WO2022205533A1 - Method for preparing low-impurity electrolytic manganese dioxide - Google Patents
Method for preparing low-impurity electrolytic manganese dioxide Download PDFInfo
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- WO2022205533A1 WO2022205533A1 PCT/CN2021/088582 CN2021088582W WO2022205533A1 WO 2022205533 A1 WO2022205533 A1 WO 2022205533A1 CN 2021088582 W CN2021088582 W CN 2021088582W WO 2022205533 A1 WO2022205533 A1 WO 2022205533A1
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- Prior art keywords
- manganese
- electrolytic
- filtrate
- powder
- manganese dioxide
- Prior art date
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000012535 impurity Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 61
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 25
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims abstract description 23
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 21
- 239000011028 pyrite Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims abstract description 17
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000011085 pressure filtration Methods 0.000 claims abstract 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 239000011268 mixed slurry Substances 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001447 ferric ion Inorganic materials 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention belongs to the technical field of electrolytic manganese dioxide production, and in particular relates to a preparation method of low-impurity electrolytic manganese dioxide.
- the "two-ore method” is often used to produce manganese sulfate solution, and then electrolytically prepare electrolytic manganese dioxide (EMD). Therefore, the preparation of EMD with low impurity is the focus of production process research.
- the present invention discloses a preparation method of low-impurity electrolytic manganese dioxide, which can effectively remove impurities, and refine the EMD semi-finished product to obtain low-impurity EMD.
- the present invention adopts following technical scheme to realize:
- a preparation method of low impurity electrolytic manganese dioxide which comprises the following steps:
- the weight ratio of the manganese oxide ore powder and the pyrite powder is 1: (0.16 ⁇ 0.30), the sum of the weight of the manganese oxide ore powder and the pyrite powder and the weight of the sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid
- the ratio of the sum is 1:(0.25 ⁇ 0.35), and the ratio of the weight sum of the described manganese oxide ore powder and the pyrite powder to the weight of the described electrolytic waste liquid is 1:(5 ⁇ 7);
- the manganese sulfate solution is sent into the electrolytic cell for electrolysis.
- the temperature of the electrolyte is 98 to 100°C
- the anode current density is 55 to 80A/m2
- the concentration of sulfuric acid in the electrolyte is 0.35 to 0.70mol/L
- the concentration of manganese sulfate is 0.30-0.50 mol/L
- the cell voltage is 2.0-4.0V
- the electrolysis period is 10-12 days
- the semi-finished electrolytic manganese dioxide and electrolytic waste liquid are obtained after electrolysis;
- the semi-finished electrolytic manganese dioxide is crushed into particles with a particle size of 10mm to 30mm, and then rinsed with hot water at a rinsing temperature of 90 to 95°C until the content of sulfuric acid in the rinse solution is less than 1g/L, and then the use of hydroxide Rinse the lithium solution at 60 ⁇ 70°C, adjust pH to 6.5 ⁇ 7.0, then rinse with hot water at 90 ⁇ 95°C for 8 ⁇ 10h, then grind the particles to obtain electrolytic manganese dioxide powder with particle size less than 325 mesh;
- step (1) the manganese oxide ore powder with a particle size smaller than 200 mesh accounts for 90% to 95% and the mass content of metal manganese is 16 to 18%; the pyrite powder with a particle size smaller than 120 mesh accounts for 90%-95%. 90% to 95% and the mass content of the available sulfur participating in the reaction is 30 to 40%, and the industrial sulfuric acid is an industrial sulfuric acid with a mass fraction of 98%.
- the particle size smaller than 325 mesh accounts for 90% to 95%, and the calcium carbonate is nano calcium carbonate.
- the stirring speed in step (3) is 200-300 r/min.
- the stirring speed in step (4) is 50-100 r/min.
- the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%.
- the weight ratio of the potassium permanganate solution added in the step (7) to the electrolytic manganese dioxide powder is 25:1000.
- the weight ratio of the lithium hydroxide solution added in step (7) to the electrolytic manganese dioxide powder is 30:1000.
- the present invention removes heavy metal ions by quantitatively adding manganese sulfide.
- a large amount of manganese sulfide needs to be added.
- the viscosity of the solution increases, resulting in The manganese sulfide sticks together in a block shape, and it is difficult to diffuse in the solution, so that the impurity removal effect of the manganese sulfide is greatly reduced.
- One or more additives A formulated to reduce the viscosity of the solution, promote the dispersion of manganese sulfide, and increase the impurity removal effect of manganese sulfide.
- the invention removes calcium and magnesium ions by quantitatively adding manganese fluoride, and at the same time adds the auxiliary agent B prepared by mixing chitosan and citric acid to synergize with the manganese fluoride, so as to improve the dispersion of the manganese fluoride in the solution, Promote the combination of manganese fluoride with calcium and magnesium ions, and improve the impurity removal effect of manganese fluoride.
- lithium hydroxide solution and potassium permanganate solution in the rinsing process can avoid introducing impurity sodium into EMD products; adding a small amount of potassium permanganate can oxidize and remove low-valent manganese remaining in EMD.
- the present invention can effectively remove impurities in the manganese sulfate solution, avoid being brought into EMD products, reduce the difficulty of subsequent product refining, and improve production efficiency, thereby obtaining low-impurity EMD products.
- the method of the present invention has the advantages of simple process, simplified production process and high controllability, and is suitable for large-scale and automated production of low-impurity EMD products.
- Figure 1 is a data table of the test results of the EMD product in Experimental Example 1.
- Figure 2 is a data table of the detection results of the EMD product in Experimental Example 2.
- FIG. 3 is a data table of test results of EMD products in Experimental Example 3.
- FIG. 3 is a data table of test results of EMD products in Experimental Example 3.
- a preparation method of low impurity electrolytic manganese dioxide which comprises the following steps:
- the weight ratio of described manganese oxide ore powder and pyrite powder is 1:0.22, the ratio of the weight sum of described manganese oxide ore powder and pyrite powder and the weight sum of sulfuric acid in described industrial sulfuric acid and electrolytic waste liquid It is 1:0.28, and the ratio of the weight sum of the described manganese oxide ore powder and pyrite powder to the weight of the described electrolytic waste liquid is 1:6.5; in the described manganese oxide ore powder less than 200 mesh particle size accounts for 90% ⁇ 95% and the mass content of metal manganese is 16 ⁇ 18%; in the pyrite powder less than 120 mesh particle size accounts for 90% ⁇ 95% and the mass content of the effective sulfur participating in the reaction is 30 ⁇ 40%, the Industrial sulfuric acid is industrial sulfur
- the manganese sulfate solution is sent into the electrolytic cell for electrolysis.
- the temperature of the electrolyte is 98 to 100°C
- the anode current density is 55 to 80A/m2
- the concentration of sulfuric acid in the electrolyte is 0.35 to 0.70mol/L
- the concentration of manganese sulfate is 0.30-0.50 mol/L
- the cell voltage is 2.0-4.0V
- the electrolysis period is 10-12 days
- the semi-finished electrolytic manganese dioxide and electrolytic waste liquid are obtained after electrolysis;
- the semi-finished electrolytic manganese dioxide is crushed into particles with a particle size of 10mm to 30mm, and then rinsed with hot water at a rinsing temperature of 90 to 95°C until the content of sulfuric acid in the rinse solution is less than 1g/L, and then the use of hydroxide Rinse the lithium solution at 60 ⁇ 70°C, adjust pH to 6.5 ⁇ 7.0, then rinse with hot water at 90 ⁇ 95°C for 8 ⁇ 10h, then grind the particles to obtain electrolytic manganese dioxide powder with particle size less than 325 mesh;
- the blending time is 16-24h to obtain a low-impurity electrolytic manganese dioxide product; the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%; the added The weight ratio of the potassium permanganate solution to the electrolytic manganese dioxide powder is 25:1000; the weight ratio of the added lithium hydroxide solution to the electrolytic manganese dioxide powder is 30:1000.
- the weight ratio of the manganese oxide ore powder to the pyrite powder is 1:0.16, and the sum of the weights of the manganese oxide ore powder and the pyrite powder is the same as the The ratio of the weight sum of sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid is 1:0.25, and the ratio of the weight sum of the described manganese oxide ore powder and the pyrite powder to the weight of the described electrolytic waste liquid is 1:5;
- the filtrate A was heated to 80°C, the pH was adjusted to 3.5, then manganese sulfide and auxiliary B were slowly added, and the reaction was carried out under stirring at 250 r/min for 2 h; the weight ratio of the manganese sulfide to the filtrate A was 55 g: 1 L,
- the auxiliary agent B is ethanol, and the volume ratio of the auxiliary agent B to the filtrate A is 2:100; the filtrate C is slowly added manganese fluoride and
- the reaction was carried out for 2.5h under the stirring of 80r/min; the volume ratio of the weight of the manganese fluoride to the filtrate C was 80g:1L, and the volume ratio of the weight of the auxiliary agent D to the filtrate C was 10g:1000L.
- the weight ratio of the manganese oxide ore powder to the pyrite powder is 1:0.30, and the sum of the weights of the manganese oxide ore powder and the pyrite powder is the same as the The ratio of the weight sum of sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid is 1:0.35, and the ratio of the weight sum of the described manganese oxide ore powder and pyrite powder to the weight of the described electrolytic waste liquid is 1:7;
- the filtrate A was heated to 90°C, adjusted to pH 4.0, then slowly added manganese sulfide and auxiliary B, and reacted for 1.5h under stirring at 300r/min; the volume ratio of the weight of the manganese sulfide to the filtrate A was 60g:1L , the auxiliary agent B is propanol, and the volume ratio of the auxiliary agent B to the filtrate A is 3:100; the filtrate C is at 90 ° C and the pH is
- step (3) only barium sulfide is added.
- step (3) only manganese sulfide is added.
- step (4) only a polyacrylamide solution with a concentration of 100 ppm is added; the weight ratio of the polyacrylamide solution to the filtrate B is 10g:80m3.
- step (4) only manganese fluoride is added.
- EMD samples 1 to 3 were produced, and EMD samples 4 to 7 were produced according to the methods described in Comparative Examples 1 to 4. The purity and impurity content of the samples were tested. The specific results are shown in the attached figure 1.
- the volume ratio of the auxiliary agent B to the filtrate A is 0.5:100, 0.8:100, 1:100, 2:100, 3:100, 4:100, respectively.
- 100,5:100 detect the purity and impurity content of the obtained product, the specific results are shown in accompanying drawing 2, as can be seen from the data, the dosage ratio between auxiliary agent B and filtrate A and filtrate A and manganese sulfide needs to be controlled within a certain range
- too much additive B will make manganese sulfide too dispersed, and the resulting heavy metal sulfides are not easy to aggregate, precipitate and remove, and reduce the impurity removal effect; if additive B is too small, manganese sulfide will bond with the increase of concentration. , cannot diffuse effectively, reduce the binding efficiency with heavy metal ions, and cannot achieve the effect of impurity removal.
- the weight of the auxiliary agent D and the volume ratio of the filtrate C are respectively 1g:1000L, 5g:1000L, 10g:1000L, 15g:1000L, 20g:1000L, 25g: 1000L, 30g: 1000L, 35g: 1000L, 40g: 1000L, detect the purity and impurity content of the obtained product, the specific results are shown in Figure 3, as can be seen from the data, auxiliary D and filtrate C and filtrate C and manganese fluoride The dosage ratio between them needs to be controlled within a certain range, in order to promote the dispersion of manganese fluoride, so as to achieve the impurity removal effect of calcium and magnesium ions.
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Disclosed in the present invention is a method for preparing low-impurity electrolytic manganese dioxide, comprising: reacting manganese oxide ore powder, pyrite powder, industrial sulfuric acid, and a waste electrolyte; then adding calcium carbonate or extremely fine manganese oxide ore powder to remove iron, and then performing pressure filtration; adding manganese sulfide to the filtrate to remove impurities, and then performing pressure filtration; next, adding manganese fluoride to remove impurities, and performing filtering to obtain an electrolyte; then electrolyzing the obtained semi-finished electrolytic manganese dioxide product, and then performing procedures such as crushing, rinsing, pressure filtration, and drying to obtain a product. According to the method, a semi-finished electrolytic manganese dioxide product is refined, to effectively remove impurities in the product, and thus, low-impurity electrolytic manganese dioxide is obtained.
Description
本发明属于电解二氧化锰生产技术领域，具体涉及一种低杂质电解二氧化锰的制备方法。The invention belongs to the technical field of electrolytic manganese dioxide production, and in particular relates to a preparation method of low-impurity electrolytic manganese dioxide.
目前常采用“两矿法”生产硫酸锰溶液，然后电解制备电解二氧化锰（EMD），但是在锰矿的浸出和浸出液的净化过程中，易带入了大量的杂质，如何有效去除这些杂质，从而制备得到低杂质的EMD是生产工艺研究的重点。At present, the "two-ore method" is often used to produce manganese sulfate solution, and then electrolytically prepare electrolytic manganese dioxide (EMD). Therefore, the preparation of EMD with low impurity is the focus of production process research.
针对上述不足，本发明公开了一种低杂质电解二氧化锰的制备方法，有效去除杂质，并且对EMD半成品进行精制，得到低杂质的EMD。In view of the above deficiencies, the present invention discloses a preparation method of low-impurity electrolytic manganese dioxide, which can effectively remove impurities, and refine the EMD semi-finished product to obtain low-impurity EMD.
本发明是采用如下技术方案实现的：The present invention adopts following technical scheme to realize:
一种低杂质电解二氧化锰的制备方法，其包括以下步骤：A preparation method of low impurity electrolytic manganese dioxide, which comprises the following steps:
（1）将氧化锰矿粉、硫铁矿粉、工业硫酸和电解废液加入至浸出反应槽中，在90～95℃、200～300r/min的搅拌下反应3～4h，得到混合浆液；所述氧化锰矿粉与硫铁矿粉的重量比为1:（0.16～0.30），所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的工业硫酸和电解废液中硫酸的重量之和的比为1:（0.25～0.35），所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的电解废液的重量之比为1:（5～7）；(1) Add manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into the leaching reaction tank, and react for 3-4 hours at 90-95 °C and 200-300 r/min stirring to obtain a mixed slurry; The weight ratio of the manganese oxide ore powder and the pyrite powder is 1: (0.16～0.30), the sum of the weight of the manganese oxide ore powder and the pyrite powder and the weight of the sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid The ratio of the sum is 1:(0.25～0.35), and the ratio of the weight sum of the described manganese oxide ore powder and the pyrite powder to the weight of the described electrolytic waste liquid is 1:(5～7);
（2）在90～95℃下，向混合浆液中加入碳酸钙调节pH至4.0～4.5，检测混合浆液中二价铁离子含量，若二价铁离子含量大于或等于10-5mol/L时，加入极细氧化锰矿粉直到二价铁离子含量小于10-5mol/L，再继续向混合浆液中加入碳酸钙调节pH至6.0～6.5，检测混合浆液中三价铁离子含量，若三价铁离子含量大于或等于10-5mol/L时，继续加入碳酸钙直到三价铁离子含量小于10-5mol/L，然后将混合浆液压滤得到滤液A；(2) At 90~95℃, add calcium carbonate to the mixed slurry to adjust the pH to 4.0~4.5, and detect the content of ferrous ions in the mixed slurry. If the content of ferrous ions is greater than or equal to 10-5mol/L, Add ultra-fine manganese oxide ore powder until the content of ferrous ions is less than 10-5mol/L, then continue to add calcium carbonate to the mixed slurry to adjust the pH to 6.0-6.5, and detect the content of ferric ions in the mixed slurry. When the content is greater than or equal to 10-5mol/L, continue to add calcium carbonate until the ferric ion content is less than 10-5mol/L, and then filter the mixed slurry to obtain filtrate A;
（3）将滤液A加热至80～90℃，加入电解废液调节pH至3.5～4.0，然后缓慢加入硫化锰和助剂B，搅拌反应1～2h，压滤得到滤液C；所述硫化锰的重量与滤液A的体积比为（50～60）g:1L，所述助剂B为乙醇、丙醇和异丙醇中的任意一种或多种组合，所述助剂B与滤液A的体积比为（1～3）:100；(3) Heating the filtrate A to 80-90°C, adding electrolytic waste liquid to adjust the pH to 3.5-4.0, then slowly adding manganese sulfide and auxiliary B, stirring and reacting for 1-2 hours, and press-filtering to obtain filtrate C; the manganese sulfide The volume ratio of the weight to the filtrate A is (50～60) g:1L, and the auxiliary agent B is any one or more combinations of ethanol, propanol and isopropanol. The volume ratio is (1～3):100;
（4）将滤液C在80～90℃、pH为6.0～6.5的条件下，缓慢加入氟化亚锰和助剂D，搅拌反应2～3h，过滤得到净化的硫酸锰溶液；所述氟化亚锰的重量与滤液C的体积比为（80～100）g:1L，所述助剂D是将壳聚糖和柠檬酸等体积混合反应得到的，所述助剂D的重量与滤液C的体积比为（10～20）g:1000L；(4) Under the conditions of 80～90℃ and pH of 6.0～6.5, slowly add manganese fluoride and auxiliary D to the filtrate C, stir and react for 2～3h, and filter to obtain purified manganese sulfate solution; The weight ratio of manganese to the volume of filtrate C is (80-100) g: 1L. The auxiliary agent D is obtained by mixing equal volumes of chitosan and citric acid. The weight of the auxiliary agent D is the same as that of the filtrate C. The volume ratio of (10～20) g:1000L;
（5）将硫酸锰溶液送入电解槽中进行电解，电解液温度为98～100℃，阳极电流密度为55～80A/m2，电解液硫酸浓度为0.35～0.70mol/L、硫酸锰浓度为0.30～0.50 mol/L，槽电压为2.0～4.0V，电解周期为10～12天，电解后得到电解二氧化锰半成品和电解废液；(5) The manganese sulfate solution is sent into the electrolytic cell for electrolysis. The temperature of the electrolyte is 98 to 100°C, the anode current density is 55 to 80A/m2, the concentration of sulfuric acid in the electrolyte is 0.35 to 0.70mol/L, and the concentration of manganese sulfate is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and the semi-finished electrolytic manganese dioxide and electrolytic waste liquid are obtained after electrolysis;
（6）将电解二氧化锰半成品破碎成粒度为10mm～30mm的颗粒，然后加入热水漂洗，漂洗温度为90～95℃，直到漂洗液中硫酸的含量低于1g/L，接着采用氢氧化锂溶液在60～70℃下漂洗，调节pH至6.5～7.0，然后用热水在90～95℃下漂洗8～10h，然后将颗粒进行磨粉得到粒度小于325目的电解二氧化锰粉末；(6) The semi-finished electrolytic manganese dioxide is crushed into particles with a particle size of 10mm to 30mm, and then rinsed with hot water at a rinsing temperature of 90 to 95°C until the content of sulfuric acid in the rinse solution is less than 1g/L, and then the use of hydroxide Rinse the lithium solution at 60～70℃, adjust pH to 6.5～7.0, then rinse with hot water at 90～95℃ for 8～10h, then grind the particles to obtain electrolytic manganese dioxide powder with particle size less than 325 mesh;
（7）向电解二氧化锰粉末中加入高锰酸钾溶液反应1h，反应温度为90～95℃，接着加入氢氧化锂溶液，继续反应0.5h，反应温度为90～95℃，当pH达到6.5～7.0时为合格，然后先进行压滤再在100～105℃下进行闪蒸旋流烘干得到电解二氧化锰粉末后，采用密相气力输送方式输送到重力掺混仓进行掺混，掺混时间为16～24h，得到低杂质电解二氧化锰产品。(7) Add potassium permanganate solution to electrolytic manganese dioxide powder to react for 1 hour, the reaction temperature is 90～95℃, then add lithium hydroxide solution, continue to react for 0.5h, the reaction temperature is 90～95℃, when pH reaches 90～95℃ 6.5～7.0 is qualified, then press filter and then flash cyclone drying at 100～105℃ to obtain electrolytic manganese dioxide powder, which is transported to gravity blending bin for blending by dense phase pneumatic conveying. The mixing time is 16-24h, and the low-impurity electrolytic manganese dioxide product is obtained.
进一步的，步骤（1）中所述氧化锰矿粉中小于200目粒度的占90%～95%且金属锰的质量含量为16～18%；所述硫铁矿粉中小于120目粒度的占90%～95%且参与反应的有效硫的质量含量为30～40%，所述工业硫酸是质量分数为98%的工业硫酸。Further, in step (1), the manganese oxide ore powder with a particle size smaller than 200 mesh accounts for 90% to 95% and the mass content of metal manganese is 16 to 18%; the pyrite powder with a particle size smaller than 120 mesh accounts for 90%-95%. 90% to 95% and the mass content of the available sulfur participating in the reaction is 30 to 40%, and the industrial sulfuric acid is an industrial sulfuric acid with a mass fraction of 98%.
进一步的，步骤（2）中所述极细氧化锰矿粉中小于325目粒度的占90%～95%，所述碳酸钙为纳米碳酸钙。Further, in the ultrafine manganese oxide ore powder in step (2), the particle size smaller than 325 mesh accounts for 90% to 95%, and the calcium carbonate is nano calcium carbonate.
进一步的，步骤（3）中所述搅拌的速度为200～300r/min。Further, the stirring speed in step (3) is 200-300 r/min.
进一步的，步骤（4）中所述搅拌的速度为50～100r/min。Further, the stirring speed in step (4) is 50-100 r/min.
进一步的，所述氢氧化锂溶液的质量分数为20～25%，所述高锰酸钾溶液的质量分数为30～40%。Further, the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%.
进一步的，步骤（7）中加入的高锰酸钾溶液与电解二氧化锰粉末的重量比为25:1000。Further, the weight ratio of the potassium permanganate solution added in the step (7) to the electrolytic manganese dioxide powder is 25:1000.
进一步的，步骤（7）中加入的氢氧化锂溶液与电解二氧化锰粉末的重量比为30:1000。Further, the weight ratio of the lithium hydroxide solution added in step (7) to the electrolytic manganese dioxide powder is 30:1000.
本发明通过定量添加硫化锰去除重金属离子，为保证有效去除重金属离子（特别是铅、锑等金属离子）需要加入大量硫化锰，但是随着硫化锰的浓度增加，使得溶液的粘度增大，导致硫化锰呈块状粘连在一起，难以在溶液中扩散，从而使得硫化锰的除杂效果大幅降低，所以本发明在加入硫化锰的同时，还定量加入由乙醇、丙醇和异丙醇中的任意一种或多种配制的助剂A，降低溶液粘度，促进硫化锰分散，增加硫化锰的除杂效果。The present invention removes heavy metal ions by quantitatively adding manganese sulfide. In order to ensure the effective removal of heavy metal ions (especially metal ions such as lead and antimony), a large amount of manganese sulfide needs to be added. However, as the concentration of manganese sulfide increases, the viscosity of the solution increases, resulting in The manganese sulfide sticks together in a block shape, and it is difficult to diffuse in the solution, so that the impurity removal effect of the manganese sulfide is greatly reduced. One or more additives A formulated to reduce the viscosity of the solution, promote the dispersion of manganese sulfide, and increase the impurity removal effect of manganese sulfide.
本发明通过定量添加氟化亚锰去除钙、镁离子，同时添加由壳聚糖和柠檬酸混合配制的助剂B与氟化亚锰协同作用，改善氟化亚锰在溶液中的分散度，促进氟化亚锰与钙、镁离子的结合，提高氟化亚锰的除杂效果。The invention removes calcium and magnesium ions by quantitatively adding manganese fluoride, and at the same time adds the auxiliary agent B prepared by mixing chitosan and citric acid to synergize with the manganese fluoride, so as to improve the dispersion of the manganese fluoride in the solution, Promote the combination of manganese fluoride with calcium and magnesium ions, and improve the impurity removal effect of manganese fluoride.
漂洗过程中使用氢氧化锂溶液和高锰酸钾溶液，可以避免向EMD产品中带入杂质钠；加入少量的高锰酸钾起到氧化作用，去除残留在EMD中的低价锰。The use of lithium hydroxide solution and potassium permanganate solution in the rinsing process can avoid introducing impurity sodium into EMD products; adding a small amount of potassium permanganate can oxidize and remove low-valent manganese remaining in EMD.
本技术方案与现有技术相比较具有以下有益效果：Compared with the prior art, the technical solution has the following beneficial effects:
1、本发明可以有效去除硫酸锰溶液中的杂质，避免带入到EMD产品中，减轻后续产品精制的难度，提高了生产效率，从而获得低杂质EMD产品。1. The present invention can effectively remove impurities in the manganese sulfate solution, avoid being brought into EMD products, reduce the difficulty of subsequent product refining, and improve production efficiency, thereby obtaining low-impurity EMD products.
2、本发明方法工艺简单，简化生产流程，而且可操控性高，适合规模化、自动化生产低杂质EMD产品。2. The method of the present invention has the advantages of simple process, simplified production process and high controllability, and is suitable for large-scale and automated production of low-impurity EMD products.
图1是实验例1中EMD产品的检测结果数据表。Figure 1 is a data table of the test results of the EMD product in Experimental Example 1.
图2是实验例2中EMD产品的检测结果数据表。Figure 2 is a data table of the detection results of the EMD product in Experimental Example 2.
图3是实验例3中EMD产品的检测结果数据表。FIG. 3 is a data table of test results of EMD products in Experimental Example 3. FIG.
以下通过实施例进一步说明本发明，但不作为对本发明的限制。The following examples further illustrate the present invention, but are not intended to limit the present invention.
实施例1：Example 1:
一种低杂质电解二氧化锰的制备方法，其包括以下步骤：A preparation method of low impurity electrolytic manganese dioxide, which comprises the following steps:
（1）将氧化锰矿粉、硫铁矿粉、工业硫酸和电解废液加入至浸出反应槽中，在90～95℃、200～300r/min的搅拌下反应3～4h，得到混合浆液；所述氧化锰矿粉与硫铁矿粉的重量比为1:0.22，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的工业硫酸和电解废液中硫酸的重量之和的比为1:0.28，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的电解废液的重量之比为1:6.5；所述氧化锰矿粉中小于200目粒度的占90%～95%且金属锰的质量含量为16～18%；所述硫铁矿粉中小于120目粒度的占90%～95%且参与反应的有效硫的质量含量为30～40%，所述工业硫酸是质量分数为98%的工业硫酸；(1) Add manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into the leaching reaction tank, and react for 3-4 hours at 90-95 °C and 200-300 r/min stirring to obtain a mixed slurry; The weight ratio of described manganese oxide ore powder and pyrite powder is 1:0.22, the ratio of the weight sum of described manganese oxide ore powder and pyrite powder and the weight sum of sulfuric acid in described industrial sulfuric acid and electrolytic waste liquid It is 1:0.28, and the ratio of the weight sum of the described manganese oxide ore powder and pyrite powder to the weight of the described electrolytic waste liquid is 1:6.5; in the described manganese oxide ore powder less than 200 mesh particle size accounts for 90% ～95% and the mass content of metal manganese is 16～18%; in the pyrite powder less than 120 mesh particle size accounts for 90%～95% and the mass content of the effective sulfur participating in the reaction is 30～40%, the Industrial sulfuric acid is industrial sulfuric acid with a mass fraction of 98%;
（2）在90～95℃下，向混合浆液中加入纳米碳酸钙调节pH至4.0～4.5，检测混合浆液中二价铁离子含量，若二价铁离子含量大于或等于10-5mol/L时，加入极细氧化锰矿粉直到二价铁离子含量小于10-5mol/L，再继续向混合浆液中加入纳米碳酸钙调节pH至6.0～6.5，检测混合浆液中三价铁离子含量，若三价铁离子含量大于或等于10-5mol/L时，继续加入纳米碳酸钙直到三价铁离子含量小于10-5mol/L，然后将混合浆液压滤得到滤液A；所述极细氧化锰矿粉中小于325目粒度的占95%；(2) At 90～95℃, add nano calcium carbonate to the mixed slurry to adjust the pH to 4.0～4.5, and detect the content of ferrous ions in the mixed slurry. If the content of ferrous ions is greater than or equal to 10-5mol/L , add ultra-fine manganese oxide ore powder until the content of ferric ions is less than 10-5mol/L, and then continue to add nano-calcium carbonate to the mixed slurry to adjust the pH to 6.0-6.5, and detect the content of ferric ions in the mixed slurry. When the iron ion content is greater than or equal to 10-5mol/L, continue to add nano calcium carbonate until the ferric ion content is less than 10-5mol/L, then the mixed slurry is hydraulically filtered to obtain filtrate A; 325 mesh size accounts for 95%;
（3）将滤液A加热至86℃，加入电解废液调节pH至3.8，然后缓慢加入硫化锰和助剂B，在200r/min的搅拌下反应1h，压滤得到滤液C；所述硫化锰的重量与滤液A的体积比为50g:1L，所述助剂B为丙醇和异丙醇的组合，所述助剂B与滤液A的体积比为1:100；(3) Heat the filtrate A to 86°C, add electrolytic waste liquid to adjust the pH to 3.8, then slowly add manganese sulfide and auxiliary B, react under stirring at 200 r/min for 1 hour, and press filter to obtain filtrate C; the manganese sulfide The volume ratio of the weight and the filtrate A is 50g:1L, and the auxiliary agent B is the combination of propanol and Virahol, and the volume ratio of the auxiliary agent B and the filtrate A is 1:100;
（4）将滤液C在85℃、pH为6.0的条件下，缓慢加入氟化亚锰和助剂D，在50r/min的搅拌下反应2h，过滤得到净化的硫酸锰溶液；所述氟化亚锰的重量与滤液C的体积比为100g:1L，所述助剂D是将壳聚糖和柠檬酸等体积混合反应得到的，所述助剂D的重量与滤液C的体积比为15g:1000L；(4) Under the conditions of 85°C and pH of 6.0, the filtrate C was slowly added with manganese fluoride and auxiliary D, reacted under stirring at 50r/min for 2 hours, and filtered to obtain a purified manganese sulfate solution; The weight of manganese and the volume ratio of filtrate C are 100g: 1L, and the auxiliary agent D is obtained by mixing chitosan and citric acid in equal volumes, and the weight of the auxiliary agent D and the volume ratio of filtrate C are 15g. :1000L;
（5）将硫酸锰溶液送入电解槽中进行电解，电解液温度为98～100℃，阳极电流密度为55～80A/m2，电解液硫酸浓度为0.35～0.70mol/L、硫酸锰浓度为0.30～0.50 mol/L，槽电压为2.0～4.0V，电解周期为10～12天，电解后得到电解二氧化锰半成品和电解废液；(5) The manganese sulfate solution is sent into the electrolytic cell for electrolysis. The temperature of the electrolyte is 98 to 100°C, the anode current density is 55 to 80A/m2, the concentration of sulfuric acid in the electrolyte is 0.35 to 0.70mol/L, and the concentration of manganese sulfate is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and the semi-finished electrolytic manganese dioxide and electrolytic waste liquid are obtained after electrolysis;
（6）将电解二氧化锰半成品破碎成粒度为10mm～30mm的颗粒，然后加入热水漂洗，漂洗温度为90～95℃，直到漂洗液中硫酸的含量低于1g/L，接着采用氢氧化锂溶液在60～70℃下漂洗，调节pH至6.5～7.0，然后用热水在90～95℃下漂洗8～10h，然后将颗粒进行磨粉得到粒度小于325目的电解二氧化锰粉末；(6) The semi-finished electrolytic manganese dioxide is crushed into particles with a particle size of 10mm to 30mm, and then rinsed with hot water at a rinsing temperature of 90 to 95°C until the content of sulfuric acid in the rinse solution is less than 1g/L, and then the use of hydroxide Rinse the lithium solution at 60～70℃, adjust pH to 6.5～7.0, then rinse with hot water at 90～95℃ for 8～10h, then grind the particles to obtain electrolytic manganese dioxide powder with particle size less than 325 mesh;
（7）向电解二氧化锰粉末中加入高锰酸钾溶液反应1h，反应温度为90～95℃，接着加入氢氧化锂溶液，继续反应0.5h，反应温度为90～95℃，当pH达到6.5～7.0时为合格，然后先进行压滤再在100～105℃下进行闪蒸旋流烘干得到电解二氧化锰粉末后，采用密相气力输送方式输送到重力掺混仓进行掺混，掺混时间为16～24h，得到低杂质电解二氧化锰产品；所述氢氧化锂溶液的质量分数为20～25%，所述高锰酸钾溶液的质量分数为30～40%；加入的高锰酸钾溶液与电解二氧化锰粉末的重量比为25:1000；加入的氢氧化锂溶液与电解二氧化锰粉末的重量比为30:1000。(7) Add potassium permanganate solution to electrolytic manganese dioxide powder to react for 1 hour, the reaction temperature is 90～95℃, then add lithium hydroxide solution, continue to react for 0.5h, the reaction temperature is 90～95℃, when pH reaches 90～95℃ 6.5～7.0 is qualified, then press filter and then flash cyclone drying at 100～105℃ to obtain electrolytic manganese dioxide powder, which is transported to gravity blending bin for blending by dense phase pneumatic conveying. The blending time is 16-24h to obtain a low-impurity electrolytic manganese dioxide product; the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%; the added The weight ratio of the potassium permanganate solution to the electrolytic manganese dioxide powder is 25:1000; the weight ratio of the added lithium hydroxide solution to the electrolytic manganese dioxide powder is 30:1000.
实施例2：Example 2:
其与实施例1所述方法的区别仅在于：所述氧化锰矿粉与硫铁矿粉的重量比为1:0.16，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的工业硫酸和电解废液中硫酸的重量之和的比为1:0.25，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的电解废液的重量之比为1:5；将滤液A加热至80℃，调节pH至3.5，然后缓慢加入硫化锰和助剂B，在250r/min的搅拌下反应2h；所述硫化锰的重量与滤液A的体积比为55g:1L，所述助剂B为乙醇，所述助剂B与滤液A的体积比为2:100；将滤液C在80℃、pH为6.2的条件下，缓慢加入氟化亚锰和助剂D，在80r/min的搅拌下反应2.5h；所述氟化亚锰的重量与滤液C的体积比为80g:1L，所述助剂D的重量与滤液C的体积比为10g:1000L。The only difference between it and the method described in Example 1 is that the weight ratio of the manganese oxide ore powder to the pyrite powder is 1:0.16, and the sum of the weights of the manganese oxide ore powder and the pyrite powder is the same as the The ratio of the weight sum of sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid is 1:0.25, and the ratio of the weight sum of the described manganese oxide ore powder and the pyrite powder to the weight of the described electrolytic waste liquid is 1:5; The filtrate A was heated to 80°C, the pH was adjusted to 3.5, then manganese sulfide and auxiliary B were slowly added, and the reaction was carried out under stirring at 250 r/min for 2 h; the weight ratio of the manganese sulfide to the filtrate A was 55 g: 1 L, The auxiliary agent B is ethanol, and the volume ratio of the auxiliary agent B to the filtrate A is 2:100; the filtrate C is slowly added manganese fluoride and auxiliary agent D at 80° C. and the pH is 6.2. The reaction was carried out for 2.5h under the stirring of 80r/min; the volume ratio of the weight of the manganese fluoride to the filtrate C was 80g:1L, and the volume ratio of the weight of the auxiliary agent D to the filtrate C was 10g:1000L.
实施例3：Example 3:
其与实施例1所述方法的区别仅在于：所述氧化锰矿粉与硫铁矿粉的重量比为1:0.30，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的工业硫酸和电解废液中硫酸的重量之和的比为1:0.35，所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的电解废液的重量之比为1:7；将滤液A加热至90℃，调节pH至4.0，然后缓慢加入硫化锰和助剂B，在300r/min的搅拌下反应1.5h；所述硫化锰的重量与滤液A的体积比为60g:1L，所述助剂B为丙醇，所述助剂B与滤液A的体积比为3:100；将滤液C在90℃、pH为6.5的条件下，缓慢加入氟化亚锰和助剂D，在100r/min的搅拌下反应3h；所述氟化亚锰的重量与滤液C的体积比为90g:1L，所述助剂D的重量与滤液C的体积比为20g:1000L。The only difference between it and the method described in Example 1 is that the weight ratio of the manganese oxide ore powder to the pyrite powder is 1:0.30, and the sum of the weights of the manganese oxide ore powder and the pyrite powder is the same as the The ratio of the weight sum of sulfuric acid in the industrial sulfuric acid and the electrolytic waste liquid is 1:0.35, and the ratio of the weight sum of the described manganese oxide ore powder and pyrite powder to the weight of the described electrolytic waste liquid is 1:7; The filtrate A was heated to 90°C, adjusted to pH 4.0, then slowly added manganese sulfide and auxiliary B, and reacted for 1.5h under stirring at 300r/min; the volume ratio of the weight of the manganese sulfide to the filtrate A was 60g:1L , the auxiliary agent B is propanol, and the volume ratio of the auxiliary agent B to the filtrate A is 3:100; the filtrate C is at 90 ° C and the pH is 6.5, slowly add manganese fluoride and auxiliary agent D , and reacted for 3h under stirring at 100r/min; the weight of the manganese fluoride and the volume ratio of the filtrate C were 90g:1L, and the weight of the auxiliary agent D and the volume ratio of the filtrate C were 20g:1000L.
对比例1：Comparative Example 1:
其与实施例1所述方法的区别仅在于，在步骤（3）中，只加入硫化钡。The only difference between it and the method described in Example 1 is that, in step (3), only barium sulfide is added.
对比例2：Comparative Example 2:
其与实施例1所述方法的区别仅在于，在步骤（3）中，只加入硫化锰。The only difference between it and the method described in Example 1 is that, in step (3), only manganese sulfide is added.
对比例3：Comparative Example 3:
其与实施例1所述方法的区别仅在于，在步骤（4）中，只加入浓度为100ppm的聚丙烯酰胺溶液；所述聚丙烯酰胺溶液的重量与滤液B的体积比为10g:80m3。The only difference between it and the method described in Example 1 is that in step (4), only a polyacrylamide solution with a concentration of 100 ppm is added; the weight ratio of the polyacrylamide solution to the filtrate B is 10g:80m3.
对比例4：Comparative Example 4:
其与实施例1所述方法的区别仅在于，在步骤（4）中，只加入氟化亚锰。The only difference between it and the method described in Example 1 is that, in step (4), only manganese fluoride is added.
实验例1：Experimental example 1:
按照实施例1～3中所述方法生产对应得到EMD样品1～3，按照对比例1～4中所述方法生产对应得到EMD样品4～7，检测样品的纯度和杂质含量，具体结果见附图1。According to the methods described in Examples 1 to 3, EMD samples 1 to 3 were produced, and EMD samples 4 to 7 were produced according to the methods described in Comparative Examples 1 to 4. The purity and impurity content of the samples were tested. The specific results are shown in the attached figure 1.
实验例2：Experimental example 2:
按照实施例1所述方法，在步骤（3）中，所述助剂B与滤液A的体积比分别为0.5:100，0.8:100，1:100，2:100，3:100，4:100，5:100，检测所得产品的纯度和杂质含量，具体结果见附图2，由数据可见，助剂B与滤液A以及滤液A与硫化锰之间的用量比例需要控制在一定的范围内，才能促进硫化锰的除杂效果，助剂B过多使硫化锰过于分散，生成重金属硫化物不易聚集沉淀除去，降低除杂效果；助剂B过少，硫化锰随着浓度增加而粘结，无法有效扩散，降低与重金属离子结合效率，无法达到除杂效果。According to the method described in Example 1, in step (3), the volume ratio of the auxiliary agent B to the filtrate A is 0.5:100, 0.8:100, 1:100, 2:100, 3:100, 4:100, respectively. 100,5:100, detect the purity and impurity content of the obtained product, the specific results are shown in accompanying drawing 2, as can be seen from the data, the dosage ratio between auxiliary agent B and filtrate A and filtrate A and manganese sulfide needs to be controlled within a certain range In order to promote the impurity removal effect of manganese sulfide, too much additive B will make manganese sulfide too dispersed, and the resulting heavy metal sulfides are not easy to aggregate, precipitate and remove, and reduce the impurity removal effect; if additive B is too small, manganese sulfide will bond with the increase of concentration. , cannot diffuse effectively, reduce the binding efficiency with heavy metal ions, and cannot achieve the effect of impurity removal.
实验例3：Experimental example 3:
按照实施例1所述方法，在步骤（4）中，所述助剂D的重量与滤液C的体积比分别为1g:1000L，5g:1000L，10g:1000L，15g:1000L，20g:1000L，25g:1000L，30g:1000L，35g:1000L，40g:1000L，检测所得产品的纯度和杂质含量，具体结果见附图3，由数据可见，助剂D与滤液C以及滤液C与氟化亚锰之间的用量比例需要控制在一定的范围内，才能促进氟化亚锰的分散，从而达到钙、镁离子的除杂效果。According to the method described in Example 1, in step (4), the weight of the auxiliary agent D and the volume ratio of the filtrate C are respectively 1g:1000L, 5g:1000L, 10g:1000L, 15g:1000L, 20g:1000L, 25g: 1000L, 30g: 1000L, 35g: 1000L, 40g: 1000L, detect the purity and impurity content of the obtained product, the specific results are shown in Figure 3, as can be seen from the data, auxiliary D and filtrate C and filtrate C and manganese fluoride The dosage ratio between them needs to be controlled within a certain range, in order to promote the dispersion of manganese fluoride, so as to achieve the impurity removal effect of calcium and magnesium ions.
Claims (1)
- 一种低杂质电解二氧化锰的制备方法，其特征在于：包括以下步骤：A preparation method of low impurity electrolytic manganese dioxide, is characterized in that: comprises the following steps:（1）将氧化锰矿粉、硫铁矿粉、工业硫酸和电解废液加入至浸出反应槽中，在温度为90～95℃、搅拌速度为200～300r/min的条件下反应3～4h，得到混合浆液；所述氧化锰矿粉与硫铁矿粉的重量比为1:（0.16～0.30），所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的工业硫酸和电解废液中硫酸的重量之和的比为1:（0.25～0.35），所述的氧化锰矿粉和硫铁矿粉的重量之和与所述的电解废液的重量之比为1:（5～7）；(1) Add manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into the leaching reaction tank, and react for 3 to 4 hours at a temperature of 90 to 95 °C and a stirring speed of 200 to 300 r/min. A mixed slurry is obtained; the weight ratio of the manganese oxide ore powder and the pyrite powder is 1: (0.16-0.30), the sum of the weight of the manganese oxide ore powder and the pyrite powder and the industrial sulfuric acid and electrolysis waste The ratio of the sum of the weight of sulfuric acid in the liquid is 1: (0.25～0.35), and the ratio of the sum of the weight of the described manganese oxide ore powder and pyrite powder to the weight of the described electrolytic waste liquid is 1: (5～0.35) 7);（2）在温度为90～95℃的条件下，向混合浆液中加入碳酸钙，调节混合浆液的pH至4.0～4.5，然后检测混合浆液中二价铁离子含量，若二价铁离子含量大于或等于10 -5mol/L时，向混合浆液中加入极细氧化锰矿粉，直到二价铁离子含量小于10 -5mol/L，再继续向混合浆液中加入碳酸钙，调节混合浆液的pH至6.0～6.5，然后检测混合浆液中三价铁离子含量，若三价铁离子含量大于或等于10 -5mol/L时，向混合浆液中继续加入碳酸钙，直到三价铁离子含量小于10 -5mol/L，然后将混合浆液进行压滤得到滤液A； (2) Add calcium carbonate to the mixed slurry at a temperature of 90 to 95 °C, adjust the pH of the mixed slurry to 4.0 to 4.5, and then detect the content of ferrous ions in the mixed slurry. If the content of ferrous ions is greater than When equal to or equal to 10 -5 mol/L, add ultrafine manganese oxide ore powder to the mixed slurry until the ferrous ion content is less than 10 -5 mol/L, then continue to add calcium carbonate to the mixed slurry to adjust the pH of the mixed slurry To 6.0～6.5, then detect the content of ferric ions in the mixed slurry, if the content of ferric ions is greater than or equal to 10 -5 mol/L, continue to add calcium carbonate to the mixed slurry until the content of ferric ions is less than 10 -5 mol/L, then the mixed slurry is subjected to pressure filtration to obtain filtrate A;（3）将滤液A加热至80～90℃，用电解废液调节滤液A的pH至3.5～4.0，然后缓慢加入硫化锰和助剂B，搅拌反应1～2h，压滤得到滤液C；所述硫化锰的重量与滤液A的体积比为（50～60）g:1L，所述助剂B为乙醇、丙醇和异丙醇中的任意一种或多种组合，所述助剂B与滤液A的体积比为（1～3）:100；(3) Heat the filtrate A to 80-90°C, adjust the pH of the filtrate A to 3.5-4.0 with the electrolytic waste liquid, then slowly add manganese sulfide and auxiliary B, stir and react for 1-2 hours, and press-filter to obtain the filtrate C; The weight ratio of the manganese sulfide to the volume of the filtrate A is (50～60) g:1L, and the auxiliary agent B is any one or more combinations of ethanol, propanol and isopropanol. The volume ratio of filtrate A is (1～3):100;（4）将滤液C在温度为80～90℃、pH为6.0～6.5的条件下，缓慢加入氟化亚锰和助剂D，搅拌反应2～3h，过滤得到净化的硫酸锰溶液；所述氟化亚锰的重量与滤液C的体积比为（80～100）g:1L，所述助剂D是将壳聚糖和柠檬酸等体积混合反应得到的，所述助剂D的重量与滤液C的体积比为（10～20）g:1000L；(4) Under the condition that the temperature is 80～90℃ and the pH is 6.0～6.5, the filtrate C is slowly added with manganese fluoride and auxiliary D, the reaction is stirred for 2～3h, and the purified manganese sulfate solution is obtained by filtration; The ratio of the weight of manganese fluoride to the volume of the filtrate C is (80-100) g: 1L. The auxiliary agent D is obtained by mixing and reacting chitosan and citric acid in equal volumes. The volume ratio of filtrate C is (10～20) g:1000L;（5）将硫酸锰溶液送入电解槽中进行电解，电解液温度为98～100℃，阳极电流密度为55～80A/m 2，电解液硫酸浓度为0.35～0.70mol/L、硫酸锰浓度为0.30～0.50 mol/L，槽电压为2.0～4.0V，电解周期为10～12天，电解后得到电解二氧化锰半成品和电解废液； (5) The manganese sulfate solution is sent into the electrolytic cell for electrolysis, the temperature of the electrolyte is 98～100℃, the anode current density is 55～80A/m 2 , the concentration of sulfuric acid in the electrolyte is 0.35～0.70mol/L, and the concentration of manganese sulfate is 0.35～0.70mol/L. It is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and the semi-finished electrolytic manganese dioxide and electrolytic waste liquid are obtained after electrolysis;（6）将电解二氧化锰半成品破碎成粒度为10mm～30mm的颗粒，然后加入热水漂洗，漂洗温度为90～95℃，直到漂洗液中硫酸的含量低于1g/L，接着采用氢氧化锂溶液在温度为60～70℃下漂洗，调节pH至6.5～7.0，然后用热水在温度为90～95℃下漂洗8～10h，然后将颗粒进行磨粉得到粒度小于325目的电解二氧化锰粉末；(6) The semi-finished electrolytic manganese dioxide is crushed into particles with a particle size of 10mm to 30mm, and then rinsed with hot water at a rinsing temperature of 90 to 95°C until the content of sulfuric acid in the rinse solution is less than 1g/L, and then the use of hydroxide The lithium solution was rinsed at a temperature of 60-70 °C, adjusted to pH 6.5-7.0, and then rinsed with hot water at a temperature of 90-95 °C for 8-10 hours, and then the particles were ground to obtain electrolytic dioxide with a particle size of less than 325 meshes. manganese powder;（7）向电解二氧化锰粉末中加入高锰酸钾溶液反应1h，反应温度为90～95℃，接着加入氢氧化锂溶液，继续反应0.5h，反应温度为90～95℃，当pH达到6.5～7.0时为合格，然后先进行压滤再在100～105℃的温度下进行闪蒸旋流烘干得到电解二氧化锰粉末，接着将电解二氧化锰粉末采用密相气力输送方式输送到重力掺混仓进行掺混，掺混时间为16～24h，得到低杂质电解二氧化锰产品。(7) Add potassium permanganate solution to electrolytic manganese dioxide powder to react for 1 hour, the reaction temperature is 90～95℃, then add lithium hydroxide solution, continue to react for 0.5h, the reaction temperature is 90～95℃, when pH reaches 90～95℃ 6.5～7.0 is qualified, then press filtration and then flash cyclone drying at a temperature of 100～105℃ to obtain electrolytic manganese dioxide powder, and then the electrolytic manganese dioxide powder is transported by dense phase pneumatic conveying to The gravity mixing bin is used for mixing, and the mixing time is 16-24 hours to obtain a low-impurity electrolytic manganese dioxide product.2根据权利要求1所述的低杂质电解二氧化锰的制备方法，其特征在于：步骤（2）中所述极细氧化锰矿粉中小于325目粒度的占90%～95%，所述碳酸钙为纳米碳酸钙。2. The preparation method of low-impurity electrolytic manganese dioxide according to claim 1, characterized in that: in the ultrafine manganese oxide ore powder described in step (2), the particle size smaller than 325 mesh accounts for 90% to 95%, and the carbonic acid Calcium is nano calcium carbonate.
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2021
- 2021-03-31 CN CN202110345289.0A patent/CN113088997B/en active Active
- 2021-04-21 LU LU500575A patent/LU500575B1/en active IP Right Grant
- 2021-04-21 WO PCT/CN2021/088582 patent/WO2022205533A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011085438A1 (en) * | 2010-01-13 | 2011-07-21 | Galaxy Resources Limited | Process for the production of electrolytic manganese dioxide |
| CN103556172A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Method for deeply removing impurities in manganese dioxide electrolyte |
| CN103572316A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide specially used for low-impurity battery |
| CN103579608A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide for positive material-lithium manganate of lithium battery |
| CN103572055A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of manganese sulfate for electrolytic manganese dioxide |
| CN111235390A (en) * | 2020-01-15 | 2020-06-05 | 贵州合众锰业科技有限公司 | Resource recycling method for pyrolusite leaching slag |
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| Publication number | Publication date |
|---|---|
| CN113088997B (en) | 2022-11-29 |
| LU500575B1 (en) | 2022-02-25 |
| CN113088997A (en) | 2021-07-09 |
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