EP0268319B1 - Method for extracting mn metal and manganese dioxide from divalent mn salt solutions - Google Patents
Method for extracting mn metal and manganese dioxide from divalent mn salt solutions Download PDFInfo
- Publication number
- EP0268319B1 EP0268319B1 EP87202092A EP87202092A EP0268319B1 EP 0268319 B1 EP0268319 B1 EP 0268319B1 EP 87202092 A EP87202092 A EP 87202092A EP 87202092 A EP87202092 A EP 87202092A EP 0268319 B1 EP0268319 B1 EP 0268319B1
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- EP
- European Patent Office
- Prior art keywords
- manganese
- anode
- current density
- manganese dioxide
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
Definitions
- This invention relates to a method for simultaneously extracting Mn metal and manganese dioxide in gamma form from divalent manganese salt solutions.
- the invention relates to a method for simultaneously extracting Mn metal and manganese dioxide in gamma form from manganese sulphate solutions.
- Manganese dioxide is used in dry batteries in intimate mixture with graphite or acetylene black.
- manganese dioxide for batteries is in gamma form, and this can be obtained electrolytically by the following production process.
- the production process comprises the following steps:
- the manganese salt which is dissolved in the electrolyte is the sulphate. It is obtained from various raw materials, those mostly used being the manganese minerals pyrolusite and rhodochrosite. A description of the preliminary heat treatments will be omitted for brevity. It will merely be stated that the crude manganese oxide is reacted with sulphuric acid, and the manganese sulphate solution formed is purified because minerals based on manganese dioxide generally have a certain heavy metals content. Purification with lime or limestone is followed by purification with calcium sulphide or hydrogen sulphide.
- the solution fed to electrolysis has an average MnSO4 content of 80-150 g/l and an average H2SO4 content of 50-100 g/l.
- a further component is ammonium sulphate (120-150 g/l) to act as a pH "stabiliser" during electrolysis.
- the electrolyte cycle can vary. In one cycle, the electrolyte is fed into the lower part of the cells in a quantity of 3% of the entire volume per minute; every one or two hours the electrolyte is cleaned by feeding 10-20% of it to treatment with MnCO3 or MnO, and replacing this with fresh electrolyte. In another cycle, electrolyte is fed in such a quantity that the spent electrolyte leaves the cells containing 50 g/l of MnSO4; this is mixed with an equal quantity of fresh electrolyte containing 150 g/l of MnSO4 and the mixture is returned to the cycle.
- the anode assembly is removed from the cell in order to recover the product. This operation, which can be carried out either manually or automatically, is the most onerous of the process.
- the MnO2 fragments obtained from the anode deposits are washed with water and ground to less than 74 microns.
- the powder is again washed a number of times to eliminate any remaining acidity, and is again dried at low temperature, namely 80-85°C. All the various process steps are important in terms of production economy and the quality of the commercial product.
- the electrolysis operating conditions are also determining with regard to product quality and electricity consumption.
- the cells are normally rectangular steel tanks clad with material which is resistant to both corrosion and temperature and is of very low conductivity, such as glass-fibre reinforced resins, rubber or acid-resistant cement or brick.
- the electrodes can be flat or round bars or tubes.
- the cathodes are generally of graphite, lead or stainless steel. Graphite anodes are mostly used, as they tolerate high current density without becoming passive, but their mechanical strength falls progressively due to corrosive attack.
- Lead anodes normally containing 3-8% of antimony have the drawback that at high current density they are subject to chemical attack and contaminate the dioxide produced. They have the advantage that when they are no longer usable the lead can be recovered by smelting. Titanium anodes would perhaps be the ideal, but certainly very costly; they have excellent mechanical stability and a useful life of some years; they tend to become passive, but this drawback can be obviated by careful monitoring of the current density and the H2SO4 concentration in the electrolyte.
- the useful anode:cathode surface area ratio is about 2:1.
- the distance between anodes and cathode is about 25-50 mm.
- a production cell can contain as many as 220 graphite anodes (flat bars of 1100 x 175 x 25 mm) arranged in 44 rows of 5 anodes each.
- the manganese dioxide obtained by known methods has an average chemical composition of 62% Mn by weight, of which 92% is in the form of MnO2, 1.6% is in the form of soluble Mn and the remainder is in the form of oxides other than MnO2, together with traces of As, about 0.0004/% of copper by weight, traces of Ni and Co, 0.0001-0.05% of Pb by weight, about 0. 02% of Fe, about 1.2% of SO4 by weight, and about 0.01% of SiO2 by weight, the remainder to 100% being oxygen.
- the solution to be electrolysed generally consist of manganous sulphate and ammonium sulphate, and is practically neutral.
- Cathodic electrodeposition in accordance with the overall reaction; Mn2+ + H2O ⁇ Mn + 2H+ + 1 ⁇ 2O2 takes place under the following conditions.
- Catholyte Mn as MnSO4 30-40 g/l (NH4)2SO4 125-150 g/l SO2 0.3-0.5 g/l pH 6-7.2
- Anolyte Mn as MnSO4 10-20 g/l H2SO4 25-40 g/l (NH4)2SO4 125-150 g/l Current density: 430-650 A/m2
- Anode composition Pb + 1% Ag
- Cathode composition Hastelloy or AISI 316 or Titanium Cell voltage: 5.2 V
- Diaphragm acrylic, cotton Current yield: 65-75%
- a method has been surprisingly found, and constitutes the subject of the present invention, for simultaneously obtaining Mn metal and manganese dioxide, ie for combining the separate processes heretofore described, by electrolysing a manganese sulphate solution in an electrolytic cell provided with an anionic membrane.
- the present invention provides a method for simultaneously obtaining Mn metal and manganese dioxide in gamma form according to present cl.1
- the reaction which takes place at the anode is as follows: 2Mn2+ ⁇ 2 Mn3+ + 2e
- the electrolysis proceeds with the passage of SO42 ⁇ ions from the cathode compartment to the anode compartment of the cell divided by the anionic membrane.
- the electrolysis is implemented with a cell which is shown diagrammatically on the accompanying figure.
- the cell consists of a cylindrical container 1, particularly of PVC, in which a lead alloy anode 2 and a stainless steel cathode 3 are disposed.
- the anode region 4 is separated from the cathode region 5 by an anionic membrane 6 having a funnel-shaped base.
- the membrane 6 is of the aforesaid type, its purpose being to allow the SO42 ⁇ ions to pass from the cathode region to the anode region.
- the feed to the anode region is represented by the reference numeral 7; the feed to the cathode region is represented by the reference numeral 8.
- the discharge from the cathode region is indicated by the reference numeral 9 and the discharge from the anode region is indicated by the reference numeral 10.
- the reference numeral 11 indicates the anode recycling, and 12 the feed and discharge pipes for the cooling water of the anode 2.
- the height of the anode discharge offtake is adjustable so as to obtain a level difference between the free surface of the anolyte and that of the catholyte.
- EXAMPLE 1 Overall feed solution Mn 40 g/l (NH4)2SO4 170 g/l SO2 0.1 g/l pH 6.3 Cathode current density 350 A/m2 Temperature of cathode region 30°C Anode current density 4500 A/m2 Temperature of anode region 30°C Cathode current yield (Mn) 56% Anode current yield (MnO2) 83% EXAMPLE 2 Overall feed solution Mn 38 g/l (NH4)2SO4 200 g/l SO2 0.2g/l pH 6.5 Cathode current density 300 A/m2 Temperature of cathode region 28°C Anode current density 3850 A/m2 Temperature of anode region 30°C Cathode current yield (Mn) 60% Anode current yield (MnO2) 95% EX
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
- This invention relates to a method for simultaneously extracting Mn metal and manganese dioxide in gamma form from divalent manganese salt solutions.
- More particularly, the invention relates to a method for simultaneously extracting Mn metal and manganese dioxide in gamma form from manganese sulphate solutions.
- The description given hereinafter refers to this second case, which is that of greatest interest.
- The known art described separate methods for producing manganese dioxide or manganese metal.
- Manganese dioxide is used in dry batteries in intimate mixture with graphite or acetylene black.
- Preferably, manganese dioxide for batteries is in gamma form, and this can be obtained electrolytically by the following production process.
- The overall electrochemical reaction on which manganese dioxide production is based is as follows:
- at the anode:
-
- at the cathode:
-
- The production process comprises the following steps:
- 1) Preparing the solution to be electrolysed
- 2) Electrolysis
- 3) Recovering the crude manganese dioxide
- 4) Treatment to obtain the commercial product
- The manganese salt which is dissolved in the electrolyte is the sulphate. It is obtained from various raw materials, those mostly used being the manganese minerals pyrolusite and rhodochrosite. A description of the preliminary heat treatments will be omitted for brevity. It will merely be stated that the crude manganese oxide is reacted with sulphuric acid, and the manganese sulphate solution formed is purified because minerals based on manganese dioxide generally have a certain heavy metals content. Purification with lime or limestone is followed by purification with calcium sulphide or hydrogen sulphide. The solution fed to electrolysis has an average MnSO₄ content of 80-150 g/l and an average H₂SO4 content of 50-100 g/l. A further component is ammonium sulphate (120-150 g/l) to act as a pH "stabiliser" during electrolysis.
- Electrolysis takes place in suitable cells under the following average conditions:
- current density at the anode: 70-120 A/m²
- voltage: 1.8-2.5 V
- electrolyte temperature: 90-95°C
- To reduce the heat and evaporation losses, either closed cells are used or, more practically, the electrolyte is covered with a layer of oil or paraffin.
- The electrolyte cycle can vary. In one cycle, the electrolyte is fed into the lower part of the cells in a quantity of 3% of the entire volume per minute; every one or two hours the electrolyte is cleaned by feeding 10-20% of it to treatment with MnCO₃ or MnO, and replacing this with fresh electrolyte. In another cycle, electrolyte is fed in such a quantity that the spent electrolyte leaves the cells containing 50 g/l of MnSO₄; this is mixed with an equal quantity of fresh electrolyte containing 150 g/l of MnSO₄ and the mixture is returned to the cycle.
- When the dioxide deposited on the electrodes has reached the scheduled thickness, the anode assembly is removed from the cell in order to recover the product. This operation, which can be carried out either manually or automatically, is the most onerous of the process.
- The MnO₂ fragments obtained from the anode deposits are washed with water and ground to less than 74 microns. The powder is again washed a number of times to eliminate any remaining acidity, and is again dried at low temperature, namely 80-85°C. All the various process steps are important in terms of production economy and the quality of the commercial product. The electrolysis operating conditions are also determining with regard to product quality and electricity consumption.
- Both the labour requirement and the electrode life depend on the method used for recovering the dioxide from the electrodes.
- The cells are normally rectangular steel tanks clad with material which is resistant to both corrosion and temperature and is of very low conductivity, such as glass-fibre reinforced resins, rubber or acid-resistant cement or brick.
- The electrodes can be flat or round bars or tubes.
- The cathodes are generally of graphite, lead or stainless steel. Graphite anodes are mostly used, as they tolerate high current density without becoming passive, but their mechanical strength falls progressively due to corrosive attack.
- Lead anodes normally containing 3-8% of antimony have the drawback that at high current density they are subject to chemical attack and contaminate the dioxide produced. They have the advantage that when they are no longer usable the lead can be recovered by smelting. Titanium anodes would perhaps be the ideal, but certainly very costly; they have excellent mechanical stability and a useful life of some years; they tend to become passive, but this drawback can be obviated by careful monitoring of the current density and the H₂SO₄ concentration in the electrolyte.
- The useful anode:cathode surface area ratio is about 2:1. The distance between anodes and cathode is about 25-50 mm. A production cell can contain as many as 220 graphite anodes (flat bars of 1100 x 175 x 25 mm) arranged in 44 rows of 5 anodes each.
- The manganese dioxide obtained by known methods has an average chemical composition of 62% Mn by weight, of which 92% is in the form of MnO₂, 1.6% is in the form of soluble Mn and the remainder is in the form of oxides other than MnO₂, together with traces of As, about 0.0004/% of copper by weight, traces of Ni and Co, 0.0001-0.05% of Pb by weight, about 0. 02% of Fe, about 1.2% of SO₄ by weight, and about 0.01% of SiO₂ by weight, the remainder to 100% being oxygen.
- Having described the conventional system for producing electrolytic MnO₂, the known processes for producing Mn metal will now be described, as the process according to the present invention relates to the simultaneous electrolytic production of MnO₂ and Mn.
- The solution to be electrolysed generally consist of manganous sulphate and ammonium sulphate, and is practically neutral. Cathodic electrodeposition in accordance with the overall reaction;
takes place under the following conditions.Conditions: Catholyte: Mn as MnSO₄ 30-40 g/l (NH₄)₂SO₄ 125-150 g/l SO₂ 0.3-0.5 g/l pH 6-7.2 Anolyte: Mn as MnSO₄ 10-20 g/l H₂SO₄ 25-40 g/l (NH₄)₂SO₄ 125-150 g/l Current density: 430-650 A/m² Anode composition: Pb + 1% Ag Cathode composition: Hastelloy or AISI 316 or Titanium Cell voltage: 5.2 V Diaphragm: acrylic, cotton Current yield: 65-75% - The following table shows the impurities usually contained.
ELEMENT CONTENT Fe 15 mg/l Cu 10 g/l As 5 g/l Co 25 g/l Ni 25 g/l Pb 25 g/l Mo 10 g/l - A method has been surprisingly found, and constitutes the subject of the present invention, for simultaneously obtaining Mn metal and manganese dioxide, ie for combining the separate processes heretofore described, by electrolysing a manganese sulphate solution in an electrolytic cell provided with an anionic membrane.
-
-
-
- The electrolysis proceeds with the passage of SO₄²⁻ ions from the cathode compartment to the anode compartment of the cell divided by the anionic membrane.
-
- In a preferred embodiment of the method according to the present invention, the electrolysis is implemented with a cell which is shown diagrammatically on the accompanying figure.
- The cell consists of a
cylindrical container 1, particularly of PVC, in which alead alloy anode 2 and astainless steel cathode 3 are disposed. - The
anode region 4 is separated from thecathode region 5 by ananionic membrane 6 having a funnel-shaped base. - The
membrane 6 is of the aforesaid type, its purpose being to allow the SO₄²⁻ ions to pass from the cathode region to the anode region. - The feed to the anode region is represented by the reference numeral 7; the feed to the cathode region is represented by the
reference numeral 8. The discharge from the cathode region is indicated by the reference numeral 9 and the discharge from the anode region is indicated by thereference numeral 10. Thereference numeral 11 indicates the anode recycling, and 12 the feed and discharge pipes for the cooling water of theanode 2. - It should be noted that the height of the anode discharge offtake is adjustable so as to obtain a level difference between the free surface of the anolyte and that of the catholyte.
- The conditions additional to the aforesaid under which the method according to the present invention is operated are as follows:
- anode current density between 3000 A/m² and 5500 A/m²
- cathode current density between 250 A/m² and 400 A/m²
- anolyte consisting of a solution containing 20-40 g/l of Mn and 100-300 g/l of H₂SO₄
- catholyte consisting of a solution containing 30-50 g/l of manganese and 150-200 g/l of ammonium sulphate, at a pH of between 6 and 7
- anolyte temperature between 15 and 30°C
- catholyte temperature between 20 and 35°C
- Some examples are given hereinafter in order to better illustrate the invention, which however is not limited by them or to them. The described apparatus shown on the figure and comprising an anionic membrane is used in the examples.
EXAMPLE 1 Overall feed solution Mn 40 g/l (NH₄)₂SO₄ 170 g/l SO₂ 0.1 g/l pH 6.3 Cathode current density 350 A/m² Temperature of cathode region 30°C Anode current density 4500 A/m² Temperature of anode region 30°C Cathode current yield (Mn) 56% Anode current yield (MnO₂) 83% EXAMPLE 2 Overall feed solution Mn 38 g/l (NH₄)₂SO₄ 200 g/l SO₂ 0.2g/l pH 6.5 Cathode current density 300 A/m² Temperature of cathode region 28°C Anode current density 3850 A/m² Temperature of anode region 30°C Cathode current yield (Mn) 60% Anode current yield (MnO₂) 95% EXAMPLE 3 Overall feed solution Mn 42 g/l (NH₄)₂SO₄ 150 g/l SO₂ 0.1g/l pH 6.1 Cathode current density 400 A/m² Temperature of cathode region 35°C Anode current density 5100 A/m² Temperature of anode region 30°C Cathode current yield (Mn) 55% Anode current yield (MnO₂) 93% EXAMPLE 4 Overall feed solution Mn 35 g/l (NH₄)₂SO₄ 180 g/l SO₂ 0.2g/l pH 6.8 Cathode current density 250 A/m² Temperature of cathode region 22°C Anode current density 3100 A/m² Temperature of anode region 25°C Cathode current yield (Mn) 58% Anode currant yield (MnO₂) 89%
Claims (5)
- A process for electrolytically preparing metallic manganese and gamma manganese dioxide simultaneously by electrolyzing two streams of an aqueous solution of manganese salt separated by a porous membrane, characterized in that said separatory membrane consists of a hydrocarbon or a fluorocarbon polymer containing quaternary ammonium groups, the anolyte being an aqueous solution of manganese sulphate acidified by sulphuric acid and the catholyte being an aqueous solution of manganese sulphate acidified by sulphuric acid and supplemented by ammonium sulphate and SO₂, under an anodic current density of from 3000 A/m² to 5500 A/m² and a cathodic current density of from 250 A/m² to 400 A/m².
- Process according to Claim 1, wherein the anolyte contains from 20 g/l to 40 g/l of Mn and from 100 g/l to 300 g/l of H₂SO₄.
- Process according to Claim 1, wherein the catholyte contains from 30 g/l to 50 g/l of Mn and from 150 g/l to 200 g/l of ammonium sulphate, and has a pH of from 6 to 7.
- Process according to Claim 1, wherein the anolyte temperature is of from 15°C to 30°C.
- Process according to Claim 1, wherein the catholyte temperature is of from 20°C to 35°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT2228786 | 1986-11-11 | ||
IT22287/86A IT1199841B (en) | 1986-11-11 | 1986-11-11 | PROCEDURE FOR THE EXTRACTION OF METALLIC MN AND MANGANESE DIOXIDE FROM SOLUTIONS OF BIVALENT MN SALTS |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0268319A2 EP0268319A2 (en) | 1988-05-25 |
EP0268319A3 EP0268319A3 (en) | 1989-05-24 |
EP0268319B1 true EP0268319B1 (en) | 1992-05-06 |
Family
ID=11194205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87202092A Expired EP0268319B1 (en) | 1986-11-11 | 1987-10-30 | Method for extracting mn metal and manganese dioxide from divalent mn salt solutions |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0268319B1 (en) |
DE (1) | DE3778834D1 (en) |
ES (1) | ES2032816T3 (en) |
FI (1) | FI874969A (en) |
GR (1) | GR3004734T3 (en) |
IT (1) | IT1199841B (en) |
NO (1) | NO874652L (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2704098B1 (en) * | 1993-04-16 | 1995-07-21 | Inst Nat Polytech Grenoble | PROCESS FOR TREATING USED BATTERIES BY ELECTROLYSIS. |
AU5050100A (en) * | 1999-05-05 | 2001-10-08 | Michael John Thom | Removal of manganese from electrolytes |
US6682644B2 (en) | 2002-05-31 | 2004-01-27 | Midamerican Energy Holdings Company | Process for producing electrolytic manganese dioxide from geothermal brines |
CN109112569B (en) * | 2018-09-19 | 2023-07-25 | 兰州交通大学 | Production method for simultaneously preparing manganese metal and manganese dioxide by ion exchange membrane electrolysis method |
CN113373461B (en) * | 2021-04-27 | 2022-12-02 | 宁夏天元锰材料研究院(有限公司) | Process and equipment for producing battery-grade manganese dioxide by same-bath electrolysis |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417259A (en) * | 1942-04-15 | 1947-03-11 | American Manganese Corp | Electrolytic process for preparing manganese and manganese dioxide simultaneously |
SU380742A1 (en) * | 1970-07-20 | 1973-05-15 | Method for Simultaneous Production of Manganese and Manganese Dioxide by Electrolysis | |
US3790458A (en) * | 1972-10-18 | 1974-02-05 | N Demuria | Method of electrochemical processing of manganese ores and their concentration wastes |
-
1986
- 1986-11-11 IT IT22287/86A patent/IT1199841B/en active
-
1987
- 1987-10-30 EP EP87202092A patent/EP0268319B1/en not_active Expired
- 1987-10-30 ES ES198787202092T patent/ES2032816T3/en not_active Expired - Lifetime
- 1987-10-30 DE DE8787202092T patent/DE3778834D1/en not_active Expired - Fee Related
- 1987-11-09 NO NO874652A patent/NO874652L/en unknown
- 1987-11-11 FI FI874969A patent/FI874969A/en not_active IP Right Cessation
-
1992
- 1992-05-27 GR GR920401083T patent/GR3004734T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
NO874652L (en) | 1988-05-13 |
FI874969A (en) | 1988-05-12 |
EP0268319A2 (en) | 1988-05-25 |
IT8622287A1 (en) | 1988-05-11 |
IT8622287A0 (en) | 1986-11-11 |
ES2032816T3 (en) | 1993-03-01 |
IT1199841B (en) | 1989-01-05 |
GR3004734T3 (en) | 1993-04-28 |
EP0268319A3 (en) | 1989-05-24 |
NO874652D0 (en) | 1987-11-09 |
FI874969A0 (en) | 1987-11-11 |
DE3778834D1 (en) | 1992-06-11 |
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