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EP0268319A2 - Procédé d'extraction de manganèse et de dioxyde de manganèse à partir de solutions de sel de manganèse divalent - Google Patents

Procédé d'extraction de manganèse et de dioxyde de manganèse à partir de solutions de sel de manganèse divalent Download PDF

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Publication number
EP0268319A2
EP0268319A2 EP87202092A EP87202092A EP0268319A2 EP 0268319 A2 EP0268319 A2 EP 0268319A2 EP 87202092 A EP87202092 A EP 87202092A EP 87202092 A EP87202092 A EP 87202092A EP 0268319 A2 EP0268319 A2 EP 0268319A2
Authority
EP
European Patent Office
Prior art keywords
manganese
anode
membrane
sulphate
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.)
Granted
Application number
EP87202092A
Other languages
German (de)
English (en)
Other versions
EP0268319A3 (en
EP0268319B1 (fr
Inventor
Renato Guerriero
Italo Vittadini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nuova Samim SpA
Original Assignee
Nuova Samim SpA
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Filing date
Publication date
Application filed by Nuova Samim SpA filed Critical Nuova Samim SpA
Publication of EP0268319A2 publication Critical patent/EP0268319A2/fr
Publication of EP0268319A3 publication Critical patent/EP0268319A3/en
Application granted granted Critical
Publication of EP0268319B1 publication Critical patent/EP0268319B1/fr
Expired legal-status Critical Current

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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 overall electrochemical reaction on which manganese dioxide production is based is as follows: at the anode: 2Mn2+ ⁇ 2Mn3+ + 2e 2Mn+3 ⁇ Mn4+ + Mn+2 Mn+4 + 2H2O ⁇ MnO2 + 4H+ at the cathode: 2H+ + 2e ⁇ H2
  • 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.
  • 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
  • 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 consists of manganous sulphate and ammonium sulphate, and is practically neutral.
  • 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 by electrolysis of a manganese sulphate solution, comprising feeding a manganese salt solution into the two parts into which an electrolytic cell provided with a separating membrane is divided; said method being characterised in that the membrane is anionic and is a membrane consisting of a hydrocarbon or fluorocarbon polymer containing quaternary ammonium groups, and the anode compartment of the electrolytic cell divided by said membrane is fed with an aqueous sulphuric solution of manganese sulphate, whereas the cathode compartment of said cell is fed with an aqueous solution of manganese sulphate, ammonium sulphate and SO2.
  • 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.
  • 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

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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)
EP87202092A 1986-11-11 1987-10-30 Procédé d'extraction de manganèse et de dioxyde de manganèse à partir de solutions de sel de manganèse divalent Expired EP0268319B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2228786 1986-11-11
IT22287/86A IT1199841B (it) 1986-11-11 1986-11-11 Procedimento per l'estrazione di mn metallico e biossido di manganese da soluzioni di sali di mn bivalente

Publications (3)

Publication Number Publication Date
EP0268319A2 true EP0268319A2 (fr) 1988-05-25
EP0268319A3 EP0268319A3 (en) 1989-05-24
EP0268319B1 EP0268319B1 (fr) 1992-05-06

Family

ID=11194205

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87202092A Expired EP0268319B1 (fr) 1986-11-11 1987-10-30 Procédé d'extraction de manganèse et de dioxyde de manganèse à partir de solutions de sel de manganèse divalent

Country Status (7)

Country Link
EP (1) EP0268319B1 (fr)
DE (1) DE3778834D1 (fr)
ES (1) ES2032816T3 (fr)
FI (1) FI874969A (fr)
GR (1) GR3004734T3 (fr)
IT (1) IT1199841B (fr)
NO (1) NO874652L (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620607A1 (fr) * 1993-04-16 1994-10-19 Institut National Polytechnique De Grenoble Procédé de traitement de piles usagées par électrolyse
WO2001073165A1 (fr) * 1999-05-05 2001-10-04 Michael John Thom Extraction de manganese dans des electrolytes
US6682644B2 (en) 2002-05-31 2004-01-27 Midamerican Energy Holdings Company Process for producing electrolytic manganese dioxide from geothermal brines
CN109112569A (zh) * 2018-09-19 2019-01-01 兰州交通大学 一种离子交换膜电解法同时制备金属锰与二氧化锰的生产方法
CN113373461A (zh) * 2021-04-27 2021-09-10 宁夏天元锰材料研究院(有限公司) 一种同槽电解生产电池级二氧化锰的工艺及设备

Citations (3)

* Cited by examiner, † Cited by third party
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 (ru) * 1970-07-20 1973-05-15 Способ одновременного получения марганца и двуокиси марганца электролизом
US3790458A (en) * 1972-10-18 1974-02-05 N Demuria Method of electrochemical processing of manganese ores and their concentration wastes

Patent Citations (3)

* Cited by examiner, † Cited by third party
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 (ru) * 1970-07-20 1973-05-15 Способ одновременного получения марганца и двуокиси марганца электролизом
US3790458A (en) * 1972-10-18 1974-02-05 N Demuria Method of electrochemical processing of manganese ores and their concentration wastes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 108, no. 3, February 1988, page 568, abstract no. 64666c, Columbus, Ohio, US; & JP-A-85 104 334 (FUJIAN REACHER'S UNIVERSITY) *
CHEMICAL ABSTRACTS, vol. 79, no. 16, 22nd October 1973, page 548, abstract no. 99888m; & SU-A-380 742 (LENIN, V.I., GEORGIAN POLYTECHNIC INSTITUTE) 20-07-1970 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620607A1 (fr) * 1993-04-16 1994-10-19 Institut National Polytechnique De Grenoble Procédé de traitement de piles usagées par électrolyse
FR2704098A1 (fr) * 1993-04-16 1994-10-21 Inst Nat Polytech Grenoble Procédé de traitement de piles usagée ar électrolyse.
WO2001073165A1 (fr) * 1999-05-05 2001-10-04 Michael John Thom Extraction de manganese dans des electrolytes
US6682644B2 (en) 2002-05-31 2004-01-27 Midamerican Energy Holdings Company Process for producing electrolytic manganese dioxide from geothermal brines
US7776202B2 (en) 2002-05-31 2010-08-17 Midamerican Energy Holdings Company Process for producing electrolytic manganese dioxide
US8313653B2 (en) 2002-05-31 2012-11-20 Midamerican Energy Holdings Company Method of removing iron and calcium from a geothermal brine
US8894865B2 (en) 2002-05-31 2014-11-25 Berkshire Hathaway Energy Company Process for depleting calcium and/or iron from geothermal brines
CN109112569A (zh) * 2018-09-19 2019-01-01 兰州交通大学 一种离子交换膜电解法同时制备金属锰与二氧化锰的生产方法
CN109112569B (zh) * 2018-09-19 2023-07-25 兰州交通大学 一种离子交换膜电解法同时制备金属锰与二氧化锰的生产方法
CN113373461A (zh) * 2021-04-27 2021-09-10 宁夏天元锰材料研究院(有限公司) 一种同槽电解生产电池级二氧化锰的工艺及设备

Also Published As

Publication number Publication date
ES2032816T3 (es) 1993-03-01
FI874969A (fi) 1988-05-12
GR3004734T3 (fr) 1993-04-28
NO874652L (no) 1988-05-13
FI874969A0 (fi) 1987-11-11
IT1199841B (it) 1989-01-05
IT8622287A0 (it) 1986-11-11
EP0268319A3 (en) 1989-05-24
DE3778834D1 (de) 1992-06-11
EP0268319B1 (fr) 1992-05-06
IT8622287A1 (it) 1988-05-11
NO874652D0 (no) 1987-11-09

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