JP5764207B2 - Method for producing electrolytic manganese dioxide for mercury-free alkaline manganese batteries - Google Patents
Method for producing electrolytic manganese dioxide for mercury-free alkaline manganese batteries Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 100
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052748 manganese Inorganic materials 0.000 title claims description 45
- 239000011572 manganese Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 238000002386 leaching Methods 0.000 claims description 48
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 44
- 229940099596 manganese sulfate Drugs 0.000 claims description 36
- 235000007079 manganese sulphate Nutrition 0.000 claims description 36
- 239000011702 manganese sulphate Substances 0.000 claims description 36
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052683 pyrite Inorganic materials 0.000 claims description 11
- 239000011028 pyrite Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 239000003518 caustics Substances 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000007664 blowing Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000265 homogenisation Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 38
- 238000001914 filtration Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 235000006748 manganese carbonate Nutrition 0.000 description 3
- 239000011656 manganese carbonate Substances 0.000 description 3
- 229940093474 manganese carbonate Drugs 0.000 description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- 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
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
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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
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- 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
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Description
本願は、２０１０年７月１５日に出願された中国出願第２０１０１０２２７９８８．７号、発明名称「無水銀アルカリマンガン型電解二酸化マンガンの製造法」の利益を主張するものである。 This application claims the benefit of Chinese application 201010227988.7, filed on July 15, 2010, the title of the invention “Method for producing anhydrous silver alkali manganese electrolytic manganese dioxide”.
本願発明は、無水銀アルカリマンガン電池用電解二酸化マンガンの製造法に関するものであり、具体的には、著しくグレードの低い酸化マンガン鉱石から「二鉱石法」による浸出工程を経て、無水銀アルカリマンガン電池用電解二酸化マンガンを製造する方法に関する。 The present invention relates to a method for producing electrolytic manganese dioxide for an anhydrous silver alkaline manganese battery , specifically, a leaching process by a “two-ore method” from a manganese oxide ore having a significantly low grade, and then an anhydrous mercury alkaline manganese battery. The present invention relates to a method for producing electrolytic manganese dioxide for industrial use .
電池業界において、高出力で対価格性能比に最も優れた電池として、アルカリマンガン電池は、安定した供給電圧のもとで長期にわたって大電流を流し続けることができるという優れた性能に加えて、最長３〜５年の長期貯蔵が可能で、低温でも優れた性能を発揮し、液漏れもしない等の特徴を有し、国内外を問わず高い評価を得ている。 In the battery industry, as the battery with the highest output and price / performance ratio, alkaline manganese batteries have the longest performance in addition to the ability to keep a large current flowing for a long time under a stable supply voltage. Long-term storage of 3 to 5 years is possible, it exhibits excellent performance even at low temperatures, and does not leak, and has been highly evaluated both domestically and internationally.
このアルカリマンガン電池の主原料である無水銀アルカリマンガン電池用電解二酸化マンガンは、年間３０万トン以上が消費され、その量は、毎年１０％以上の勢いで伸びつつあり、その市場の将来の見通しは明るい。 More than 300,000 tons of electrolytic manganese dioxide for mercury-free alkaline manganese batteries, the main raw material for alkaline manganese batteries, is consumed at a rate of more than 10% annually. Is bright.
ところで、従来の電解二酸化マンガンの製法においては、原料として主に炭酸マンガン鉱石または酸化マンガン鉱石が用いられている。ところが、国内で産出された炭酸マンガン鉱石を精錬する場合、その鉱石の炭酸マンガン含有量が低いため（３０％未満）、大量のマンガン鉱石を消費せねばならず、最終製品が高価格となる原因となっていた。 By the way, in the conventional manufacturing method of electrolytic manganese dioxide, manganese carbonate ore or manganese oxide ore is mainly used as a raw material. However, when refining domestically produced manganese carbonate ore, the manganese carbonate content of the ore is low (less than 30%), so a large amount of manganese ore must be consumed, and the final product is expensive. It was.
一方、酸化マンガンを原料とする場合、酸化マンガン鉱石を焙焼により還元した後に溶液を浸出する方法と、「二鉱石法」により電解二酸化マンガンを製造する方法とが、近年主流となっている。しかし、酸化マンガン鉱石を焙焼により還元した後に溶液を浸出する手法は、その工程が長くなり、製造コストがかさみ、また、その生産工場周辺の環境が汚染されやすい等の欠点があった。 On the other hand, when manganese oxide is used as a raw material, a method of leaching a solution after reducing manganese oxide ore by roasting and a method of producing electrolytic manganese dioxide by the “two-ore method” have become mainstream in recent years. However, the method of leaching the solution after reducing the manganese oxide ore by roasting has disadvantages such as a long process, a high manufacturing cost, and an environment around the production factory being easily contaminated.
また、主として、グレードの高い二酸化マンガンが原料として用いられる「二鉱石法」による二酸化マンガンの製造法、すなわち、二酸化マンガン鉱石と還元剤として黄鉄鉱石とを含む溶液を浸出する方法、をグレートの低いマンガン鉱石、すなわち、含有量が２５％未満のグレードのものを用いて行った場合、浸出効率が低下し、装置における反応物質の処理時間が長くなり、製造設備の数が増えるほか、近年、国内のマンガン精錬業界で行われている非連続式の浸出工程、すなわち、マンガン鉱石を単一の浸出タンク内に蓄えられた溶液に直接溶解する工程では、作業効率が劣るという欠点を有していた。 In addition, the manufacturing method of manganese dioxide by the “two ore method”, in which high-grade manganese dioxide is used as a raw material, that is, a method of leaching a solution containing manganese dioxide ore and pyrite ore as a reducing agent is low in great Manganese ore, that is, when the content is less than 25%, the leaching efficiency is lowered, the processing time of the reactants in the equipment is increased, the number of production facilities is increased, and in recent years In the discontinuous leaching process performed in the manganese refining industry, that is, the process in which manganese ore is directly dissolved in the solution stored in a single leaching tank, the work efficiency is inferior. .
グレードの高いマンガン鉱石資源がますます減少してきているなか、将来にわたって現在の手法を維持していくのは困難となることが予想される。また、広西チワン族自治区のマンガン鉱石資源は、その量こそ豊富であるものの、その大部分はグレードの低いマンガン鉱石で、特にマンガン成分の含有量が低く不純物の含有量が高いため、長く有効利用されないままであった。 It is expected that it will be difficult to maintain current methods in the future as high-grade manganese ore resources are decreasing. In addition, although the amount of manganese ore resources in the Guangxi Zhuang Autonomous Region is abundant, most of them are low-grade manganese ores, especially because they contain a low content of manganese and a high content of impurities. It was not done.
前記諸問題を解決するため、本発明は、著しくグレードの低い酸化マンガン鉱石を原料とした、「二鉱石法」による無水銀アルカリマンガン電池用電解二酸化マンガンの製造法を提供することを課題とする。 In order to solve the above problems, an object of the present invention is to provide a method for producing electrolytic manganese dioxide for anhydrous mercury alkaline manganese batteries by a “two-ore method” using a manganese oxide ore of a remarkably low grade as a raw material. .
前記技術的諸問題を解決するための本発明の技術的概要は、以下の、連続する（１）〜（３）の工程からなる、無水銀アルカリマンガン電池用電解二酸化マンガンの製造法を提供することである。
（１）酸化マンガン鉱石と黄鉄鉱石を混合し、当該混合物と硫酸とを１〜７槽の攪拌浸出槽からなる連続浸出槽中に連続的に供給し、反応温度を９０〜９５℃に制御し、３〜４時間かけて１段または多段連続浸出を行って、カリウムイオンを除去し、次いで中和鉄分離法により鉄分を除去し、当該鉄成分除去処理の後段で石灰粉を添加して、９０〜９５℃で３〜４時間かけて溶液のｐＨ値を６〜６．５に調整することにより、硫酸マンガン溶液を得る工程。
（２）２段階の連続精製処理により前記硫酸マンガン溶液から不純物を除去する精製を行うため、前記連続精製処理の第１段階として、温度を６０℃に制御した前記硫酸マンガン溶液にポリ硫化カルシウムを添加し、前記精製処理の第２段階として、精製した前記溶液を樋を通して通流することで、カルシウムとマグネシウムを除去し、その後、精製した前記硫酸マンガン溶液を貯蔵タンクへ移送して、そのまま前記貯蔵タンク内で３２時間静置させた後、静置した前記硫酸マンガン溶液からカルシウムおよびマグネシウムの不純物を沈殿物として除去する工程。
（３）（２）で得られた溶液を限外濾過した後、精製された硫酸マンガン溶液をプレート熱変換器を用いて９０〜１００℃に加熱し、これに乳化剤および発泡剤を同時に添加して得られた生成物を配管を通じて電解層に供給し、電解温度１００〜１０３℃、アノード電流密度８０〜８５Ａ/ｍ２、電解電圧２．２〜３．５Ｖ、電解期間１２〜２０日の条件で電気分解を行うことにより、無水銀アルカリマンガン電池用電解二酸化マンガンを得る工程。
The technical outline of the present invention for solving the above technical problems provides a method for producing electrolytic manganese dioxide for anhydrous silver alkaline manganese batteries , comprising the following steps (1) to (3). That is.
(1) Manganese oxide ore and pyrite ore are mixed, the mixture and sulfuric acid are continuously fed into a continuous leaching tank consisting of 1 to 7 stirred leaching tanks, and the reaction temperature is controlled to 90 to 95 ° C. , One-stage or multi-stage continuous leaching over 3 to 4 hours to remove potassium ions, then remove iron by neutralized iron separation method, add lime powder at the latter stage of the iron component removal treatment, A step of obtaining a manganese sulfate solution by adjusting the pH value of the solution to 6 to 6.5 at 90 to 95 ° C. over 3 to 4 hours.
(2) In order to carry out purification to remove impurities from the manganese sulfate solution by two-stage continuous purification treatment, as the first stage of the continuous purification treatment, calcium sulfide is added to the manganese sulfate solution whose temperature is controlled at 60 ° C. As a second step of the purification treatment, calcium and magnesium are removed by passing the purified solution through a trough , and then the purified manganese sulfate solution is transferred to a storage tank and directly after allowed to stand 32 hours in the storage tank, standing the step of removing the calcium from manganese sulfate solution and magnesium impurities as a precipitate.
(3) After ultrafiltration of the solution obtained in (2), the purified manganese sulfate solution is heated to 90-100 ° C. using a plate heat converter, and an emulsifier and a foaming agent are simultaneously added thereto. The product obtained in this way is supplied to the electrolytic layer through a pipe, conditions of electrolysis temperature 100 to 103 ° C., anode current density 80 to 85 A / m 2 , electrolysis voltage 2.2 to 3.5 V, electrolysis period 12 to 20 days The step of obtaining electrolytic manganese dioxide for anhydrous silver alkaline manganese batteries by performing electrolysis in
本発明は、以下の、既存の技術に比して優位な効果を有する。すなわち、本発明の無水銀アルカリマンガン電池用電解二酸化マンガンの製造法によれば、用いる酸化マンガンのグレードを含有量１６％にまで落とすことができ、著しくグレードの低い酸化マンガン鉱石を主原料として使用することができる。また、「二鉱石法」により、著しくグレードの低い酸化マンガン鉱石をから直接、浸出によりマンガン成分を取り出すことができ、得られた硫酸マンガン溶液から、十分な精製により不純物を除去し、その後電解法により無水銀アルカリマンガン電池用電解二酸化マンガンを生成することができる。 The present invention has the following advantages over the existing technologies. That is, according to the method for producing electrolytic manganese dioxide for anhydrous mercury-alkaline manganese batteries of the present invention, the manganese oxide grade used can be reduced to a content of 16%, and a manganese oxide ore having a significantly lower grade is used as a main raw material. can do. In addition, with the “two-ore method”, manganese components can be extracted directly from leached manganese oxide ores of extremely low grade by leaching, and impurities are removed from the resulting manganese sulfate solution by sufficient purification, followed by electrolysis. Can produce electrolytic manganese dioxide for anhydrous silver alkaline manganese batteries .
本発明に用いられる工程は、取り扱いが複雑なグレードの低い酸化マンガン鉱石のみならず、グレードの高い酸化マンガン鉱石をも使用することができる。そのため、様々な酸化マンガン鉱石を用いることができ、処理工程が短く、製造コストも抑えることができる等の効果がある。 The process used in the present invention can use not only low-grade manganese oxide ore, which is complicated to handle, but also high-grade manganese oxide ore. Therefore, various manganese oxide ores can be used, and there are effects such as a short processing step and reduction in manufacturing cost.
また、本発明により無水銀アルカリマンガン電池用電解二酸化マンガンを生産することで、広西チワン族自治区に大量に存在するグレードの低いマンガン鉱石の十全な活用を図ることができ、マンガン鉱石資源の合理的な利用、製造コストの削減と併せて、非常に大きな経済的社会的利益をもたらすことができる。 In addition, by producing electrolytic manganese dioxide for mercury-free alkaline manganese batteries according to the present invention, it is possible to make full use of low-grade manganese ores that exist in large quantities in the Guangxi Zhuang Autonomous Region. Combined with efficient use and reduced manufacturing costs, it can bring tremendous economic and social benefits.
以下、参照する図面および実施例により、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings and examples.
前述の無水銀アルカリマンガン電池用電解二酸化マンガンの製造法において、前記工程（１）では、酸化マンガン鉱石と黄鉄鉱石とを１：０．２４の比率で直接、連続浸出槽に供給し、同時に、硫酸および電解廃棄物質と混合してもよい。このとき、鉱石と酸の質量比率は１：０．４７としてもよい。 In the above-described method for producing electrolytic manganese dioxide for anhydrous silver alkaline manganese batteries, in the step (1), manganese oxide ore and pyrite ore are directly supplied to the continuous leaching tank at a ratio of 1: 0.24, It may be mixed with sulfuric acid and electrolytic waste material. At this time, the mass ratio of the ore and the acid may be 1: 0.47.
ここにおいて、前述の無水銀アルカリマンガン電池用電解二酸化マンガンの製造法における、電解廃棄物質は、前記工程（３）の電気分解中に発生した残渣物由来の硫酸としてもよい。 Here, the electrolytic waste material in the above-described method for producing electrolytic manganese dioxide for a mercury-free alkaline manganese battery may be sulfuric acid derived from a residue generated during the electrolysis in the step (3).
また、前述の無水銀アルカリマンガン電池用電解二酸化マンガンの製造法において、前記工程（３）では、未精製の電解二酸化マンガン生成物を破砕し、得られた粒状物を洗浄タンクに投入して３段階の洗滌処理を行っても良い。ここにおいて、前記洗滌処理は、水洗、苛性洗滌、水洗の３段階からなるものとしてもよい。 In the method for producing electrolytic manganese dioxide for an anhydrous silver alkaline manganese battery described above, in the step (3), the unpurified electrolytic manganese dioxide product is crushed, and the obtained granular material is put into a washing tank. A stage washing process may be performed. Here, pre SL washing treatment, water washing, caustic washing, may consist of three stages of water washing.
このとき、第１段階の水の温度、および第２段階の苛性洗滌におけるアルカリ溶液の温度は、いずれも６０〜７０℃としてもよい。最終段階における水の温度は８０〜９０℃としてもよい。そして、洗滌時間は４０時間としてもよい。洗滌液は、蒸気により直接加熱してもよい。その後、粉砕工程により、電解二酸化マンガンの粒径を必要とされる大きさにしてもよい。 At this time, the temperature of the first stage water and the temperature of the alkaline solution in the second stage caustic washing may both be 60-70 ° C. The temperature of water in the final stage may be 80 to 90 ° C. The washing time may be 40 hours. The washing liquid may be directly heated with steam. Then, you may make the particle size of electrolytic manganese dioxide into the required magnitude | size by a grinding | pulverization process.
更に、前述の無水銀アルカリマンガン電池用電解二酸化マンガンの製造法においては、前記粉砕された電解二酸化マンガンを、緻密相輸送法により重力型混合器に移送した後、当該混合器にて均一化してもよい。このときの混合時間は、約１６時間としてもよい。 Furthermore, in the above-described method for producing electrolytic manganese dioxide for anhydrous mercury-alkaline manganese batteries , the pulverized electrolytic manganese dioxide is transferred to a gravity mixer by a dense phase transport method, and then homogenized by the mixer. Also good. The mixing time at this time may be about 16 hours.
以上、本発明をその望ましい実施態様にて説明したが、これら実施態様は本発明の技術的範囲を制限するものではない。また、本願発明の保護範囲は特許請求の範囲に規定された発明の主題に基づき定まるものであり、当該技術分野における当業者であれば可能な変更のなされた前記実施態様のいくつかも、本発明の技術的範囲に含まれるものである。 As mentioned above, although this invention was demonstrated in the preferable embodiment, these embodiments do not restrict | limit the technical scope of this invention. The protection scope of the present invention is determined based on the subject matter of the invention defined in the claims, and some of the above-described embodiments that can be changed by those skilled in the art are also included in the present invention. It is included in the technical scope of
＜実施例１＞
マンガン含有率１４．３２％の酸化マンガン鉱石粉と硫黄含有率４４．５４％の黄鉄鉱粉とを乾燥重量比１：０．２４で混合し、また、９８％濃度の硫酸に水を加えて濃度１００ｇ／Ｌの希硫酸を調製する。次いで、酸化マンガンと黄鉄鉱粉との混合物と、調製した硫酸とを１：０．４７の質量比率で連続浸出槽に連続供給すると同時に連続的に攪拌する。ここにおいて、前記連続浸出槽は、１段連続浸出用の１槽の浸出槽からなり、当該浸出槽の実効容積は、１ｍ３である。また、当該浸出槽の温度は９５℃である。
<Example 1>
A manganese oxide ore powder having a manganese content of 14.32% and a pyrite powder having a sulfur content of 44.54% are mixed at a dry weight ratio of 1: 0.24, and water is added to 98% sulfuric acid to obtain a concentration. Prepare 100 g / L of dilute sulfuric acid. Next, the mixture of manganese oxide and pyrite powder and the prepared sulfuric acid are continuously fed to the continuous leaching tank at a mass ratio of 1: 0.47 and simultaneously stirred. Here, the continuous leaching tank is composed of one leaching tank for one-stage continuous leaching, and the effective volume of the leaching tank is 1 m 3 . Moreover, the temperature of the said leaching tank is 95 degreeC.
前記混合物が前記浸出槽に供給されてから、前記浸出槽外に排出されるまでの、浸出処理に係る反応は、当該反応の完了したことを示す、そのｐＨ値が３〜３．５となるまで行い、その反応時間は３時間である。さらに、当該反応中は、常時攪拌が続けられる。 The reaction relating to the leaching process from the time when the mixture is supplied to the leaching tank until the mixture is discharged outside the leaching tank indicates that the reaction has been completed, and the pH value is 3 to 3.5. The reaction time is 3 hours. Furthermore, stirring is always continued during the reaction.
前記浸出槽から流出する液状物質は、連続した実効容積１．５ｍ３の中和槽に入る。これに、連続的に石灰粉を添加して中和反応を行わせ、３時間かけてそのｐＨ値を６．０に調整する。中和後、前記液状物質を濾過し、濾過残渣を貯留地に移送する。 The liquid substance flowing out of the leaching tank enters a continuous neutralizing tank having an effective volume of 1.5 m 3 . To this, lime powder is continuously added to carry out a neutralization reaction, and the pH value is adjusted to 6.0 over 3 hours. After neutralization, the liquid substance is filtered and the filtration residue is transferred to a storage area.
以上のようにして、未精製の硫酸マンガン溶液が得られる。当該溶液には、銅、コバルト、ニッケル、鉛等の重金属、およびカルシウム、マグネシウム等の不純物が含まれている。 As described above, an unpurified manganese sulfate solution is obtained. The solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
次いで、２段階連続精製法により、未精製の前記硫酸マンガン溶液の連続精製処理を行う。すなわち、前記連続精製処理の第１段階として、前記硫酸マンガン溶液の温度を６０℃に制御して、これにポリ硫化カルシウムを添加し、濾過残渣を貯留地に移送する。次いで、前記精製処理の第２段階として、前記硫酸マンガン溶液を樋を通して通流し、液の流動過程でカルシウムとマグネシウムを除去する。 Subsequently, the unpurified manganese sulfate solution is continuously purified by a two-stage continuous purification method. That is, as the first stage of the continuous purification treatment, the temperature of the manganese sulfate solution is controlled at 60 ° C., calcium polysulfide is added thereto, and the filtration residue is transferred to a storage site. Then, the second step of the purification process, the flows through the manganese sulfate solution through the trough, removing calcium and magnesium in a fluidized process liquid.
次いで、前記硫酸マンガン溶液を貯蔵タンクへ移送し、そのまま前記貯蔵タンク内で、３２時間静置させることにより、カルシウム、マグネシウム等の不純物を沈殿物として除去し、精製硫酸マンガン溶液を得る。その後、濾過残渣は貯留地に搬送され、濾液は、電解層に移送される。 Next, the manganese sulfate solution is transferred to a storage tank, and left as it is in the storage tank for 32 hours, thereby removing impurities such as calcium and magnesium as precipitates to obtain a purified manganese sulfate solution. Thereafter, the filtration residue is transported to the storage site, and the filtrate is transferred to the electrolytic layer.
前記濾液として、十分に精製された硫酸マンガン溶液を限外濾過し、プレート熱変換器を用いて９０℃に加熱した後、高架タンクに移送して懸濁電解を行う。すなわち、調製した乳化剤および発泡剤を同時に添加し、電解温度１００℃、アノード電流密度８１Ａ/ｍ２、電解槽電圧２．４Ｖ、電解期間１２日の条件で電気分解を行う。 As the filtrate, a sufficiently purified manganese sulfate solution is ultrafiltered, heated to 90 ° C. using a plate heat converter, and then transferred to an elevated tank for suspension electrolysis. That is, the prepared emulsifier and foaming agent are added simultaneously, and electrolysis is performed under the conditions of an electrolysis temperature of 100 ° C., an anode current density of 81 A / m 2 , an electrolytic cell voltage of 2.4 V, and an electrolysis period of 12 days.
その後、電解槽のアノードから未精製の二酸化マンガン生成物を剥ぎ取り、破砕機により粒径６〜８ｍｍの粒状物に破砕した後、実効容積１ｍ３の洗滌タンクに移送する。前記洗滌タンク内では、水洗、苛性洗滌、水洗からなる３段階の洗滌処理を行う。ここで、第１段階の水の温度、および第２段階の苛性洗滌におけるアルカリ溶液の温度は、いずれも６０℃、最終段階における水の温度は８０℃、そして、洗滌時間は４０時間である。なお、洗滌液は、蒸気により直接加熱する。 Thereafter, the unpurified manganese dioxide product is peeled off from the anode of the electrolytic cell, and is crushed into granules having a particle diameter of 6 to 8 mm by a crusher, and then transferred to a washing tank having an effective volume of 1 m 3 . In the washing tank, a three-stage washing process including washing with water, caustic washing, and washing with water is performed. Here, the temperature of the first stage water and the temperature of the alkaline solution in the second stage caustic washing are both 60 ° C., the temperature of the water in the final stage is 80 ° C., and the washing time is 40 hours. The washing liquid is directly heated with steam.
前記洗滌した、電解二酸化マンガンを振子式粉砕機にて粉砕し、得られた粉体生成物（３２５メッシュの篩を通過した粒径サイズを有するもの）を捕集する。その後、品質の差をなくし生成物の均一性を確保するため、前記粉砕された電解二酸化マンガンを、緻密相輸送法により重力型混合器に移送した後、当該混合器にて１６時間均一混合を行い、高品質の無水銀アルカリマンガン電池用電解二酸化マンガンを得る。
＜実施例２＞
The washed electrolytic manganese dioxide is pulverized with a pendulum pulverizer, and the obtained powder product (having a particle size of a particle size that has passed through a 325 mesh sieve) is collected. Thereafter, in order to eliminate the difference in quality and ensure the uniformity of the product, the pulverized electrolytic manganese dioxide is transferred to a gravitational mixer by a dense phase transport method, and then mixed uniformly for 16 hours in the mixer. To obtain high quality electrolytic manganese dioxide for anhydrous mercury-alkaline manganese batteries .
<Example 2>
マンガン含有率１５．５６％の酸化マンガン鉱石粉と硫黄含有率４０．５４％の黄鉄鉱粉とを乾燥重量比１：０．２４で混合し、また、９８％濃度の硫酸に水を加えて濃度１００ｇ／Ｌの希硫酸を調製する。次いで、酸化マンガンと黄鉄鉱粉との混合物と、調製した硫酸とを１：０．４７の質量比率で連続浸出槽に連続供給すると同時に連続的に攪拌する。ここにおいて、前記連続浸出槽は、３段連続浸出用の３槽の浸出槽からなり、処理される液体は２番目の浸出槽を出た後に３番目の浸出槽へ入る。当該浸出槽の実効容積は、各々１ｍ３である。また、当該浸出槽の温度は各々９３℃である。 A manganese oxide ore powder having a manganese content of 15.56% and a pyrite powder having a sulfur content of 40.54% are mixed at a dry weight ratio of 1: 0.24, and water is added to 98% sulfuric acid to obtain a concentration. Prepare 100 g / L of dilute sulfuric acid. Next, the mixture of manganese oxide and pyrite powder and the prepared sulfuric acid are continuously fed to the continuous leaching tank at a mass ratio of 1: 0.47 and simultaneously stirred. Here, the continuous leaching tank is composed of three leaching tanks for three-stage continuous leaching, and the liquid to be treated enters the third leaching tank after leaving the second leaching tank. The effective volumes of the leaching tanks are 1 m 3 each. Moreover, the temperature of the said leaching tank is 93 degreeC respectively.
前記混合物が前記浸漬槽に供給されてから、前記３番目の浸出槽外に排出されるまでの、浸出処理に係る反応時間は３．５時間である。また、当該反応中は、常時攪拌が続けられる。 The reaction time relating to the leaching process from when the mixture is supplied to the immersing tank to when the mixture is discharged out of the third leaching tank is 3.5 hours. During the reaction, stirring is always continued.
前記３番目の浸出槽から流出する液状物質は、連続した実効容積１．５ｍ３の中和槽に入る。これに、連続的に石灰粉を添加して中和反応を行わせ、３．５時間かけてそのｐＨ値を６．３に調整する。中和後、前記液状物質を濾過し、濾過残渣を貯留地に移送する。 The liquid material flowing out of the third leaching tank enters a neutralization tank having a continuous effective volume of 1.5 m 3 . To this, lime powder is continuously added to carry out a neutralization reaction, and the pH value is adjusted to 6.3 over 3.5 hours. After neutralization, the liquid substance is filtered and the filtration residue is transferred to a storage area.
以上のようにして、未精製の硫酸マンガン溶液が得られる。当該溶液には、銅、コバルト、ニッケル、鉛等の重金属、およびカルシウム、マグネシウム等の不純物が含まれている。 As described above, an unpurified manganese sulfate solution is obtained. The solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
次いで、２段階連続精製法により、未精製の前記硫酸マンガン溶液の連続精製処理を行う。すなわち、前記連続精製処理の第１段階として、前記硫酸マンガン溶液の温度を６０℃に制御して、これにポリ硫化カルシウムを添加し、濾過残渣を貯留地に移送する。次いで、前記精製処理の第２段階として、前記硫酸マンガン溶液を樋を通して通流し、液の流動過程でカルシウムとマグネシウムを除去する。 Subsequently, the unpurified manganese sulfate solution is continuously purified by a two-stage continuous purification method. That is, as the first stage of the continuous purification treatment, the temperature of the manganese sulfate solution is controlled at 60 ° C., calcium polysulfide is added thereto, and the filtration residue is transferred to a storage site. Then, the second step of the purification process, the flows through the manganese sulfate solution through the trough, removing calcium and magnesium in a fluidized process liquid.
次いで、前記硫酸マンガン溶液を貯蔵タンクへ移送し、そのまま前記貯蔵タンク内で、３２時間静置させることにより、カルシウム、マグネシウム等の不純物を沈殿物として除去し、精製硫酸マンガン溶液を得る。その後、濾過残渣は貯留地に搬送され、濾液は、電解層に移送される。 Next, the manganese sulfate solution is transferred to a storage tank, and left as it is in the storage tank for 32 hours, thereby removing impurities such as calcium and magnesium as precipitates to obtain a purified manganese sulfate solution. Thereafter, the filtration residue is transported to the storage site, and the filtrate is transferred to the electrolytic layer.
前記濾液として、十分に精製された硫酸マンガン溶液を限外濾過し、プレート熱変換器を用いて９５℃に加熱した後、高架タンクに移送して懸濁電解を行う。すなわち、調製した乳化剤および発泡剤を同時に添加し、電解温度１０２℃、アノード電流密度８３Ａ/ｍ２、電解槽電圧２．９Ｖ、電解期間１５日の条件で電気分解を行う。 As the filtrate, a sufficiently purified manganese sulfate solution is ultrafiltered, heated to 95 ° C. using a plate heat converter, and then transferred to an elevated tank for suspension electrolysis. That is, the prepared emulsifier and foaming agent are added simultaneously, and electrolysis is performed under the conditions of an electrolysis temperature of 102 ° C., an anode current density of 83 A / m 2 , an electrolytic cell voltage of 2.9 V, and an electrolysis period of 15 days.
その後、電解槽のアノードから未精製の二酸化マンガン生成物を剥ぎ取り、破砕機により粒径６〜８ｍｍの粒状物に破砕した後、実効容積１ｍ３の洗滌タンクに移送する。前記洗滌タンク内では、水洗、苛性洗滌、水洗からなる３段階の洗滌処理を行う。ここで、第１段階の水の温度、および第２段階の苛性洗滌におけるアルカリ溶液の温度は、いずれも６５℃、最終段階における水の温度は８５℃、そして、洗滌時間は４０時間である。なお、洗滌液は、蒸気により直接加熱する。 Thereafter, the unpurified manganese dioxide product is peeled off from the anode of the electrolytic cell, and is crushed into granules having a particle diameter of 6 to 8 mm by a crusher, and then transferred to a washing tank having an effective volume of 1 m 3 . In the washing tank, a three-stage washing process including washing with water, caustic washing, and washing with water is performed. Here, the temperature of the first stage water and the temperature of the alkaline solution in the second stage of caustic washing are both 65 ° C., the temperature of water in the final stage is 85 ° C., and the washing time is 40 hours. The washing liquid is directly heated with steam.
前記洗滌した、電解二酸化マンガンを振子式粉砕機にて粉砕し、得られた粉体生成物（３２５メッシュの篩を通過した粒径サイズを有するもの）を捕集する。その後、品質の差をなくし生成物の均一性を確保するため、前記粉砕された電解二酸化マンガンを、緻密相輸送法により重力型混合器に移送した後、当該混合器にて１６時間均一混合を行い、高品質の無水銀アルカリマンガン電池用電解二酸化マンガンを得る。
＜実施例３＞
The washed electrolytic manganese dioxide is pulverized with a pendulum pulverizer, and the obtained powder product (having a particle size of a particle size that has passed through a 325 mesh sieve) is collected. Thereafter, in order to eliminate the difference in quality and ensure the uniformity of the product, the pulverized electrolytic manganese dioxide is transferred to a gravitational mixer by a dense phase transport method, and then mixed uniformly for 16 hours in the mixer. To obtain high quality electrolytic manganese dioxide for anhydrous mercury-alkaline manganese batteries .
<Example 3>
マンガン含有率１３．５８％の酸化マンガン鉱石粉と硫黄含有率４７．４４％の黄鉄鉱粉とを乾燥重量比１：０．２４で混合し、また、９８％濃度の硫酸に水を加えて濃度１００ｇ／Ｌの希硫酸を調製する。次いで、酸化マンガンと黄鉄鉱粉との混合物と、調製した硫酸とを１：０．４７の質量比率で連続浸出槽に連続供給すると同時に連続的に攪拌する。ここにおいて、前記連続浸出槽は、７段連続浸出用の７槽の浸出槽からなり、処理される液体は２番目の浸出槽を出た後に３番目から７番目の浸出槽へ入る。当該浸出槽の実効容積は、各々１ｍ３である。また、当該浸出槽の温度は各々９５℃である。 Manganese oxide ore powder having a manganese content of 13.58% and pyrite ore powder having a sulfur content of 47.44% are mixed at a dry weight ratio of 1: 0.24, and water is added to 98% sulfuric acid to obtain a concentration. Prepare 100 g / L of dilute sulfuric acid. Next, the mixture of manganese oxide and pyrite powder and the prepared sulfuric acid are continuously fed to the continuous leaching tank at a mass ratio of 1: 0.47 and simultaneously stirred. Here, the continuous leaching tank comprises seven leaching tanks for seven-stage continuous leaching, and the liquid to be treated enters the third to seventh leaching tanks after leaving the second leaching tank. The effective volumes of the leaching tanks are 1 m 3 each. Moreover, the temperature of the said leaching tank is 95 degreeC, respectively.
前記混合物が前記浸漬槽に供給されてから、前記７番目の浸出槽外に排出されるまでの、浸出処理に係る反応時間は４時間である。また、当該反応中は、常時攪拌が続けられる。 The reaction time for the leaching process from when the mixture is supplied to the immersing tank until the mixture is discharged out of the seventh leaching tank is 4 hours. During the reaction, stirring is always continued.
前記７番目の浸出槽から流出する液状物質は、連続した実効容積１．５ｍ３の中和槽に入る。これに、連続的に石灰粉を添加して中和反応を行わせ、そのｐＨ値を６．５に調整する。中和後、前記液状物質を濾過し、濾過残渣を貯留地に移送する。 The liquid substance flowing out from the seventh leaching tank enters a neutralization tank having a continuous effective volume of 1.5 m 3 . To this, lime powder is continuously added to cause a neutralization reaction, and the pH value is adjusted to 6.5. After neutralization, the liquid substance is filtered and the filtration residue is transferred to a storage area.
以上のようにして、未精製の硫酸マンガン溶液が得られる。当該溶液には、銅、コバルト、ニッケル、鉛等の重金属、およびカルシウム、マグネシウム等の不純物が含まれている。 As described above, an unpurified manganese sulfate solution is obtained. The solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
次いで、２段階連続精製法により、前記未精製の硫酸マンガン溶液の連続精製処理を行う。すなわち、前記連続精製処理の第１段階として、前記硫酸マンガン溶液の温度を６０℃に制御して、これにポリ硫化カルシウムを添加し、濾過残渣を貯留地に移送する。次いで、前記精製処理の第２段階として、前記硫酸マンガン溶液を樋を通して通流し、液の流動過程でカルシウムとマグネシウムを除去する。 Subsequently, the unpurified manganese sulfate solution is continuously purified by a two-stage continuous purification method. That is, as the first stage of the continuous purification treatment, the temperature of the manganese sulfate solution is controlled at 60 ° C., calcium polysulfide is added thereto, and the filtration residue is transferred to a storage site. Then, the second step of the purification process, the flows through the manganese sulfate solution through the trough, removing calcium and magnesium in a fluidized process liquid.
次いで、前記硫酸マンガン溶液を貯蔵タンクへ移送し、そのまま前記貯蔵タンク内で、３２時間静置させることにより、カルシウム、マグネシウム等の不純物を沈殿物として除去し、精製硫酸マンガン溶液を得る。その後、濾過残渣は貯留地に搬送され、濾液は、電解層に移送される。 Next, the manganese sulfate solution is transferred to a storage tank, and left as it is in the storage tank for 32 hours, thereby removing impurities such as calcium and magnesium as precipitates to obtain a purified manganese sulfate solution. Thereafter, the filtration residue is transported to the storage site, and the filtrate is transferred to the electrolytic layer.
前記濾液として、十分に精製された硫酸マンガン溶液を限外濾過し、プレート熱変換器を用いて１００℃に加熱した後、高架タンクに移送して懸濁電解を行う。すなわち、調製した乳化剤および発泡剤を同時に添加し、電解温度１０３℃、アノード電流密度８５Ａ/ｍ２、電解槽電圧３．５Ｖ、電解期間２０日の条件で電気分解を行う。 As the filtrate, a sufficiently purified manganese sulfate solution is ultrafiltered, heated to 100 ° C. using a plate heat converter, and then transferred to an elevated tank for suspension electrolysis. That is, the prepared emulsifier and foaming agent are added simultaneously, and electrolysis is performed under the conditions of an electrolysis temperature of 103 ° C., an anode current density of 85 A / m 2 , an electrolytic cell voltage of 3.5 V, and an electrolysis period of 20 days.
その後、電解槽のアノードから未精製の二酸化マンガン生成物を剥ぎ取り、破砕機により粒径６〜８ｍｍの粒状物に破砕した後、実効容積１ｍ３の洗滌タンクに移送する。前記洗滌タンク内では、水洗、苛性洗滌、水洗からなる３段階の洗滌処理を行う。ここで、第１段階の水の温度、および第２段階の苛性洗滌におけるアルカリ溶液の温度は、いずれも７０℃、最終段階における水の温度は８５℃、そして、洗滌時間は４０時間である。なお、洗滌液は、蒸気により直接加熱する。 Thereafter, the unpurified manganese dioxide product is peeled off from the anode of the electrolytic cell, and is crushed into granules having a particle diameter of 6 to 8 mm by a crusher, and then transferred to a washing tank having an effective volume of 1 m 3 . In the washing tank, a three-stage washing process including washing with water, caustic washing, and washing with water is performed. Here, the temperature of the first stage water and the temperature of the alkaline solution in the second stage of caustic washing are both 70 ° C., the temperature of water in the final stage is 85 ° C., and the washing time is 40 hours. The washing liquid is directly heated with steam.
前記洗滌した、電解二酸化マンガンを振子式粉砕機にて粉砕し、得られた粉体生成物（３２５メッシュの篩を通過した粒径サイズを有するもの）を捕集する。その後、品質の差をなくし生成物の均一性を確保するため、前記粉砕された電解二酸化マンガンを、緻密相輸送法により重力型混合器に移送した後、当該混合器にて１６時間均一混合を行い、高品質の無水銀アルカリマンガン電池用電解二酸化マンガンを得る。 The washed electrolytic manganese dioxide is pulverized with a pendulum pulverizer, and the obtained powder product (having a particle size of a particle size that has passed through a 325 mesh sieve) is collected. Thereafter, in order to eliminate the difference in quality and ensure the uniformity of the product, the pulverized electrolytic manganese dioxide is transferred to a gravitational mixer by a dense phase transport method, and then mixed uniformly for 16 hours in the mixer. To obtain high quality electrolytic manganese dioxide for anhydrous mercury-alkaline manganese batteries .
上記３実施例で得られた二酸化マンガンにおける主成分含有率は、ＭｎＯ２≧９１．０％、Ｆｅ≦６０ｐｐｍ、Ｃｕ≦５ｐｐｍ、Ｐｂ≦５ｐｐｍ、Ｎｉ≦５ｐｐｍ、Ｃｏ≦５ｐｐｍ、Ｍｏ≦０．５ｐｐｍ、Ａｓ≦０．５ｐｐｍ、Ｓｂ≦０．５ｐｐｍ、Ｋ≦２００ｐｐｍである。 The main component content in the manganese dioxide obtained in the above three examples is MnO 2 ≧ 91.0%, Fe ≦ 60 ppm, Cu ≦ 5 ppm, Pb ≦ 5 ppm, Ni ≦ 5 ppm, Co ≦ 5 ppm, Mo ≦ 0.5 ppm. As ≦ 0.5 ppm, Sb ≦ 0.5 ppm, K ≦ 200 ppm.
Claims (5)
酸化マンガン鉱石と黄鉄鉱石を混合し、当該混合物と硫酸とを１〜７槽の攪拌浸出槽からなる連続浸出槽中に連続的に供給し、反応温度を９０〜９５℃に制御し、３〜４時間かけて１段または多段連続浸出を行って、カリウムイオンを除去し、次いで中和による鉄分分離手段により鉄分を除去し、当該鉄分除去処理の後段で石灰粉を添加して、９０〜９５℃で３〜４時間かけて溶液のｐＨ値を６〜６．５に調整することにより、硫酸マンガン溶液を得る工程（１）と、
２段階連続精製処理により前記硫酸マンガン溶液から不純物を除去する精製を行うため、前記硫酸マンガン溶液の連続精製処理の第１段階として、温度を６０℃に制御した前記硫酸マンガン溶液にポリ硫化カルシウムを添加し、前記精製処理の第２段階として、前記第１段階で処理した前記硫酸マンガン溶液を樋を通して通流することで、カルシウムとマグネシウムを液の流動過程で除去し、その後、精製した前記硫酸マンガン溶液を貯蔵タンクへ移送して、そのまま前記貯蔵タンク内で３２時間静置させた後、静置した前記硫酸マンガン溶液からカルシウムおよびマグネシウムの不純物を沈殿物として除去する工程（２）と、
前記工程（２）で得られた精製した硫酸マンガン溶液を限外濾過した後、得られた硫酸マンガン溶液をプレート熱変換器を用いて９０〜１００℃に加熱し、これに乳化剤および発泡剤を同時に添加して得られた生成物を配管を通じて電解槽に供給し、電解温度１００〜１０３℃、アノード電流密度８０〜８５Ａ/ｍ２、電解電圧２．２〜３．５Ｖ、電解期間１２〜２０日の条件で電気分解を行うことにより、無水銀アルカリマンガン電池用電解二酸化マンガンを得る工程（３）と、
からなることを特徴とする、無水銀アルカリマンガン電池用電解二酸化マンガンの製造方法。 A method for producing electrolytic manganese dioxide for mercury-free alkaline manganese batteries, comprising three consecutive steps:
Manganese oxide ore and pyrite ore are mixed, the mixture and sulfuric acid are continuously fed into a continuous leaching tank consisting of 1 to 7 stirred leaching tanks, the reaction temperature is controlled to 90 to 95 ° C., One-step or multi-stage continuous leaching is carried out over 4 hours to remove potassium ions, then iron is removed by means of iron separation by neutralization, lime powder is added at the latter stage of the iron removal treatment, and 90 to 95 A step (1) of obtaining a manganese sulfate solution by adjusting the pH value of the solution to 6 to 6.5 at 3 ° C. over 3 to 4 hours;
In order to carry out purification to remove impurities from the manganese sulfate solution by a two-stage continuous purification process, as a first stage of the continuous purification process of the manganese sulfate solution, calcium sulfide is added to the manganese sulfate solution whose temperature is controlled at 60 ° C. was added, the second stage of the refining process, the first step wherein the manganese sulfate solution treated with that flowing through the trough and to remove calcium and magnesium in a fluidized process liquid, then purified the sulfate by transferring the solution of manganese to the storage tank, after it is 32 hours standing at the storage tank, and the step (2) to remove the standing said calcium and magnesium impurities from manganese sulfate solution as a precipitate,
After ultrafiltered purified manganese sulfate solution obtained in the step (2), the resulting manganese sulfate solution was heated to 90 to 100 ° C. with a plate heat converter, to which emulsifying agents and blowing The product obtained by adding the agent at the same time is supplied to the electrolytic cell through the pipe, electrolysis temperature 100 to 103 ° C., anode current density 80 to 85 A / m 2 , electrolysis voltage 2.2 to 3.5 V, electrolysis period 12 Step (3) of obtaining electrolytic manganese dioxide for anhydrous mercury-alkaline manganese battery by electrolysis under the condition of -20 days;
The manufacturing method of the electrolytic manganese dioxide for anhydrous silver alkaline manganese batteries characterized by comprising.
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- 2011-07-09 US US13/521,952 patent/US20130037416A1/en not_active Abandoned
- 2011-07-09 JP JP2013518940A patent/JP5764207B2/en active Active
- 2011-07-09 WO PCT/CN2011/077011 patent/WO2012006935A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN101892384B (en) | 2011-09-21 |
| WO2012006935A1 (en) | 2012-01-19 |
| CN101892384A (en) | 2010-11-24 |
| US20130037416A1 (en) | 2013-02-14 |
| JP2013538936A (en) | 2013-10-17 |
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