WO2012006935A1 - 无汞碱锰型电解二氧化锰的生产方法 - Google Patents

无汞碱锰型电解二氧化锰的生产方法 Download PDF

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Publication number
WO2012006935A1
WO2012006935A1 PCT/CN2011/077011 CN2011077011W WO2012006935A1 WO 2012006935 A1 WO2012006935 A1 WO 2012006935A1 CN 2011077011 W CN2011077011 W CN 2011077011W WO 2012006935 A1 WO2012006935 A1 WO 2012006935A1
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manganese
manganese dioxide
tank
stage
leaching
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PCT/CN2011/077011
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English (en)
French (fr)
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陈奇志
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广西有色金属集团汇元锰业有限公司
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Priority to JP2013518940A priority Critical patent/JP5764207B2/ja
Priority to US13/521,952 priority patent/US20130037416A1/en
Publication of WO2012006935A1 publication Critical patent/WO2012006935A1/zh

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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
    • 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
    • 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
    • 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
    • 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 relates to a method for producing mercury-free alkali-manganese electrolytic manganese dioxide, in particular to a method for producing mercury-free alkali-manganese electrolytic manganese dioxide by using the "two-mine method" to extract ultra-low-grade manganese oxide ore. Background technique
  • the alkaline manganese battery As the best high-power battery in the battery industry, the alkaline manganese battery has stable working voltage, high current continuous discharge, excellent performance, long storage time (up to 3 ⁇ 5 years), low temperature performance and good leakproof performance. And so on, it is well received by consumers at home and abroad.
  • the main raw material for the production of alkaline manganese batteries mercury-free alkali-manganese electrolytic manganese dioxide, has a worldwide annual consumption of more than 300,000 tons and is increasing at a rate of more than 10% per year, which has broad market prospects.
  • manganese carbonate or manganese oxide ore is used as raw material.
  • domestic manganese carbonate ore is used as raw material, and manganese ore consumption is low due to low manganese carbonate content in the ore (30% or less).
  • the main methods currently used are reduction roasting of manganese oxide ore after leaching to produce liquid or using "two-mine method” to produce electrolytic manganese dioxide, and using reduced roasting manganese oxide ore after leaching
  • the liquid preparation process has the disadvantages of long process flow, high production cost, and easy pollution to the surrounding environment of the plant; high-grade manganese oxide ore is used as raw material, and electrolytic manganese dioxide is produced by the "two-mine method", that is, two The manganese oxide ore is leached together with the reducing agent pyrite, because the manganese ore in the domestic manganese metallurgy industry adopts the intermittent leaching process, that is, the manganese ore is directly dissolved into the solution in only one leaching tank, and the process has a grade of 25% for the low grade manganese ore.
  • the following ore has a low leaching rate, a long turnaround time between materials, and the number of equipment
  • the disadvantages of increased and low utilization rate; and the use of such high-grade manganese ore resources (with grades above 25%) are decreasing, making it difficult to maintain long-term production.
  • Guangxi manganese ore resources are abundant, but most of them are low-grade manganese ore, which is characterized by low manganese content and high impurity content, which has not been fully exploited for a long time. Summary of the invention
  • the technical problem to be solved by the present invention is to provide an ultra-low-grade manganese oxide ore as a main material,
  • the "two-mine method" produces a mercury-free alkaline manganese type electrolytic manganese dioxide.
  • the technical solution adopted by the present invention to solve the above technical problems is to provide a mercury-free alkaline manganese type electrolytic manganese dioxide production method, which comprises the following steps in sequence: (1) mixing manganese oxide ore with pyrite and continuously simultaneously with sulfuric acid Continuously put into a continuous leaching tank consisting of 1 ⁇ 7 stirred leaching tanks in series to form one or more stages of continuous leaching, the process reaction temperature is controlled at 90 ⁇ 95 ° C, the reaction time is about 3 ⁇ 4 hours, leaching After the reaction is completed, the potassium ion is removed first, and then the iron is removed by neutralization and iron removal. The lime powder is added to the lime solution to adjust the solution ra to 6 to 6.
  • the reaction time is about 3 to 4 hours, and the temperature is 90 to 95 ° C.
  • the chute is dynamically removed from calcium and magnesium, and then sent to a static tank for 32 hours to precipitate the solution to remove calcium and magnesium impurities.
  • the prepared suspending agent and foaming agent are added to the respective electrolytic cells through the pipeline.
  • the electrolysis conditions are as follows: The electrolyte temperature is 100 ⁇ 103 °C, the anode current density is 80 ⁇ 85A/m 2 , the cell voltage is 2. 2 ⁇ 3. 5V, the electrolysis cycle is 12 ⁇ 20 days, and the mercury-free alkaline manganese type electrolytic manganese dioxide is obtained after electrolysis.
  • the manganese oxide ore and pyrite are directly fed into the continuous leaching tank at a ratio of 1:0.4, and at the same time, 1:4.7.
  • the mineral acid ratio is blended with sulfuric acid and waste electrolyte.
  • the waste electrolyte is derived from the tail liquid after the electrolysis in the step 3.
  • the anodic electrolytic manganese dioxide crude product obtained by electrolysis is crushed into particles of 6 to 8 mm, and is washed into a rinsing tank and washed with water and alkali.
  • the three-stage rinsing process the temperature of the second rinsing lye is 60 ⁇ 7 (TC, the temperature of the last rinsing water is 80 ⁇ 90 °C, the rinsing period is about 40 hours, and the rinsing liquid is directly heated by steam, after Electrolyzed manganese dioxide that has been milled to the desired particle size.
  • the milled electrolytic manganese dioxide is fed into a gravity-type mixing silo by means of dense phase transportation for homogenization, and the mixing time is about 16 hours.
  • the method for producing mercury-free alkali-manganese electrolytic manganese dioxide uses ultra-low-grade manganese oxide ore as a main raw material, and uses the "two-mine method" to directly extract ultra-low Manganese in manganese oxide ore, after obtaining manganese sulfate solution, deep purification and impurity removal, re-electrolysis to produce mercury-free alkali manganese
  • the type of electrolytic manganese dioxide can be reduced to 16% using manganese oxide ore, and the production process is not only applicable to manganese oxide ore with low grade and complex source, but also to high-grade manganese oxide ore.
  • the ferromanganese ore powder containing 14.32% of manganese and the pyrite powder having a sulfur content of 44.4% is mixed according to the dry specific gravity of 1:24, and the sulfuric acid having a concentration of 98% is added with water to prepare 100 g/L.
  • the dilute sulfuric acid solution, the mixed manganese oxide powder and the pyrite powder and the prepared sulfuric acid are continuously added to the continuous leaching tank at a ratio of 1:0.7, and continuously stirred, and the continuous leaching tank is composed of one
  • the leaching tank is formed to form a first-stage continuous leaching, the effective volume of the leaching tank is lm 3 , the bath temperature is 95 ° C, and the leaching reaction time is 3 hours from the feeding to the liquid leaching tank, and the PH value is 3 ⁇ 3.
  • the leaching reaction is completed, and the reaction is continuously stirred.
  • the liquid flowing out of the leaching tank enters the neutralization tank in series with the neutralization tank.
  • the effective volume of the neutralization tank is 1. 5 m 3 , and the lime powder is continuously added.
  • the neutralization reaction was carried out to control the ra value to be 6.0.
  • the reaction time was 3 hours.
  • the filtrate after neutralization was filtered, and the filter residue was sent to a slag field to obtain a crude manganese sulfate solution.
  • the crude manganese sulfate solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
  • the two-stage continuous purification process is used.
  • the crude manganese sulfate solution enters a continuous purification process to add calcium polysulfide, and the temperature is controlled at 60 ° C.
  • the filter residue is sent to the slag field, and the solution enters the second stage purification.
  • the calcium and magnesium are dynamically removed through the chute, and then sent to the static storage tank, and allowed to stand for 32 hours to precipitate the solution, and the calcium and magnesium impurities are precipitated and removed, thereby obtaining refined manganese sulfate.
  • the solution, the filter residue is sent to the slag field, and the filtrate is sent to the electrolysis.
  • the refined qualified manganese sulfate solution is subjected to ultrafine filtration, and is heated to 9 CTC through a plate heat exchanger to enter a high-level tank for suspension electrolysis.
  • the prepared suspending agent and foaming agent were added, the electrolyte temperature was 100 ° C, the anode current density was 81 A/m 2 , the cell voltage was 2. 4 V, the electrolysis cycle was 12 days, and the manganese dioxide was stripped from the anode.
  • the product is crushed to 6 ⁇ 8mm particles by the crusher and then into the rinsing tank.
  • the effective volume of each rinsing tank is Lm 3 , a three-stage rinsing process using water-washing-alkaline washing and one-washing.
  • the temperature of the second rinsing lye is 60 ° C
  • the temperature of the last rinsing water is 80 ° C
  • the rinsing period is 40 hours
  • the rinsing liquid is used.
  • the steam is heated directly.
  • the electrolytic manganese dioxide is sent to the pendulum mill to collect the product powder (particle size -325 mesh).
  • the dense phase conveying method is used to send the gravity mixing bin. Homogenization blending was carried out for about 16 hours to produce a qualified mercury-free alkali manganese-type manganese dioxide product.
  • the ferromanganese ore powder containing 15.56% of manganese, the pyrite powder having a sulfur content of 40.4% is mixed according to the dry specific gravity of 1:24, and the sulfuric acid having a concentration of 98% is added with water to prepare 100g/L.
  • the dilute sulfuric acid solution, the mixed manganese oxide powder and the pyrite powder and the prepared sulfuric acid are continuously added to the continuous leaching tank at a ratio of 1:0.7, and continuously stirred, and the continuous leaching tank is composed of three
  • the leaching tanks are arranged in series to form a three-stage continuous leaching.
  • the effective volume of each leaching tank is lm 3 , and the liquid enters the second-stage leaching tank and then enters the third-stage leaching tank.
  • the temperature of each tank is 93 ° C.
  • the leaching reaction time of the feed liquid from the third-stage leaching tank is 3.5 hours, and the stirring is continued during the reaction, and the liquid flowing out of the tertiary leaching tank enters the neutralization tank connected in series, and the neutralization tank is The effective volume is 1.5 m 3 , and then the lime powder is continuously added for the neutralization reaction, the control 13 ⁇ 4 value is 6.3, the reaction time is 3.5 hours, the filtrate after the neutralization is filtered, and the filter residue is sent to the slag field to obtain a coarse Making manganese sulfate solution.
  • the crude manganese sulfate solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
  • the two-stage continuous purification process is used.
  • the crude manganese sulfate solution enters a continuous purification process to add calcium polysulfide, and the temperature is controlled at 60 ° C.
  • the filter residue is sent to the slag field, and the solution enters the second stage purification.
  • the calcium and magnesium are dynamically removed through the chute, and then sent to the static storage tank, and allowed to stand for 32 hours to precipitate the solution, and the calcium and magnesium impurities are precipitated and removed, thereby obtaining refined manganese sulfate.
  • the solution, the filter residue is sent to the slag field, and the filtrate is sent to the electrolysis.
  • the refined qualified manganese sulfate solution is subjected to ultrafine filtration, and is heated to 95 ° C in a plate heat exchanger to enter a high-position tank for suspension electrolysis.
  • the prepared suspending agent and foaming agent were added, the electrolyte temperature was 102 ° C, the anode current density was 83 A/m 2 , the cell voltage was 2. 9 V, the electrolysis cycle was 15 days, and the manganese dioxide was stripped from the anode.
  • the product is crushed to 6 ⁇ 8mm particles by the crusher, and then enters the rinsing tank.
  • each rinsing tank The effective volume of each rinsing tank is lm 3 , and the three-stage rinsing process is washed with water and alkali, and the lye is washed twice.
  • the temperature is 65 ° C
  • the last rinse water temperature is 85 ° C
  • the rinse cycle is 40 hours
  • the rinse liquid is directly heated by steam.
  • the electrolytic manganese dioxide is sent to the pendulum mill to collect the product powder (particle size -325 mesh).
  • the dense phase conveying method is used to send the gravity mixing bin. Homogenization blending was carried out for about 16 hours to produce a qualified mercury-free alkali manganese-type manganese dioxide product.
  • Example 3 The ferromanganese ore powder containing 13.58% of manganese and the pyrite powder having a sulfur content of 47.48% are mixed according to the dry specific gravity of 1:24, and the sulfuric acid having a concentration of 98% is added with water to prepare 100 g/L.
  • the dilute sulfuric acid solution, the mixed manganese oxide powder and the pyrite powder and the prepared sulfuric acid are continuously added to the continuous leaching tank at a ratio of 1:0.7 while continuously stirring, and the continuous leaching tank is composed of seven
  • the leaching tanks are arranged in series to form a seven-stage continuous leaching.
  • the effective volume of each leaching tank is lm 3 .
  • the feed liquid enters the second-stage leaching tank and then enters the third to seventh-stage leaching tanks.
  • the temperature of each tank is 95°. C
  • the leaching reaction time from the feeding to the feed liquid from the seventh-stage leaching tank is 4 hours
  • the stirring is continued during the reaction
  • the liquid flowing out from the seventh-stage leaching tank enters the neutralization tank connected in series, and the neutralization tank
  • the effective volume is 1.5 m 3
  • the lime powder is continuously subjected to the neutralization reaction
  • the control 13 ⁇ 4 value is 6.5.
  • the neutralized filtrate is filtered, and the filter residue is sent to the slag field to obtain a crude manganese sulfate solution.
  • the crude manganese sulfate solution contains heavy metals such as copper, cobalt, nickel and lead, and impurities such as calcium and magnesium.
  • the two-stage continuous purification process is used.
  • the crude manganese sulfate solution enters a continuous purification process to add calcium polysulfide, and the temperature is controlled at 60 ° C.
  • the filter residue is sent to the slag field, and the solution enters the second stage purification.
  • the calcium and magnesium are dynamically removed through the chute, and then sent to the static storage tank, and allowed to stand for 32 hours to precipitate the solution, and the calcium and magnesium impurities are precipitated and removed, thereby obtaining refined manganese sulfate.
  • the solution, the filter residue is sent to the slag field, and the filtrate is sent to the electrolysis.
  • the refined qualified manganese sulfate solution is subjected to ultrafine filtration, and is heated to locrc through a plate heat exchanger to enter a high-position tank for suspension electrolysis.
  • the prepared suspending agent and foaming agent were added, the electrolyte temperature was 103 ° C, the anode current density was 85 A/m 2 , the cell voltage was 3.5 V, the electrolysis cycle was 20 days, and the manganese dioxide was stripped from the anode.
  • the product is crushed to 6 ⁇ 8mm particles by the crusher, and then enters the rinsing tank.
  • each rinsing tank The effective volume of each rinsing tank is lm 3 , and the three-stage rinsing process is washed with water and alkali, and the lye is washed twice.
  • the temperature is 70 ° C
  • the last rinse water temperature is 85 ° C
  • the rinse cycle is 40 hours
  • the rinse liquid is directly heated by steam.
  • the electrolytic manganese dioxide is sent to the pendulum mill to collect the product powder (particle size -325 mesh).
  • the dense phase conveying method is used to send the gravity mixing bin. Homogenization blending was carried out for about 16 hours to produce a qualified mercury-free alkali manganese-type manganese dioxide product.
  • the main indicators of the obtained manganese dioxide products are Mn0 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. 200ppm.

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Abstract

提供一种无汞碱锰型电解二氧化锰的生产方法，依次包括如下步骤：（1）将氧化锰矿与硫铁矿混合后与硫酸同时连续不断投入到连续浸出槽中，形成一级或多级连续浸出，浸出反应完成后先除去钾离子，再采用中和除铁法除铁，除铁后期加入石灰粉调节溶液pH为6〜6.5，在90〜95°C下反应3〜4小时后得硫酸锰溶液；（2）采用二段连续净化工艺对硫酸锰溶液进行净化除杂，硫酸锰溶液进入一段连续净化加入多硫化钙，进入二段净化先经过溜槽动态除钙、镁，后送至静置槽，静置陈化，将钙、镁杂质沉淀除去；（3）净化后的硫酸锰溶液经过超细过滤后，经板式换热器加热到90〜100°C后进入高位槽，同时加入制备好的悬浮剂和发泡剂，通过管道供至各个电解槽，电解后得到无汞碱锰型电解二氧化锰。该方法具有对氧化锰矿适应性广、工艺流程短、生产成本低等优点。

Description

无汞碱锰型电解二氧化锰的生产方法
本申请要求于 2010年 7月 15日提交中国专利局、 申请号为 201010227988. 7、 发明名称为 "无汞碱锰型电解二氧化锰的生产方法" 的中国专利申请的优先权， 其 全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种无汞碱锰型电解二氧化锰的生产方法， 特别涉及一种用 "两矿 法 "浸取超低品位的氧化锰矿生产无汞碱锰型电解二氧化锰的方法。 背景技术
碱锰电池作为电池工业中性能与价格比最佳的高功率电池，具有工作电压平稳、 大电流连续放电、 性能优良、 贮存时间长 (可达 3〜5 年） 、 低温性能和防漏性能好 等特点，深受国内外广大消费者欢迎。生产碱锰电池所用的主要原料——无汞碱锰型 电解二氧化锰， 其全球每年的消耗量超过 30万吨， 并且每年以 10 %以上的速度递 增， 具有广阔的市场前景。
目前生产电解二氧化锰的工艺中， 主要以碳酸锰矿或氧化锰矿为原料， 在冶炼 生产过程中， 以国产碳酸锰矿为原料， 因矿石中碳酸锰含量低 （30%以下）， 导致锰 矿消耗量很大、 生产成本过高； 以氧化锰矿为原料， 目前主要采用的工艺方法有还 原焙烧氧化锰矿后浸出制液或用 "两矿法" 生产电解二氧化锰， 而采用还原焙烧氧 化锰矿后浸出制液这一工艺方法， 存在工艺流程长、 生产成本高， 并且容易对厂区 周边环境造成污染等缺点； 以高品位的氧化锰矿为原料、 用 "两矿法"生产电解二 氧化锰， 即二氧化锰矿同还原剂硫铁矿一起浸出制液， 由于目前国内锰冶金行业锰 矿采用间断浸出工艺， 即只在一个浸出槽内直接将锰矿溶解进入溶液， 该工艺对低 品位锰矿即品位在 25%以下的矿石存在浸出率低， 物料在设备之间的周转时间长， 设备数量增加且利用率低等缺点； 且所使用的该类高品位锰矿资源 （品位在 25%以 上） 日益减少， 将难以维持长久的生产。 广西锰矿资源丰富， 但是大部分为低品位 锰矿石， 其特点是锰含量低、 杂质含量高， 长期以来没有得到充分开发利用。 发明内容
本发明所要解决的技术问题是提供一种能以超低品位氧化锰矿为主要材料， 用 "两矿法"生产无汞碱锰型电解二氧化锰的方法。
本发明为解决上述技术问题而采用的技术方案是提供一种无汞碱锰型电解二 氧化锰的生产方法， 依次包括如下步骤： （1 ) 将氧化锰矿与硫铁矿混合后与硫酸同 时连续不断投入到由 1〜7个搅拌着的浸出槽串联组成的连续浸出槽中，形成一级或 多级连续浸出， 过程反应温度控制在 90〜95°C， 反应时间约 3〜4小时， 浸出反应 完成后， 先除去钾离子， 再采用中和除铁法除铁， 除铁后期加入石灰粉调节溶液 ra 为 6〜6. 5， 反应时间约 3〜4小时， 温度为 90〜95°C， 得硫酸锰溶液； （2 ) 采用二 段连续净化工艺对硫酸锰溶液进行净化除杂， 硫酸锰溶液进入一段连续净化加入多 硫化钙， 控制温度在 6(TC， 溶液进入二段净化先经过溜槽动态除钙、 镁， 后送至静 置槽， 静置 32小时， 使溶液陈化， 将钙、 镁杂质沉淀除去； （3 )将净化后的硫酸锰 溶液经过超细过滤后， 经板式换热器加热到 90〜100°C °C后进入高位槽， 同时加入 制备好的悬浮剂和发泡剂， 通过管道供至各个电解槽， 电解条件为： 电解液温度为 100〜103°C， 阳极电流密度为 80〜85A/m2， 槽电压为 2. 2〜3. 5V， 电解周期为 12〜 20天， 电解后得到无汞碱锰型电解二氧化锰。
上述无汞碱锰型电解二氧化锰的生产方法中， 所述步骤 1中氧化锰矿与硫铁矿 按 1 : 0. 24的比例直接给入连续浸出槽中， 同时按 1 : 0. 47的矿酸比配入硫酸和废电 解液。
上述无汞碱锰型电解二氧化锰的生产方法中， 所述废电解液来自步骤 3电解后 的尾液。
上述无汞碱锰型电解二氧化锰的生产方法中， 所述步骤 3中将电解得到的阳极 电解二氧化锰粗产品破碎至 6〜8mm的颗粒， 进入漂洗槽， 采用水洗一碱洗一水洗的 三级漂洗工艺， 一、 二次漂洗碱液的温度均为 60〜7(TC， 末次漂洗水温度为 80〜 90°C， 漂洗周期约为 40小时，漂洗液均采用蒸汽直接加热， 后经过磨粉达到所需颗 粒度的电解二氧化锰。
上述无汞碱锰型电解二氧化锰的生产方法中， 对经过磨粉后的电解二氧化锰采 用密相输送方式送入重力式掺混料仓进行均化， 掺混时间约为 16小时。
本发明对比现有技术有如下的有益效果： 本发明提供的无汞碱锰型电解二氧化 锰的生产方法， 以超低品位氧化锰矿作为主要原料， 使用 "两矿法"直接浸取超低 品位氧化锰矿中的锰， 得到硫酸锰溶液后进行深度净化除杂， 再电解生产无汞碱锰 型电解二氧化锰 可使用氧化锰矿的品位降低至 16%， 且采用的生产工艺不仅对品 位低、 来源复杂的氧化锰矿适用， 对高品位的氧化锰矿也同样适用， 因此， 具有对 氧化锰矿适应性广、 工艺流程短、 生产成本低等优点， 可以充分利用广西丰富的低 品位氧化锰矿来生产无汞碱锰型电解二氧化锰产品， 对合理利用锰矿资源、 降低生 产成本有着很好的经济效益和社会效益。 附图说明
图 1是本发明实施例的工艺流程图。 具体实施方式
下面结合附图和实施例对本发明作进一步的描述。
实施例 1
将含锰 14. 32%的氧化锰矿粉、 含硫量为 44. 54%的硫铁矿粉按 1 : 0. 24的干比重 进行混合， 将浓度为 98%的硫酸加水配制成 100g/L的稀硫酸溶液， 混合后的氧化锰 粉和硫铁矿粉与配制好的硫酸按 1 : 0. 47的比例同时连续不断加入到连续浸出槽中， 并同时不断搅拌， 连续浸出槽是由一个浸出槽组成， 形成一级连续浸出， 浸出槽的 有效容积为 lm3， 槽温度为 95°C， 从投料到料液从浸出槽出来浸出反应时间为 3小 时， PH值达到 3〜3. 5 时表明浸出反应已完成， 反应过程中不断搅拌， 从浸出槽中 流出的料液进入与之串联的中和槽中， 中和槽的有效容积为 1. 5 m3， 再加入石灰粉 连续进行中和反应， 控制 ra值为 6. 0， 反应时间为 3小时， 中和后的滤液经过滤， 滤渣送往渣场， 得粗制硫酸锰溶液。 粗制硫酸锰溶液含有铜、 钴、 镍、 铅等重金属 和钙、 镁等杂质， 采用二段连续净化工艺技术， 粗制硫酸锰溶液进入一段连续净化 加入多硫化钙， 控制温度在 60°C， 滤渣送往渣场， 溶液进入二段净化先经过溜槽动 态除钙、 镁， 后送至静置槽， 静置 32小时， 使溶液陈化， 将钙、 镁杂质沉淀除去， 得精制硫酸锰溶液， 滤渣送往渣场， 滤液送往电解。
精制合格的硫酸锰溶液经过超细过滤， 在经板式换热器加热到 9CTC到后进入高 位槽进行悬浮电解。 同时加入制备好的悬浮剂和发泡剂， 电解液温度为 100°C， 阳 极电流密度为 81A/m2， 槽电压为 2. 4V， 电解周期为 12天， 由阳极上剥离二氧化锰 粗产品， 经破碎机破碎至 6〜8mm的颗粒， 再进入漂洗槽， 每个漂洗槽的有效容积为 lm3， 采用水洗一碱洗一水洗的三级漂洗工艺， 一、 二次漂洗碱液的温度均为 60°C， 末次漂洗水温度为 80°C， 漂洗周期为 40小时，漂洗液均采用蒸汽直接加热。 漂洗后 的电解二氧化锰送往摆式磨粉机磨粉收集产品粉末 （粒度 -325 目）， 为消除产品质 量差异， 保证产品的均匀性， 采用密相输送方式送重力式掺混料仓进行均化掺混约 16小时， 制得合格的无汞碱锰型二氧化锰产品。
实施例 2
将含锰 15. 56%的氧化锰矿粉、 含硫量为 40. 54%的硫铁矿粉按 1 : 0. 24的干比重 进行混合， 将浓度为 98%的硫酸加水配制成 100g/L的稀硫酸溶液， 混合后的氧化锰 粉和硫铁矿粉与配制好的硫酸按 1 : 0. 47的比例同时连续不断加入到连续浸出槽中， 并同时不断搅拌， 连续浸出槽是由三个浸出槽串联组成， 形成三级连续浸出， 每个 浸出槽的有效容积为 lm3， 料液进入第二级浸出槽后再进入第三级浸出槽中， 各槽温 度为 93°C， 从投料到料液从第三级浸出槽出来浸出反应时间为 3. 5小时， 反应过程 中不断搅拌， 从三级浸出槽中流出的料液进入与之串联的中和槽中， 中和槽的有效 容积为 1. 5 m3， 再加入石灰粉连续进行中和反应， 控制 1¾值为 6. 3， 反应时间 3. 5 小时， 中和后的滤液经过滤， 滤渣送往渣场， 得粗制硫酸锰溶液。 粗制硫酸锰溶液 含有铜、 钴、 镍、 铅等重金属和钙、 镁等杂质， 采用二段连续净化工艺技术， 粗制 硫酸锰溶液进入一段连续净化加入多硫化钙， 控制温度在 60°C， 滤渣送往渣场， 溶 液进入二段净化先经过溜槽动态除钙、 镁， 后送至静置槽， 静置 32小时， 使溶液陈 化， 将钙、 镁杂质沉淀除去， 得精制硫酸锰溶液， 滤渣送往渣场， 滤液送往电解。
精制合格的硫酸锰溶液经过超细过滤， 在经板式换热器加热到 95°C到后进入高 位槽进行悬浮电解。 同时加入制备好的悬浮剂和发泡剂， 电解液温度为 102°C， 阳 极电流密度为 83A/m2， 槽电压为 2. 9V， 电解周期为 15天， 由阳极上剥离二氧化锰 粗产品， 经破碎机破碎至 6〜8mm的颗粒， 再进入漂洗槽， 每个漂洗槽的有效容积为 lm3， 采用水洗一碱洗一水洗的三级漂洗工艺， 一、 二次漂洗碱液的温度均为 65°C， 末次漂洗水温度为 85°C， 漂洗周期为 40小时，漂洗液均采用蒸汽直接加热。 漂洗后 的电解二氧化锰送往摆式磨粉机磨粉收集产品粉末 （粒度 -325 目）， 为消除产品质 量差异， 保证产品的均匀性， 采用密相输送方式送重力式掺混料仓进行均化掺混约 16小时， 制得合格的无汞碱锰型二氧化锰产品。
实施例 3 将含锰 13. 58%的氧化锰矿粉、 含硫量为 47. 44%的硫铁矿粉按 1 : 0. 24的干比重 进行混合， 将浓度为 98%的硫酸加水配制成 100g/L的稀硫酸溶液， 混合后的氧化锰 粉和硫铁矿粉与配制好的硫酸按 1 : 0. 47的比例同时连续不断加入到连续浸出槽中， 并同时不断搅拌， 连续浸出槽是由七个浸出槽串联组成， 形成七级连续浸出， 每个 浸出槽的有效容积为 lm3， 料液进入第二级浸出槽后再进入第三至第七级浸出槽中， 各槽温度为 95°C， 从投料到料液从第七级浸出槽出来浸出反应时间为 4小时， 反应 过程中不断搅拌， 从七级浸出槽中流出的料液进入与之串联的中和槽中， 中和槽的 有效容积为 1. 5 m3， 再加入石灰粉连续进行中和反应， 控制 1¾值为 6. 5， 中和后的 滤液经过滤， 滤渣送往渣场， 得粗制硫酸锰溶液。 粗制硫酸锰溶液含有铜、 钴、 镍、 铅等重金属和钙、 镁等杂质， 采用二段连续净化工艺技术， 粗制硫酸锰溶液进入一 段连续净化加入多硫化钙， 控制温度在 60°C， 滤渣送往渣场， 溶液进入二段净化先 经过溜槽动态除钙、 镁， 后送至静置槽， 静置 32小时， 使溶液陈化， 将钙、 镁杂质 沉淀除去， 得精制硫酸锰溶液， 滤渣送往渣场， 滤液送往电解。
精制合格的硫酸锰溶液经过超细过滤， 在经板式换热器加热到 locrc后进入高 位槽进行悬浮电解。 同时加入制备好的悬浮剂和发泡剂， 电解液温度为 103°C， 阳 极电流密度为 85A/m2， 槽电压为 3. 5V， 电解周期为 20天， 由阳极上剥离二氧化锰 粗产品， 经破碎机破碎至 6〜8mm的颗粒， 再进入漂洗槽， 每个漂洗槽的有效容积为 lm3， 采用水洗一碱洗一水洗的三级漂洗工艺， 一、 二次漂洗碱液的温度均为 70°C， 末次漂洗水温度为 85°C， 漂洗周期为 40小时，漂洗液均采用蒸汽直接加热。 漂洗后 的电解二氧化锰送往摆式磨粉机磨粉收集产品粉末 （粒度 -325 目）， 为消除产品质 量差异， 保证产品的均匀性， 采用密相输送方式送重力式掺混料仓进行均化掺混约 16小时， 制得合格的无汞碱锰型二氧化锰产品。
三种实施例得到得二氧化锰产品主要指标 Mn02 91. 0%、 Fe 60ppm、 Cu 5ppm、 Pb 5ppm、 Ni 5ppm、 Co 5ppm、 Mo 0. 5ppm、 As 0. 5ppm、 Sb 0. 5ppm、 K 200ppm。
虽然本发明已以较佳实施例揭示如上， 然其并非用以限定本发明， 任何本领域 技术人员， 在不脱离本发明的精神和范围内， 当可作些许的修改和完善， 因此本发 明的保护范围当以权利要求书所界定的为准。

Claims

权 利 要 求
1、 一种无汞碱锰型电解二氧化锰的生产方法， 其特征在于依次包括如下步骤:
( 1 )将氧化锰矿与硫铁矿混合后与硫酸同时连续不断投入到由 1〜7个搅拌着 的浸出槽串联组成的连续浸出槽中， 形成一级或多级连续浸出， 过程反应温度控制 在 90〜95°C， 反应时间约 3〜4小时， 浸出反应完成后， 先除去钾离子， 再采用中 和除铁法除铁，除铁后期加入石灰粉调节溶液 PH为 6〜6. 5，反应时间约 3〜4小时， 温度为 90〜95°C， 得硫酸锰溶液；
( 2 ) 采用二段连续净化工艺对硫酸锰溶液进行净化除杂， 硫酸锰溶液进入一 段连续净化加入多硫化钙， 控制温度在 60°C， 溶液进入二段净化先经过溜槽动态除 钙、 镁， 后送至静置槽， 静置 32小时， 使溶液陈化， 将钙、 镁杂质沉淀除去。；
( 3 )将净化后的硫酸锰溶液经过超细过滤后， 经板式换热器加热到 90〜100°C 后进入高位槽， 同时加入制备好的悬浮剂和发泡剂， 通过管道供至各个电解槽， 电 解条件为： 电解液温度为 100〜103°C，阳极电流密度为 80〜85A/m2，槽电压为 2. 2〜 3. 5V， 电解周期为 12〜20天， 电解后得到无汞碱锰型电解二氧化锰。
2、 根据权利要求 1 所述的无汞碱锰型电解二氧化锰的生产方法， 其特征在于 所述步骤 1中氧化锰矿与硫铁矿按 1 : 0. 24的比例直接给入连续浸出槽中， 同时按 1 : 0. 47的矿酸比配入硫酸和废电解液。
3、 根据权利要求 2所述的无汞碱锰型电解二氧化锰的生产方法， 其特征在于 所述废电解液来自步骤 3电解后的尾液。
4、 根据权利要求 1 所述的无汞碱锰型电解二氧化锰的生产方法， 其特征在于 所述步骤 3中将电解得到的阳极电解二氧化锰粗产品破碎至 6〜8mm的颗粒，进入漂 洗槽， 采用水洗一碱洗一水洗的三级漂洗工艺， 一、 二次漂洗碱液的温度均为 60〜 70°C， 末次漂洗水温度为 80〜9(TC， 漂洗周期约为 40小时，漂洗液均采用蒸汽直接 加热， 后经过磨粉达到所需颗粒度的电解二氧化锰。
5、 根据权利要求 4所述的无汞碱锰型电解二氧化锰的生产方法， 其特征在于 对经过磨粉后的电解二氧化锰采用密相输送方式送入重力式掺混料仓进行均化， 掺 混时间约为 16小时。
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