A CN110467365 A CN 110467365A
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- manganese
- desulfurization
- residues
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 184
- 239000011572 manganese Substances 0.000 title claims abstract description 184
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 89
- 230000023556 desulfurization Effects 0.000 title claims abstract description 88
- 239000002893 slag Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001914 filtration Methods 0.000 title claims abstract description 46
- 239000004568 cement Substances 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 34
- 239000011593 sulfur Substances 0.000 title claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 29
- 239000010440 gypsum Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 229910001570 bauxite Inorganic materials 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- 239000000428 dust Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000006028 limestone Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000004683 dihydrates Chemical class 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910020489 SiO3 Inorganic materials 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052634 enstatite Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000012512 characterization method Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 8
- 238000007906 compression Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000002742 anti-folding effect Effects 0.000 abstract description 6
- 238000007873 sieving Methods 0.000 abstract description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 24
- 238000002791 soaking Methods 0.000 description 21
- 238000005245 sintering Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000005864 Sulphur Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011083 cement mortar Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 235000011132 calcium sulphate Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001978 electrochemical passivation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910007266 Si2O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 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
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The present invention provides a kind of sulfur method of electrolytic manganese press filtration residues and the methods for preparing cement with the desulfurization manganese slag that this doctor treatment obtains, the following steps are included: electrolytic manganese press filtration residues are mixed with auxiliary additive, it is calcined and is cooled down, obtain desulfurization manganese slag, then it is mixed with clinker and gypsum, ball milling, sieving, finally obtained cement of the desulfurization manganese slag as mixing material.Sulfur method provided by the invention is simple and efficient, and desulphurizing ratio is high, meanwhile, cement made from the desulfurization manganese slag with the method for the present invention acquisition, anti-folding all meets related strength of cement requirement to compression strength.The present invention is not only that the rational utilization of electrolytic manganese press filtration residues has widened new method, also constructs the circular economy of electrolytic manganese industry.
Description
Technical field
The present invention relates to a kind of processing methods of metal smelt waste residue, and in particular to a kind of electrolytic manganese press filtration residues desulfurization
The application of manganese filter-press residues after method and desulfurization.
Background technique
Electrolytic manganese metal occupies highly important strategic position in national economy, in modern industry, manganese and its chemical combination
Object is applied to the every field of national economy.Wherein steel and iron industry is most important field, accounts for 90%~95% with manganese amount, master
It will be as the deoxidier and desulfurizing agent in ironmaking and steelmaking process, and for manufacturing alloy.Remaining 5%~10% manganese is used
In other industrial circles, such as chemical industry (manufacturing various manganese containing salt classes), light industry (for battery, print paint), building materials industry
(colorant and decolourant of glass and ceramics), national defense industry, electronics industry, and environmental protection and farming and animal husbandry, etc..Always
It, manganese has highly important strategic position in national economy, and the country of manganese deficiency stores it as war preparedness substance.
By the development of nearly half a century, China has become the maximum electrolytic manganese producing country in the whole world, country of consumption, exported country.
Electrolytic manganese metal is made that larger contribution as a kind of important metallurgy, chemical raw material, for China's rapid industrial development.But
Electrolytic manganese industry also belongs to resource, energy consumption height, the industrial trade of environmental pollution weight.
Although technical level increases in recent years, environmental protection work is reinforced, and electrolytic manganese manufacturing enterprise exists
It is polluted the environment in production process still serious.Electrolytic manganese production includes crushing, acidolysis filters pressing, electrolytic passivation, removes and do
The technical process such as dry.Dust, poisonous fume result from crushing, drying, acidolysis, electrolytic process；Waste water mainly have waste electrolyte,
The pole plate ejected wash water of useless passivating solution, acidolysis filters pressing waste water and electrolytic passivation process；Discarded object of power boiler discharge is what acidolysis generated
The earth of positive pole that tailing and electrolytic process generate.Have that the survey showed that, sulfuric acid in the solid waste that electrolytic manganese production generates
The very high concentrations of salt, ammonia nitrogen, manganese, highest respectively reach 63324,2987,34762mg/kg, and arsenic, mercury, the concentration of selenium are also higher,
Maximum value is respectively up to 38.9,32.3,30.8mg/kg.The maximum times of ultra standard of ammonia nitrogen, manganese, mercury, arsenic in outlet industrial wastewater
Respectively reach 6.26,1.58,6.8,1.03.The production activity of enterprise to the surface water on enterprise periphery, underground water, bed mud in river,
Soil causes serious pollution.
It being analyzed from available data, the enterprise of foreign countries' production electrolytic manganese is seldom, and the research achievement about electrolytic manganese residues is few,
It is only to be only about harm of the manganese to environment in manganese slag muck field.And China's electrolytic manganese residues were studied also in the basic starting stage,
To its basic performance, the performance study of especially comprehensive utilization angle seems to be lacked very much, and accumulation is still processing electrolytic manganese residues
Main method, existing harmlessness disposing mode is almost blank, and main basic research Land use systems include following several
Aspect: (1) using electrolytic manganese residues gypsum is replaced to be used as cement retarder；(2) construction material is produced；(3) electrolytic manganese residues are utilized
Make materials for wall；Other than mode utilized above, there is research that ultrasonic wave added acid is also utilized to extract the manganese in electrolytic manganese residues for it
Its purposes and utilization electrolytic manganese waste residue replace anthracite and clay, in addition the carbonization of sulphur-fixing agent quick lime, the dual work of gypsification
With, production civil honeycomb briquette, but all also need to verify for a long time due to various reasons, therefore also do not come into operation.
In conclusion domestic also fewer to the research of electrolytic manganese residues at present, most Land use systems are all in test rank
Section, and result of study few in number tends to be used as the retarder for cement, mainly imagines and utilizes electrolytic manganese residues
In calcium sulphate dihydrate, by the analysis to electrolytic manganese production technology, sulfate contained in electrolytic manganese residues in addition to part with
Outside dihydrate gypsum form exists, also contain other form sulfate, and the content of sulfate is in separate sources electrolytic manganese residues
Different, their effects played in building material industry are not also identical.In addition, the ammonium sulfate in filter-press residues, in water
OH- is consumed in muddy water gelatinization, harmful side effect is generated to concrete product.But come from existing documents and materials introduction
It sees, is that its whole is converted into dihydrate gypsum and is used, this is right when being related to the utilization of sulfate in electrolytic manganese residues
The building resource of electrolytic manganese residues is using can bring detrimental effect.Therefore, one of sulfate in electrolytic manganese residues is fully understood
A little fundamental propertys are the premises that electrolytic manganese residues utilize.
Summary of the invention
Based on above-mentioned technical background, present inventor has performed with keen determination, utilize and generate during Process of Electrolytic Manganese
Electrolytic Manganese Metal Residues through natural cooling, desulfurization manganese slag is obtained, then by it by mixing, calcining with auxiliary additive
It is mixed with clinker and gypsum, ball milling, sieving, finally obtained cement of the desulfurization manganese slag as mixing material.Through the present invention
The desulfurization manganese slag that method desulfurization obtains, sulfur content is lower, and its cement as mixing material preparation, anti-folding and pressure resistance
Degree all meets related strength of cement requirement.Sulfur method provided by the invention is simple and efficient, and is not only electrolytic manganese press filtration residues
Rational utilization has widened new method, also constructs the circular economy of electrolytic manganese industry.Therefore, the first aspect of the present invention mentions
Supply a kind of sulfur method of electrolytic manganese press filtration residues, comprising the following steps:
(1) electrolytic manganese press filtration residues are mixed with auxiliary additive；
(2) mixed material is calcined；
(3) cooling, obtain desulfurization manganese slag.
The second aspect of the present invention provides the method that electrolytic manganese press filtration residues after a kind of desulfurization prepare cement, after desulfurization
Electrolytic manganese press filtration residues mixed with clinker and gypsum, after measured, electrolytic manganese press filtration residues after inventive desulfurization with
Manufactured cement after clinker and gypsum mixing, resistance to compression and flexural strength can meet related strength of cement requirement.
Cement made of manganese filter-press residues after electrolytic manganese press filtration residues sulfur method provided by the invention and thus method desulfurization
Glue sand has the advantage that
(1) sulfur method provided by the invention is simple and efficient, and can reach higher desulfurization in a very short period of time
Rate；
(2) cement that the manganese filter-press residues after inventive desulfurization and clinker and gypsum are mixed, is attained by phase
Close strength of cement requirement；
(3) present invention rationally utilizes electrolytic manganese press filtration residues, while sufficiently recycling element sulphur, building electrolytic manganese industry circulation
It is economical；
(4) new method has been widened for the rational utilization of resource.
Detailed description of the invention
Fig. 1 is the XRD spectra of sintered product after calcining under manganese filter-press residues and bauxite different temperatures；
Fig. 2 is that manganese filter-press residues and bauxite are calcined under different time, the XRD spectra of sintered product；
Fig. 3 is manganese filter-press residues and bauxite different calcium silicon than calcining under coefficient, the XRD spectra of sintered product；
Fig. 4 is the XRD spectra of sintered product after calcining under manganese filter-press residues and 15% lime stone different temperatures；
Fig. 5 is the XRD spectra of sintered product after manganese filter-press residues and the calcining of+5% carbon dust of manganese filter-press residues.
Specific embodiment
The present invention is described in detail below, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
First aspect present invention provides a kind of sulfur method of electrolytic manganese press filtration residues, the described method comprises the following steps:
(1) electrolytic manganese press filtration residues are mixed with auxiliary additive；
(2) mixed material is calcined；
(3) cooling, obtain desulfurization manganese slag.
The step is specifically described and is illustrated below.
Step (1) electrolytic manganese press filtration residues are mixed with auxiliary additive.
In step of the present invention (1), first electrolytic manganese press filtration residues are dried and crushed, then it is mixed with auxiliary additive.
Since electrolytic manganese press filtration residues are half-dried slag, need to dry it before crushing.
Since manganese filter-press residues will form liquid phase in calcination process, viscosity is very big after cooling, is not easy to take the dish out of the pot, be unfavorable for
Production operation.Therefore, addition auxiliary additive is needed in calcining sweetening process, and element sulphur is made to be easier that removing is precipitated.
According to the present invention, in the step, the very high concentrations of sulfate, ammonia nitrogen, manganese, highest in the electrolytic manganese press filtration residues
Respectively reach 63324,2987,34762mg/kg, arsenic, mercury, the concentration of selenium are also higher, maximum value respectively up to 38.9,32.3,
30.8mg/kg。
A kind of preferred embodiment according to the present invention, silicon is mainly deposited in the form of quartzy phase in the electrolytic manganese press filtration residues
Calcium mainly mutually exists with the object of dihydrate gypsum, and magnesium exists in the form of magnesium sulfate, and potassium sodium mutually exists with feldspar.
In this step, the auxiliary additive is additive containing aluminium, lime stone, carbon dust and calcium additive.Preferably aluminium adds
Add agent and carbon dust, more preferably bauxite, especially contains more AlO (OH), Al2Si2O(OH)4(correspond to diaspore
And kaolin) bauxite.
When auxiliary additive is carbon dust, manganese filter-press residues equally will form liquid phase in calcination process, and viscosity is non-after cooling
Chang great is not easy to take the dish out of the pot, is unfavorable for production operation.
When auxiliary additive is calcium additive, temperature is too low, is unfavorable for the decomposition of sulfate in manganese filter-press residues, and temperature is high
When 1200 DEG C, manganese filter-press residues have then been burnt into glass phase, are unfavorable for the precipitation of element sulphur.
When auxiliary additive is bauxite, the electrolytic manganese press filtration residues can reach higher under lower calcination temperature
Desulfurization degree.
In step of the present invention (1), the additive amount of the auxiliary additive are as follows: the electrolytic manganese residues based on 10 parts by weight, it is auxiliary
Helping additive is 0.5~40 parts by weight, preferably 1~30 parts by weight, more preferably 2~25 parts by weight.
The calcining of step (2) mixed material.
The auxiliary additive and electrolytic manganese residues are mixed and are placed on horse by a kind of preferred embodiment according to the present invention
Not calcined in furnace.
In step of the present invention (2), the calcination temperature be 400~1500 DEG C, preferably 600~1400 DEG C, more preferably
It is 900~1400 DEG C.
According to the heat analysis to electrolytic manganese residues, mainly adsorbed before four: 200 DEG C are broadly divided between pyrolysis zone
The partial detachment of the crystallization water of the desorption and hydrated sulfates of water loses if dihydrate gypsum loses partially crystallizable water at 150 DEG C
Rate 9.13% again；Second decomposition temperature area is 300~600 DEG C, and in terms of object phase interpretation of result, this humidity province is mainly table
The dehydration of face hydroxyl, the decomposition of ammonium sulfate, the reactions such as decomposition of partially crystallizable water of sulfate are constituted；Third resolver be from
600 DEG C~950 DEG C, this temperature range is mainly the decomposition of sulfate and the decomposition of trace carbonate, generates gas-phase presulfiding
Object and metal oxide, weight-loss ratio 8.61%；4th resolver is 950 DEG C~1150 DEG C, the decomposition reaction of this decomposition region
Based on the thermal decomposition of calcium sulfate, SO is generated3Or SO2。
In the thermal decomposition process of electrolytic manganese, SO is just had later from 400 DEG C3Release, therefore desulfurization calcining of the invention
Temperature is not less than 400 DEG C.
According to the present invention, in the step, the mixed material calcination time be 2~90min, preferably 2~60min, more
Preferably 5~20min.
The too short removing for being unfavorable for element sulphur of calcination time, calcination time is too long, and it will cause the wastes of resource, while
It will affect manganese filter-press residues desulfuration efficiency.
Step (3) is cooling, obtains desulfurization manganese slag.
The calcined electrolytic manganese press filtration residues of step (2) are cooling, obtain desulfurization manganese slag.Preferably, described to be cooled to nature
It is cooling.
A kind of preferred embodiment according to the present invention, desulfurization manganese slag obtained, sulphur contain after the method for the present invention desulfurization
Amount≤0.48%, and the object contained is mutually Al through XRD characterization2O3、Ca(Al2Si2O8)、Al2(SiO3)3、MgSiO3。
The second aspect of the present invention provides the side that a kind of electrolytic manganese press filtration residues after the method for the present invention desulfurization prepare cement
Method the described method comprises the following steps:
(1) desulfurization manganese filter-press residues are mixed with clinker and gypsum；
(2) by mixture ball milling；
The step is specifically described and is illustrated below.
Step (1) mixes desulfurization manganese filter-press residues with clinker and gypsum.
In step of the present invention (1), desulfurization manganese filter-press residues, clinker and gypsum are mixed into mixture.
The desulfurization manganese filter-press residues are the manganese filter-press residues obtained by above method desulfurization of the present invention.Preferably use bauxite
As manganese filter-press residues obtained by auxiliary additive desulfurization, more preferably bauxite and electrolytic manganese residues amount ratio is 11.6:10 desulfurization
Obtained by manganese filter-press residues.
In this step, the clinker is Portland clinker.
According to the present invention, in this step, the type of gypsum is not limited.
In step of the present invention (1), the dosage of desulfurization manganese slag, clinker and gypsum is respectively as follows: based on 1 parts by weight
Gypsum, 1~5 parts by weight of desulfurization manganese slag, clinker 14~20.
A kind of preferred embodiment according to the present invention, based on the gypsum of 1 parts by weight, 1~4 parts by weight of desulfurization manganese slag, water
Mud clinker 16~18.
According to further preferred embodiment, based on the gypsum of 1 parts by weight, 1.2~3 parts by weight of desulfurization manganese slag, cement
Clinker 17~18.
Step (2) is by mixture ball milling.
In step of the present invention (2), the mixture in step (1) is put into ball milling in conical ball mill.
A kind of preferred embodiment according to the present invention is sieved after the mixture ball milling, guarantee mixture fineness≤
0.08mm。
According to further preferred embodiment, 200 mesh or 250 meshes are crossed after the mixture ball milling, preferably
250 meshes.Cement powder granularity is smaller, and powder active is higher, and the anti-folding and compression strength of prepared cement are higher.
A kind of preferred embodiment according to the present invention, it is equal through the anti-folding of cement made from the method for the present invention and compression strength
Meet the strength criterion of related cement.
Possessed by of the invention the utility model has the advantages that
(1) sulfur method provided by the invention is simple and efficient, and can reach higher desulfurization in a very short period of time
Rate, through desulfurization manganese slag sulfur content≤0.48% produced by the present invention；
(2) cement being mixed through desulfurization manganese slag produced by the present invention and clinker and gypsum, anti-folding and resistance to compression
Intensity is attained by related strength of cement requirement；
(3) cement produced by the present invention not only solves electrolytic manganese press filtration using the electrolytic manganese press filtration residues after desulfurization as raw material
Slag largely stacks the problems such as occupying living land, polluted-water and destroying periphery ecological environment, also reduces being produced into for cement
This.
(4) present invention rationally utilizes electrolytic manganese press filtration residues, while sufficiently recycling element sulphur, building electrolytic manganese industry circulation
It is economical；
(5) new method has been widened for the rational utilization of resource.
Embodiment
Below by way of specific example, the present invention is further explained, these embodiments are only limitted to illustrate the present invention, rather than
Limit the scope of the invention.
1 electrolytic manganese press filtration residues desulfurization of embodiment
It takes the drying of 16.9g electrolytic manganese press filtration residues, crush, it is mixed with 33.1g bauxite.Obtain manganese slag+bauxite calcium
The mixture that silicon is 1.3 than coefficient.
Mixed material is placed in Muffle furnace and is calcined, is warming up to 1250 DEG C, keeps the temperature 5min, it is then naturally cold
But to room temperature.The XRD spectrum of its sintered product is as shown in Figure 2.
2 electrolytic manganese press filtration residues desulfurization of embodiment
The preparation process of embodiment 1 is repeated, difference is only that, calcination temperature is 1300 DEG C, soaking time 20min.Its
The XRD spectrum of sintered product is as shown in Figure 1.
Embodiment 3
The preparation process of embodiment 1 is repeated, difference is only that, the sintering soak time is 20min, the XRD of sintered product
Map is as shown in Figure 1.
Embodiment 4
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 255.6g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 144.6g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 0.8 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 5
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 229.1g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 170.9g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 0.9 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 6
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 203.9g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 196.1g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 1.0 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 7
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 184.9g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 215.1g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 1.1 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 8
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 157.6g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 242.4g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 1.2 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 9
The preparation process of embodiment 1 is repeated, difference is only that, is taken the drying of 114.3g electrolytic manganese press filtration residues, is crushed, by it
It is mixed with 285.7g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 1.4 than coefficient.The XRD diagram of its sintered product
Spectrum is as shown in Figure 3.
Embodiment 10
Repeat the preparation process of embodiment 1, difference is only that, take the drying of 314g electrolytic manganese press filtration residues, crush, by its with
The mixing of 86g bauxite.Obtain the mixture that manganese slag+bauxite calcium silicon is 0.6 than coefficient.The XRD spectrum of its sintered product is as schemed
Shown in 3.
Embodiment 11
The preparation process of embodiment 1 is repeated, difference is only that, is taken 50g manganese filter-press residues not add any auxiliary additive and is forged
Burn 20min.The XRD spectrum of its sintered product is as shown in Fig. 5.
Embodiment 12
The preparation process of embodiment 1 is repeated, difference is only that, take 50g manganese filter-press residues and 7.5g lime stone to be mixed,
1250 DEG C of calcining 20min.The XRD map of its sintered product is as shown in Figure 4.
Embodiment 13
The preparation process of embodiment 12 is repeated, difference is only that, calcination temperature is 1300 DEG C.The XRD diagram of its sintered product
Spectrum is as shown in Figure 4.
Embodiment 14
Repetition is the preparation process of embodiment 1, and difference is only that, 50g manganese filter-press residues and 2.5g carbon dust is taken to be mixed,
Calcine 20min.The XRD spectrum of its sintered product is as shown in Figure 5.
Manganese filter-press residues and clinker and gypsum after 15 desulfurization of embodiment are mixed with cement
Desulfurization manganese slag made from Example 7, clinker and gypsum mixing, are subsequently placed in ball milling in conical ball mill, by ball
Mixture after mill crosses 200 meshes, and screen over-size < 10%, and mixture fineness is made to be less than or equal to 0.08mm, and cement is made.
Experimental example
Experimental example 1X ray fluorescence analysis
X-ray fluorescence analysis is carried out to manganese filter-press residues and bauxite with x-ray fluorescence analyzer, for detecting electrolytic manganese
Element species contained in filter-press residues and bauxite and content.The results are shown in Table 1.
1 raw material main component (%) of table
From table 1 it follows that containing 26% heating SO in manganese filter-press residues3, calcium oxide content 7.65%, content of MgO
It is relatively high to reach 4% or more, it must be taken into consideration in the application, furthermore K, Na ion concentration are relatively high in raw material；Bauxite mainly contains
There are aluminium and Si oxide, Ti content is higher.
2 X-ray powder diffraction of experimental example (XRD)
Using the great member X-2700X type X-ray diffractometer (XRD) in Dandong, operating voltage 40kV, electric current 40mA, scanning
2 θ of range=0-80 ° carry out material phase analysis to sample.
1) by 50g manganese filter-press residues and bauxite calcium silicon than coefficient be 1.3 mixed material respectively at 1250 DEG C, 1300 DEG C
Soaking time is to be sintered under the conditions of 20 minutes and (respectively correspond embodiment 3 and embodiment 2), sintered product is milled laggard
Row XRD characterization result.As a result as shown in Fig. 1.
From figure 1 it appears that sintered product contains Al2O3、Ca(Al2Si2O8)、Al2(SiO3)3、 MgSiO3Equal silicic acid
Salt object phase, does not detect sulfate and the substance containing element sulphur, illustrates that the sulfate in the desulfurization manganese slag has decomposed,
Tentatively illustrate that desulfurization effect is relatively good.1250 DEG C, 1300 DEG C of soaking times be 20 minutes under the conditions of, manganese filter-press residues add aluminium alum
To detected object mutually roughly the same than sintered product that coefficient is 1.3 for native calcium silicon, so sintering under the conditions of 1250 DEG C.
Energy consumption can be reduced by reducing sintering temperature, reduce production cost.
2) by 50g manganese filter-press residues and bauxite calcium silicon than coefficient be 1.3 1250 DEG C of soaking times be respectively 5 minutes and
It is sintered under the conditions of 20 minutes and (respectively corresponds embodiment 1 and embodiment 3), XRD test is carried out after sintered product is milled.
As a result as shown in Figure 2.
As shown in Figure 2, contain Al in the sintered product that 1250 DEG C of soaking times are 5 minutes2O3、Ca(Al2Si2O8)、Al2
(SiO4)O、Mg(SiO3) etc. silicates object phase, do not detect sulfate and the substance containing element sulphur, illustrate the manganese filters pressing
Sulfate in slag has decomposed, and preliminary explanation is that 5 minutes manganese filter-press residues desulfurization effects are relatively good in 1250 DEG C of soaking times.
The object phase of 20 minutes sintered products of soaking time and soaking time are 5 minutes roughly the same, are not all detected
Sulfate and sulfur-bearing at phase substance, so electrolytic manganese press filtration residues add bauxite in 1250 DEG C, soaking time to be 5 minutes conditions
Lower sintering.Energy consumption can be reduced by reducing sintering time, reduce production time and production cost.
3) add bauxite calcium silicon than coefficient to be respectively 0.6 400g manganese filter-press residues, 0.8,0.9,1.0,1.1,1.2,1.3,
1.4 mixed material, be sintered under conditions of 1250 DEG C of soaking times are 5 minutes (respectively correspond embodiment 10,4,5,
6,7,8,1 and 9), XRD test is carried out after sintered product is milled.As a result as shown in Figure 3.
From the figure 3, it may be seen that calcium silicon contains Al than the sintered product that coefficient is 0.62O3、Ca(Al2 Si2O8)、Al2(SiO4)3、
MgSiO3Equal silicates object phase, and calcium silicon is than substantially phase that the sintered product that coefficient is 0.8-1.4 is 0.6 with calcium silicon coefficient ratio
Together, sulfate and the substance containing element sulphur are not detected, illustrate that the sulfate in the manganese filter-press residues has decomposed.
4) by 50g manganese filter-press residues add 15% lime stone respectively 1250 DEG C, 1300 DEG C of soaking times be 20 minutes under the conditions of
It is sintered and (respectively corresponds embodiment 12 and embodiment 13), XRD test is carried out after product sinters are milled.As a result such as Fig. 4 institute
Show.
The peak XRD disperse in Fig. 4 is similar to random glass phase substance, can't detect the object phase of sintered product, cold
But its viscosity is very big after, is not easy to discharge, do so sintering temperature at 1250 DEG C or more, adds lime stone to be unfavorable for manganese filter-press residues
The production operation of activity of cement material, therefore other additives are added, while advantageously reducing desulfurization temperature.
5) by 50g manganese filter-press residues and+5% carbon dust of manganese filter-press residues 1250 DEG C, soaking time be 20 minutes under conditions of into
Row sintering (respectively corresponding embodiment 11 and embodiment 14) carries out XRD test after product is milled.As a result as shown in Figure 5.
From figure 5 it can be seen that compared to the sintered product that the manganese filter-press residues that carbon dust is calcined under the conditions of 1250 DEG C are not added,
Having added the manganese filter-press residues sintered product of 5% reproducibility carbon has peak value appearance, it was demonstrated that has crystal generation, measures through XRD main
Object is mutually the substances such as quartz, MgS, and reproducibility carbon dust is added to manganese filter-press residues in preliminary proof during being sintered manganese filter-press residues
Bad desulfurization effects.The manganese filter-press residues that 5% carbon dust is added during the sintering process also will form liquid phase, it is cooling after its viscosity very
Greatly, it is not easy to take the dish out of the pot, is unfavorable for production operation.
The test of 3 fume component analysis of experimental example
Fume component analysis uses high-temperature flue gas analysis system (Germany) on-line checking, and detection ingredient includes SO2, NOx,
CO, CO2, O2And flue-gas temperature.
The manganese pressure that calcium silicon is respectively 0.6,0.8,0.9,1.0,1.1,1.2,1.3 and 1.4 than coefficient is added in tube furnace
Filter residue and bauxite are warming up to 1200 DEG C, heating rate 40K/min, furnace air flow velocity 100ml/min from 217 DEG C, sampling
It is spaced 2s, apparatus measures flow velocity 1L/min calcines 30min at 1200 DEG C, the SO that manganese slag is precipitated in sintering process2Into cigarette
Gas analyzer records SO by sensor2Instantaneous concentration, air velocity 1L/min, sampling interval 2S.As a result such as 2 institute of table
Show.
Mean concentration when 2 different calcium silicon of table is sintered in tube furnace than coefficient raw material
From Table 2, it can be seen that calcium silicon than coefficient be 1.1 when, desulfurization degree is minimum, be 52.9%；Calcium silicon is than coefficient
0.8, desulfurization degree 82.38%, but be to calculate the desulfurization degree of base to be greater than 90% with solid phase, the SO in flue gas under this condition2Contain
Amount is 0.3%；And remaining desulfurization degree all concentrates on 70% or so.
Use bauxite as desulfurization auxiliary additive, desulfurization temperature reduces, and can obtain higher desulfurization at 1200 DEG C
Rate, electrolytic manganese press filtration residues can largely remove element sulphur.
The measurement of 4 sulfur content of experimental example
Sulfur content is measured using carbon and sulfur analytical instrument, under the conditions of gravity-flow ventilation, the setting calcining temperature in program-controlled furnace
Degree at such a temperature heat preservation a period of time, is milled to sintered product, carries out sulfur content to powder using carbon and sulfur analytical instrument
Measurement.
1) to not adding the electrolytic manganese press filtration residues of any auxiliary additive respectively at 1100 DEG C, 1250 DEG C and 1300 DEG C
20min is calcined, carries out sulphur content determination, the results are shown in Table 3.
Influence of 3 temperature of table to manganese slag desulfurization
The result shows that the sulfur content of manganese filter-press residues sinter is 3.65% when sintering temperature is 1100 DEG C, it is much larger than
The 0.48% of the remaining sulfur content requirement of experiment, because decomposition initial temperature of the calcium sulfate under non-reducing atmosphere is 1223 DEG C,
And final temperature is 1385 DEG C.Contain more calcium sulfate in manganese filter-press residues, so when sintering temperature is 1100 DEG C, one
Sulfate is divided to start to decompose not yet.And manganese filter-press residues are under 1250 DEG C and the sintering of 1300 DEG C of temperature, the sulfur content point of sinter
It Wei 0.1089% and 0.0712%.Under conditions of soaking time is 20 minutes, the desulfurization degree of former manganese slag with temperature raising
And increase.
2) by 50g manganese filter-press residues and bauxite calcium silicon than coefficient be 1.3 1250 DEG C of soaking times be respectively 5 minutes and
It is sintered under the conditions of 20 minutes and (respectively corresponds embodiment 1 and embodiment 3), sulfur content survey is carried out after sintered product is milled
It is fixed, as a result as shown in table 4.
4 time of table influences manganese slag+bauxite desulfurization
The result shows that when soaking time is 5 minutes, when sintering temperature is 1250 DEG C, manganese filter-press residues+bauxite calcium silicon ratio
Sulfur content for 1.3 sintered products is 0.0894%, 0.48% required less than the remaining sulfur content of experiment.Than being sintered temperature in table 4
Degree is 1250 DEG C, and soaking time is 20 minutes, and calcium silicon is more higher than the sulfur content for 1.3 sintered products, but the desulfurization degree of manganese slag
All tend to complete.So the soaking time for being suitable under conditions of 1250 DEG C is 5 minutes.
3) add bauxite calcium silicon than coefficient to be respectively 0.6 400g manganese filter-press residues, 0.8,0.9,1.0,1.1,1.2,1.3,
1.4 mixed material, be sintered under conditions of 1250 DEG C of soaking times are 5 minutes (respectively correspond embodiment 10,4,5,
6,7,8,1 and 9), sulphur content determination is carried out using carbon and sulfur analytical instrument after sintered product is milled, the results are shown in Table 5.
5 400g original manganese slag of table+bauxite sintering product desulfurization Analysis
As can be seen from Table 5, when soaking time is 5 minutes, and sintering temperature is 1250 DEG C, manganese filter-press residues+bauxite
Calcium silicon than be 1.5049% for the sulfur content of 0.6,0.8,0.9,1.0,1.1,1.2,1.3,1.4 sintered products, 1.6668%,
0.1028%, 0.1243%, 0.063%, 0.1067%, 0.0894%, 0.1222%, calcium silicon ratio is 0.6,0.8 sintered product
Sulfur content it is bigger, this may be because SO is precipitated in furnace in sintering process2Concentration is bigger, and the gas in stove does not have
There is instant exclusion, SO can be inhibited2Further precipitation.Remaining sulfur content is both less than 0.48%, and explanation uses bauxite as auxiliary
It helps additive to carry out desulfurization, facilitates the precipitation of element sulphur.
4) by 50g manganese filter-press residues add 15% lime stone respectively 1250 DEG C, 1300 DEG C of soaking times be 20 minutes under the conditions of
It is sintered and (respectively corresponds embodiment 12 and embodiment 13), carry out sulphur content determination after product sinters are milled, as a result such as table
Shown in 6.
6 manganese slag of table+lime stone desulfurization effect
It is obtained by table, when sintering temperature is respectively 1100 DEG C, 1200 DEG C, 1300 DEG C, manganese filter-press residues+calcium additive
The sulfur content of sintered product is both greater than 0.6%, and at 1100 DEG C, decomposition temperature is too low, the sulfate being unfavorable in manganese filter-press residues
Decomposition.And temperature, at 1200 DEG C or more, manganese filter-press residues have been burnt into glass phase.
5)+5% carbon dust of manganese filter-press residues is calcined into (embodiment under conditions of 1250 DEG C, soaking time are 20 minutes
14) sulphur content determination is carried out after, product is milled, the results are shown in Table 7.
7 manganese slag of table+carbon dust desulfurization effect
Compared with 1250 DEG C of sintered products of manganese filter-press residues in table 3, the burning of+5% carbon dust of manganese filter-press residues sintering at 1250 DEG C
Knot object sulfur content wants much higher, because the manganese filter-press residues in table 7 have added 5% carbon dust, under reducing atmosphere, calcium sulfate
It decomposes starting and final temperature is respectively 990 DEG C and 1330 DEG C, react mainly with reaction equation CaSO early period4+ CO→CaO+SO2+
CO2Based on, and the later period is with equation CaSO4+4CO→CaS+ 4CO2Based on, it is main after calcium sulfate decomposes in high-temperature reaction process
Exist in the form of CaS, so that the content of the sulphur of sintered product be made to improve.
To sum up, bauxite glass phase not easy to produce is added, desulfurization temperature reduces, and desulfurization effect is good；Additive amount be 40% with
When keeping the temperature 5min when upper, at 1250 DEG C, sulfur content is lower than 0.15% in solid slag.When Ca/Si ratio is 1.1 in material, above-mentioned item
Solid sulfur content is 0.6% under part, reaches 94.23% with the desulfurization degree that solid-state calculates.
The test of 5 strength of cement mortar of experimental example
The anti-folding of cement and intensity test are carried out according to national standard GB 175-2007, and 225ml water is poured into agitator,
Cement mortar mixer is opened, the cement mixed is added, machine shows automatic stirring 180 seconds and counts automatically at this time, when
Registration is shown as starting that normal sand is uniformly and stably added at 150 seconds, makes just to add at registration 120 seconds, waits until registration
When being zero machine issue " dichloro-diphenyl-dichlorothane " alarm and be automatically stopped, remove agitator.
It will assemble in advance and three gang moulds of first-class oil are placed on jarring machine, open jarring machine, then being stirred
Glue sand is added in mold, is added while shaking, and the gas in glue sand is discharged, and shows as glue sand surface and foam occurs, is used
Long straight iron plate is close to die surface and scrapes off foam, until die surface no longer apparent foam occurs.Close shake
Mold is transferred to shady and cool flat place and stands 24 hours by motivation.
Demoulding.Mold is struck pine, glue sand sample is originally taken off, and is marked with writing brush: be denoted as respectively X, P1, P2,
P3、P4。
Water-bath maintenance, the sample marked is placed in 20 DEG C of constant water bath box and is conserved, water surface lid crosses sample 3cm, wait do
Strength test.
Mechanical universal testing machine and computer are opened, strength test software is opened, selection is online, selects cement mortar strong
Degree detection-anti-folding.Two lower bottom bases are respectively aligned to 120 graduation marks, this square of glue sand sample on two pedestals, adjust briquetting
Distance is allowed to be located next to but do not contact with sample.All data is reset, operation machine is clicked, when load data rises to
When maximum and no longer variation, sample fractures, and stops machine, writes down load value.
Select strength of cement mortar test-resistance to compression.Pedestal and briquetting are installed, the half of the sample broken is placed on bottom
On seat, briquetting is also to be located next to but do not contact with sample, guarantees all contact surface cleanings, cannot there is comminutions.All data is clear
Zero, machine is then run, when load data rises to maximum and no longer variation, stops machine and writes down the numerical value of load.
X, P1, P2, P3, P4 indicate bauxite and electrolytic manganese residues amount ratio is that manganese filter-press residues obtained by 11.6:10 desulfurization add
Entering amount is respectively 0,6%, 9%, 12%, 15%, is mixed with ordinary portland cement clinker and gypsum, through ball milling, crosses 200 mesh
Cement prepared by sieve, 3 days and 28 days cement mortar strengths it is as shown in table 8:
The strength of cement mortar of 8 200 mesh high temperature desulfurizing slag Different adding amount of table
As can be seen from Table 8,3 days intensity of experiment sample have been above ordinary portland cement strength criterion grade.It is de-
When sulphur manganese slag additive amount is less than 9%, there is humidification to 3 days intensity of glue sand.Compression strength can reach corresponding intensity etc.
Grade.
It is that the intensity of cement is made in the desulfurization manganese slag that fineness is 250 mesh shown in table 9.
The strength of cement mortar of 9 250 mesh desulfurization manganese slag Different adding amount of table
The result shows that: after cement fineness increase, when the desulfurization manganese quantity of slag of addition is higher than 12%, to the flexural strength of cement
It increased, 28 days compression strength can achieve 42.5 strength grades when adding 12% desulfurization manganese slag.Cement powder granularity is got over
Small, powder active is higher.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations
It can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that without departing from spirit and scope of the invention the case where
Under, it can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within this
In the range of invention.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of method of electrolytic manganese press filtration residues desulfurization, which is characterized in that method includes the following steps:
(1) electrolytic manganese press filtration residues are mixed with auxiliary additive；
(2) mixed material is calcined；
(3) cooling, obtain desulfurization manganese slag.
2. the method according to claim 1, wherein in step (1),
Contain sulfate, ammonia nitrogen, manganese in the electrolytic manganese press filtration residues；
Preferably, silicon mainly exists in the form of quartzy phase in the electrolytic manganese press filtration residues, and calcium is mainly mutually deposited with the object of dihydrate gypsum
Magnesium exists in the form of magnesium sulfate, and potassium sodium mutually exists with feldspar.
3. method according to claim 1 or 2, which is characterized in that in step (1),
The auxiliary additive is additive containing aluminium, lime stone, carbon dust and calcium additive, and preferably additive containing aluminium and carbon dust are more excellent
It is selected as bauxite；
The additive amount of the auxiliary additive are as follows: the electrolytic manganese press filtration residues based on 10 parts by weight, auxiliary additive are 0.5~40 weight
Measure part, preferably 1~30 parts by weight, more preferably 2~25 parts by weight.
4. the method according to claim 1, wherein in step (2),
The mixed material includes auxiliary additive and electrolytic manganese press filtration residues,
Mixed material is uniformly mixed to be placed in Muffle furnace and is calcined；
The calcination temperature is 400~1500 DEG C, preferably 600~1400 DEG C, more preferably 900~1400 DEG C；
The mixed material calcination time is 2~90min, preferably 2~60min, more preferably 5~20min.
5. method according to claim 1 to 4, which is characterized in that in step (3),
It is described to be cooled to natural cooling；
Sulfur content≤0.48% in the desulfurization manganese slag, the object contained are mutually Al through XRD characterization2O3、Ca(Al2Si2O8)、Al2
(SiO3)3、MgSiO3。
6. a kind of method for preparing cement, which is characterized in that method includes the following steps:
(1) desulfurization manganese slag, clinker and gypsum are mixed；
(2) by mixture ball milling.
7. according to the method described in claim 6, it is characterized in that, the desulfurization manganese slag is according to claim 1 in step (1)
It is prepared to one of 5 the methods.
8. method according to claim 6 or 7, which is characterized in that in step (1), according to claim 1 to one of 5 institutes
Method preparation desulfurization manganese slag is stated, and desulfurization manganese slag, clinker and gypsum are mixed into mixture；
The desulfurization manganese slag preferably uses bauxite as manganese filter-press residues, more preferably bauxite obtained by auxiliary additive desulfurization
It is manganese filter-press residues obtained by 11.6:10 desulfurization with electrolytic manganese residues amount ratio.
9. the method according to one of claim 6 to 8, which is characterized in that in step (1),
The dosage of desulfurization manganese slag, clinker and gypsum is respectively as follows: the gypsum based on 1 parts by weight, 1~5 parts by weight of desulfurization manganese slag,
14~20 parts by weight of clinker；
It is preferably based on the gypsum of 1 parts by weight, 1~4 parts by weight of desulfurization manganese slag, 16~18 parts by weight of clinker；
It is highly preferred that the gypsum based on 1 parts by weight, 1.2~3 parts by weight of desulfurization manganese slag, 17~18 parts by weight of clinker.
10. the method according to one of claim 6 to 9, which is characterized in that in step (2),
Mixture in step (1) is put into ball milling in conical ball mill；
Preferably, it is sieved after the mixture ball milling,
It is highly preferred that crossing 200 mesh or 250 meshes after the mixture ball milling, mixture fineness is less than or equal to 0.08mm.
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| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 铜仁学院 | Manganese ore industrialization wet ball milling method based on electrolytic manganese metal system backwater |
| CN115594424A (en) * | 2021-06-28 | 2023-01-13 | 中南大学（Cn） | Low-clinker high-electrolysis manganese slag cementing material and preparation method thereof |
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| KR20140017178A (en) * | 2012-07-31 | 2014-02-11 | 현대제철 주식회사 | Method for pre-treating pig iron |
| CN105645793A (en) * | 2015-09-18 | 2016-06-08 | 花垣县强桦矿业有限责任公司 | Method using electrolytic manganese slag to manufacture active mixed material |
| CN108264233A (en) * | 2018-02-05 | 2018-07-10 | 北京工业大学 | The method that electrolytic manganese residues comprehensively utilize and prepare devitrified glass |
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| KR20140017178A (en) * | 2012-07-31 | 2014-02-11 | 현대제철 주식회사 | Method for pre-treating pig iron |
| CN105645793A (en) * | 2015-09-18 | 2016-06-08 | 花垣县强桦矿业有限责任公司 | Method using electrolytic manganese slag to manufacture active mixed material |
| CN108264233A (en) * | 2018-02-05 | 2018-07-10 | 北京工业大学 | The method that electrolytic manganese residues comprehensively utilize and prepare devitrified glass |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 铜仁学院 | Manganese ore industrialization wet ball milling method based on electrolytic manganese metal system backwater |
| CN115594424A (en) * | 2021-06-28 | 2023-01-13 | 中南大学（Cn） | Low-clinker high-electrolysis manganese slag cementing material and preparation method thereof |
| CN115594424B (en) * | 2021-06-28 | 2024-01-19 | 中南大学 | Low-clinker high-electrolysis manganese slag cementing material and preparation method thereof |
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