CN109399723B - Method for producing electrolytic manganese dioxide by using manganese tailings and titanium dioxide waste sulfuric acid - Google Patents
Method for producing electrolytic manganese dioxide by using manganese tailings and titanium dioxide waste sulfuric acid Download PDFInfo
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- CN109399723B CN109399723B CN201811467563.6A CN201811467563A CN109399723B CN 109399723 B CN109399723 B CN 109399723B CN 201811467563 A CN201811467563 A CN 201811467563A CN 109399723 B CN109399723 B CN 109399723B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 71
- 239000011572 manganese Substances 0.000 title claims abstract description 71
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 title claims description 25
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000000605 extraction Methods 0.000 claims description 38
- 239000000706 filtrate Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000011790 ferrous sulphate Substances 0.000 claims description 19
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 19
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 19
- 229940099596 manganese sulfate Drugs 0.000 claims description 18
- 239000011702 manganese sulphate Substances 0.000 claims description 18
- 235000007079 manganese sulphate Nutrition 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000001238 wet grinding Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- CZSABVBCTRZESY-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].OS(O)(=O)=O Chemical compound [O-2].[O-2].[Ti+4].OS(O)(=O)=O CZSABVBCTRZESY-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- 229910052603 melanterite Inorganic materials 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- LIRDHUDRLFDYAI-UHFFFAOYSA-H iron(3+);trisulfite Chemical compound [Fe+3].[Fe+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O LIRDHUDRLFDYAI-UHFFFAOYSA-H 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 15
- 238000001035 drying Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- 229910052683 pyrite Inorganic materials 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- NWTLYIZAMXLXJI-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] Chemical compound [O-2].[O-2].[O-2].O.[Ti+4].[Mn+2] NWTLYIZAMXLXJI-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium white waste sulfuric acid, which is characterized in that the titanium white waste sulfuric acid is reduced and leached to levigate the manganese tailings, white filter residues are used as diatomite after solid-liquid separation, leaching solution is extracted by a di (2-ethylhexyl) phosphate extractant, then is saponified by light burning powder (or magnesium oxide), electrolytic manganese dioxide is obtained after impurity removal and byproducts of iron black and magnesium sulfate are produced; the method for preparing the electrolytic manganese dioxide has the advantages of high quality, simple process and low production cost, realizes the complete recycling of manganese tailings and titanium white waste sulfuric acid, does not generate secondary pollution, realizes zero discharge of wastewater, and is beneficial to environmental protection and comprehensive utilization of resources.
Description
Technical Field
The invention relates to the technical field of non-ferrous metal tailing recycling, in particular to a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid.
Background
In modern industry, manganese and its compounds are used in various areas of national economy. Wherein the steel industry is the most important field, the manganese accounts for 90 to 95 percent and is mainly used as a deoxidizer and a desulfurizer in the iron and steel making processes and used for manufacturing alloys. The remaining 5% to 10% of manganese is used in other industrial fields, such as the chemical industry (for the manufacture of various manganese-containing salts), the light industry (for batteries, matches, paints, soaps, etc.), the building industry (colorants and discolorants for glass and ceramics), the defense industry, the electronics industry, as well as in environmental protection and agriculture and animal husbandry, etc. In conclusion, manganese has a very important strategic position in national economy. The manganese tailings are waste formed in the manganese production process, and many substances in the manganese tailings are dissolved out under natural conditions such as rainwater, enter soil and water and cause environmental pollution. For a long time, because the manganese tailings can not be comprehensively utilized and can only be stacked and stored, a large amount of land resources are occupied, and serious environmental pollution is caused. Therefore, a new method for comprehensive treatment and application of the manganese tailings needs to be explored.
At present, more than 98% of titanium dioxide production enterprises in China adopt a sulfuric acid method to produce titanium dioxide. The fatal weakness of the sulfuric acid method for producing titanium dioxide is the problem of environmental protection, such as the production of sulfur-containing tail gas, waste acid, ferrous sulfate and the like. At present, the titanium white waste acid treatment modes are roughly divided into two modes, wherein the first mode is to neutralize the waste acid and quicklime to generate calcium sulfate precipitation and then stack neutralized slag into a slag yard; the second mode is that the waste acid is heated by steam to be concentrated in vacuum, the concentration of the waste acid is increased to 70%, and then the waste acid is mixed with 98% concentrated sulfuric acid to be returned to the titanium dioxide acidolysis section for use. The first treatment mode can generate a large amount of sulfate slag, and the sulfate slag can only be discarded and stacked due to high impurity content and no recycling value, and occupies a large amount of land resources. The second treatment method is complex in process and high in recovery cost, so that not all titanium dioxide production enterprises have conditional application. Therefore, each titanium dioxide production enterprise needs to find a more economic and reasonable titanium dioxide waste acid recovery treatment method, so that waste materials can be changed into valuable materials, and resources can be reused.
The electrolytic manganese dioxide is an excellent depolarizer of battery, compared with the dry battery produced by natural discharging manganese dioxide, it has the characters of large discharging capacity, strong activity, small volume, long service life, etc., the dry battery made by mixing 20-30% Electrolytic Manganese Dioxide (EMD) is more than natural MnO2The discharge capacity of the dry battery can be improved by 50-100%, and 50-70% of electrolytic dioxide is mixed in the high-performance zinc chloride batteryManganese (EMD) has a discharge capacity increased by 2 to 3 times, and an alkaline manganese battery made entirely of Electrolytic Manganese Dioxide (EMD) has a discharge capacity increased by 5 to 7 times, and thus electrolytic manganese dioxide is a very important raw material in the battery industry.
At present, the Chinese published patent document CN1724697A discloses a method for preparing electrolytic manganese metal by using titanium white waste acid and manganese dioxide ore, wherein H in the titanium white waste acid is used2SO4With Fe2+Manganese dioxide ore and pyrite are added as auxiliary materials to prepare electrolytic manganese metal. The invention uses waste acid produced by titanium dioxide as auxiliary material and adds MnO2Ore and FeS2The production of electrolytic manganese metal products and by-products of manganese carbonate and ammonium sulfate is successful, and the problem of environmental pollution caused by titanium white waste acid is solved; the quality of the produced electrolytic manganese metal product is high and reaches the YB/T051-2003 DJMnA high-purity product standard; the produced manganese carbonate and ammonium sulfate both reach industrial products; the method for producing electrolytic manganese metal by treating titanium white waste acid has obvious economic benefit, social benefit and environmental protection benefit.
However, the existing process method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium white waste sulfuric acid has the defects of low recovery rate and easy generation of secondary pollution.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid of titanium white, which effectively makes up for the defects in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid comprises the following steps:
a) putting the manganese tailings into a ball mill, adding water for wet milling, and sieving a manganese tailing material subjected to wet milling through a 200-210-mesh sieve to ensure that the total mass of undersize materials is more than 95% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn6.0-22.5%, Fe3.0-7.5%, SiO235.0-60.0％、CaO0.3-5.0％、Al2O34.05-15.05％、MgO0.30-1.55％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 1-3 hours at the reaction temperature of 60-90 ℃, and performing solid-liquid separation to obtain a first filtrate and a first filter residue;
c) adding light calcined powder or magnesium oxide with the mass concentration of 10-50% as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 1.5-3h, and carrying out solid-liquid separation to obtain a second filtrate and a second filter residue;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then adopting sulfuric acid or electrolytic manganese dioxide anolyte to carry out back extraction on manganese on the obtained organic phase, then adding a saponifying agent into the obtained organic phase to saponify the di (2-ethylhexyl) phosphate, then adjusting the pH value to 5-6 by using alkali to remove silicon and aluminum, and directly producing qualified manganese sulfate extraction precursor liquid;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
Preferably, the ferrous sulfate in step b) is chemically pure, and the chemical formula of the ferrous sulfate is FeSO4·7H2O, the content is 98.0-100.0%, and the content of water-insoluble substances is less than 0.02%; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 18 to 20 percent.
Preferably, the first filter residue in the step b) is subjected to reverse-flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the volume ratio of the first filtrate to the distilled water is 3:1-9: 1.
Preferably, the second filter residue in the step c) is subjected to counter-current washing by distilled water of an MVR evaporator, then a transforming agent is added, the reaction is carried out for 0.5 to 1.5 hours at normal temperature and normal pressure, the obtained reactant is subjected to counter-current washing by distilled water of the MVR evaporator, and then the obtained reactant is dried to obtain the iron oxide black.
Preferably, the water phase obtained by the extraction in the step d) is evaporated by an MVR evaporator, and the obtained solid is dried to obtain the magnesium sulfate product.
Preferably, the qualified manganese sulfate extraction precursor liquid obtained in the step d) is evaporated by an MVR evaporator, and after solid-liquid separation, the obtained solid is dried to obtain the battery-grade manganese sulfate monohydrate.
Preferably, the saponifying agent in the step d) is light burned powder or magnesium oxide, and the alkali for removing silicon and aluminum is light burned powder or lime.
Preferably, the transformation agent is one or more of sulfur oxide, ferrous sulfate, sodium sulfite, ammonium sulfate, ferrous sulfate and ferrous chloride.
The invention has the beneficial effects that:
the invention provides a method for producing electrolytic manganese dioxide by comprehensively recycling manganese tailings and titanium dioxide waste acid, which comprises the steps of fully soaking manganese and nickel-cobalt in the manganese tailings by using ferrous sulfate as a reducing agent, producing iron oxide pigment by using ferrous ions in the titanium dioxide waste acid of the manganese dioxide titanium dioxide, neutralizing and precipitating iron oxide red by using light burning powder, and fully extracting manganese by directly saponifying the light burning powder (not the conventional sodium hydroxide solution saponification) or magnesium oxide, so that the consumption of sodium hydroxide is reduced, the production cost is reduced, then carrying out back extraction on the manganese by using sulfuric acid or electrolytic manganese dioxide anode solution, removing silicon and aluminum in the back extraction solution, and then carrying out electrolysis to produce the electrolytic manganese dioxide.
The method realizes the complete recycling of the manganese tailings and the titanium dioxide waste acid, does not generate secondary pollution, realizes zero discharge of the waste water, and is beneficial to environmental protection and comprehensive utilization of resources.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid comprises the following steps:
a) putting the manganese tailings into a ball mill, adding water, wet-milling, and sieving a manganese tailing material subjected to wet milling with a 200-mesh sieve to ensure that the total mass of undersize materials is 96% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn6.0%, Fe7.5%, SiO260.0％、CaO0.3％、Al2O34.05％、MgO1.55％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 3 hours at the reaction temperature of 60 ℃, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue; the first filter residue is subjected to reverse flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the ferrous sulfate is chemically pure and has a chemical formula of FeSO4·7H2O, the content is 98.0 percent, and the content of water-insoluble substances is less than 0.02 percent; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 20%; the volume ratio of the first filtrate to the distilled water is 9: 1;
c) adding 10% light calcined powder as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 1.5h, and carrying out solid-liquid separation to obtain a second filtrate and a second filter residue; the second filter residue is subjected to counter-current washing by distilled water of an MVR evaporator, then sulfur oxide is added to be used as a transformation agent, the reaction is carried out for 1.5 hours at normal temperature and normal pressure, and the obtained reactant is subjected to counter-current washing by the distilled water of the MVR evaporator and then dried to obtain iron oxide black;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then carrying out back extraction on the obtained organic phase by adopting sulfuric acid, adding light burning powder into the obtained organic phase as a saponifying agent to saponify the di (2-ethylhexyl) phosphate, then adjusting the pH value to 6 by using the light burning powder to remove silicon and aluminum, and directly producing a qualified manganese sulfate extraction precursor solution; evaporating the manganese sulfate extraction precursor solution by an MVR evaporator, carrying out solid-liquid separation, and drying the obtained solid to obtain battery-grade manganese sulfate monohydrate; evaporating the water phase obtained by extraction through an MVR evaporator, and drying the obtained solid to obtain a magnesium sulfate product;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
Example 2:
a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid comprises the following steps:
a) putting the manganese tailings into a ball mill, adding water, wet-milling, and sieving a manganese tailing material subjected to wet milling with a 210-mesh sieve to ensure that the total mass of undersize materials is 97% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn2.5%, Fe3.0%, SiO235.0％、CaO5.0％、Al2O315.05％、MgO0.30％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 1 hour, wherein the reaction temperature is 90 ℃, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue; the first filter residue is subjected to reverse flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the ferrous sulfate is chemically pure and has a chemical formula of FeSO4·7H2O, the content is 100.0 percent, and the water insoluble matter is less than 0.02 percent; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 18%; the volume ratio of the first filtrate to the distilled water is 3: 1;
c) adding magnesium oxide with the mass concentration of 50% as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 3 hours, and carrying out solid-liquid separation to obtain a second filtrate and second filter residue; the second filter residue is subjected to counter-current washing by distilled water of an MVR evaporator, then ferric sulfite is added to be used as a transformation agent, the reaction is carried out for 0.5h at normal temperature and normal pressure, and the obtained reactant is subjected to counter-current washing by distilled water of the MVR evaporator and then dried to obtain black iron oxide;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then adopting electrolytic manganese dioxide anolyte to carry out manganese back extraction on the obtained organic phase, adding magnesium oxide into the obtained organic phase as a saponifying agent to saponify the di (2-ethylhexyl) phosphate, then using light burning powder to adjust the pH value to 5 to remove silicon and aluminum, and directly producing qualified manganese sulfate extraction precursor liquid; evaporating the manganese sulfate extraction precursor solution by an MVR evaporator, carrying out solid-liquid separation, and drying the obtained solid to obtain battery-grade manganese sulfate monohydrate; evaporating the water phase obtained by extraction through an MVR evaporator, and drying the obtained solid to obtain a magnesium sulfate product;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
Example 3:
a method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid comprises the following steps:
a) putting the manganese tailings into a ball mill, adding water, wet-milling, and sieving a manganese tailing material subjected to wet milling with a 200-mesh sieve to ensure that the total mass of undersize materials is 96% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn22.5%, Fe3.0%, SiO260.0％、CaO0.3％、Al2O315.05％、MgO0.3％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 3 hours at the reaction temperature of 60 ℃, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue; the first filter residue is subjected to reverse flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the ferrous sulfate is chemically pure and has a chemical formula of FeSO4·7H2O, the content is 100.0 percent, and the water insoluble matter is less than 0.02 percent; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 18%%; the volume ratio of the first filtrate to the distilled water is 9: 1;
c) adding 10% light calcined powder as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 3 hours, and carrying out solid-liquid separation to obtain a second filtrate and a second filter residue; the second filter residue is subjected to countercurrent washing by distilled water of an MVR evaporator, then sodium sulfite and ammonium sulfate are added to be used as a transforming agent, the reaction is carried out for 0.5h at normal temperature and normal pressure, and the obtained reactant is subjected to countercurrent washing by distilled water of the MVR evaporator and dried to obtain black iron oxide;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then adopting electrolytic manganese dioxide anolyte to carry out manganese back extraction on the obtained organic phase, adding light burning powder into the obtained organic phase as a saponifying agent to saponify the di (2-ethylhexyl) phosphate, then using the light burning powder to adjust the pH value to 6 to remove silicon and aluminum, and directly producing a qualified manganese sulfate extraction precursor solution; evaporating the manganese sulfate extraction precursor solution by an MVR evaporator, carrying out solid-liquid separation, and drying the obtained solid to obtain battery-grade manganese sulfate monohydrate; evaporating the water phase obtained by extraction through an MVR evaporator, and drying the obtained solid to obtain a magnesium sulfate product;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
Example 4
A method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid comprises the following steps:
a) putting the manganese tailings into a ball mill, adding water, wet-milling, and sieving a manganese tailing material subjected to wet milling with a 210-mesh sieve to ensure that the total mass of undersize materials is 98% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn6.0%, Fe7.5%, SiO235.0％、CaO5.0％、Al2O34.05％、MgO1.55％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 1 hour, wherein the reaction temperature is 90 ℃, and carrying out solid-liquid separation to obtain a first filtrate and a first filter residue; the first filter residue is subjected to reverse flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the ferrous sulfate is chemically pure and has a chemical formula of FeSO4·7H2O, the content is 98.0 percent, and the content of water-insoluble substances is less than 0.02 percent; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 20%; the volume ratio of the first filtrate to the distilled water is 3: 1;
c) adding magnesium oxide with the mass concentration of 50% as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 1.5h, and carrying out solid-liquid separation to obtain a second filtrate and a second filter residue; the second filter residue is subjected to countercurrent washing by distilled water of an MVR evaporator, then ferrous sulfate and ferrous chloride are added to be used as a transforming agent, the reaction is carried out for 1.5 hours at normal temperature and normal pressure, and the obtained reactant is subjected to countercurrent washing by distilled water of the MVR evaporator and then dried to obtain iron oxide black;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then carrying out back extraction on the obtained organic phase by adopting sulfuric acid, adding magnesium oxide into the obtained organic phase as a saponifying agent to saponify the di (2-ethylhexyl) phosphate, then adjusting the pH value to 5 by using lime to remove silicon and aluminum, and directly producing a qualified manganese sulfate extraction precursor solution; evaporating the manganese sulfate extraction precursor solution by an MVR evaporator, carrying out solid-liquid separation, and drying the obtained solid to obtain battery-grade manganese sulfate monohydrate; evaporating the water phase obtained by extraction through an MVR evaporator, and drying the obtained solid to obtain a magnesium sulfate product;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for producing electrolytic manganese dioxide by utilizing manganese tailings and titanium dioxide waste sulfuric acid is characterized by comprising the following steps:
a) putting the manganese tailings into a ball mill, adding water for wet milling, and sieving a manganese tailing material subjected to wet milling through a 200-210-mesh sieve to ensure that the total mass of undersize materials is more than 95% of the total mass of the material;
the manganese tailings comprise the following components in percentage by mass: mn6.0-22.5%, Fe3.0-7.5%, SiO235.0-60.0％、CaO0.3-5.0％、Al2O34.05-15.05％、MgO0.30-1.55％；
b) Premixing the ball-milled manganese tailing materials with ferrous sulfate and waste titanium dioxide sulfuric acid, adding the mixture into a strong stirrer, stirring and dissolving for 1-3 hours at the reaction temperature of 60-90 ℃, and performing solid-liquid separation to obtain a first filtrate and a first filter residue;
c) adding light calcined powder or magnesium oxide with the mass concentration of 10-50% as a precipitator into the first filtrate obtained in the step b), fully stirring, reacting for 1.5-3h, and carrying out solid-liquid separation to obtain a second filtrate and a second filter residue;
d) adding di (2-ethylhexyl) phosphate and tributyl phosphate into the second filtrate obtained in the step c) as extracting agents to fully extract manganese, then adopting sulfuric acid or electrolytic manganese dioxide anolyte to carry out manganese back extraction on the obtained organic phase, then adding light burning powder or magnesium oxide saponified di (2-ethylhexyl) phosphate into the obtained organic phase, then using the light burning powder or lime to adjust the pH value to 5-6 to remove silicon and aluminum, and directly producing a qualified manganese sulfate extraction precursor solution;
e) and d) carrying out an electrolysis process on the manganese sulfate extraction precursor solution to obtain electrolytic manganese oxide, and carrying out back extraction on manganese on the obtained organic phase in the step d) by using the electrolytic anolyte.
2. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid of titanium white according to claim 1, wherein the ferrous sulfate in the step b) is chemically pure, and the chemical formula of the ferrous sulfate is FeSO4·7H2O, the content is 98.0-100.0%, and the content of water-insoluble substances is less than 0.02%; the titanium white waste sulfuric acid is hydrolyzed waste acid, namely mother liquor for filtering metatitanic acid, and the concentration of the titanium white waste sulfuric acid is H2SO4Calculated as 18 to 20 percent.
3. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid from titanium dioxide according to claim 1, wherein the first filter residue obtained in the step b) is subjected to reverse-flow washing by distilled water of an MVR evaporator, and the solid is dried to obtain diatomite, and the obtained washing liquid is returned to the step a) for recycling;
wherein the volume ratio of the first filtrate to the distilled water is 3:1-9: 1.
4. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid from titanium dioxide according to claim 1, wherein the second filter residue obtained in the step c) is subjected to counter-current washing with distilled water of an MVR evaporator, then a modifier is added, the mixture is reacted for 0.5 to 1.5 hours at normal temperature and normal pressure, and the obtained reactant is subjected to counter-current washing with distilled water of the MVR evaporator and then dried to obtain black iron oxide.
5. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid from titanium dioxide according to claim 1, wherein the water phase obtained by extraction in the step d) is evaporated by an MVR evaporator, and the obtained solid is dried to obtain a magnesium sulfate product.
6. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid from titanium dioxide according to claim 1, wherein the qualified manganese sulfate extraction precursor solution obtained in the step d) is evaporated by an MVR evaporator, and after solid-liquid separation, the obtained solid is dried to obtain battery-grade manganese sulfate monohydrate.
7. The method for producing electrolytic manganese dioxide by using manganese tailings and waste sulfuric acid from titanium dioxide according to claim 4, wherein the transformation agent is one or more of ferric sulfite and sodium sulfite.
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