公开(公告)号：EP2487137A1

公开(公告)日：2012-08-15

申请号：EP10821565.8

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd. ,  Shenzhen Haoyitong Investment And Development Co., Ltd. ,  Beijing Maxqueen Technology Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  WU, Fei

IPC分类号： C01G45/10 ,  B01D53/80 ,  B01D53/50

CPC分类号： C01G45/10 ,  B01D53/50 ,  B01D53/80 ,  B01D2251/60

摘要： Provided is a method for preparing manganese sulfate monohydrate by desulfurizing fume with middle-low grade manganese dioxide ore, which comprises: preparing a slurry by using middle-low grade manganese dioxide ore powder, first putting sulfur-containing fume in an absorbing device and controlling gas velocity and gas-liquid ratio, and then adding manganese dioxide slurry and controlling the slurry to backwards flow relative to the sulfur-containing fume, discharging the desulfurized fume from the absorbing device, pressure-filtering and separating the slurry discharged from the absorbing device, recycling the mother liquor to the absorbing device, and continuing the recycling operation until the manganese sulfate in the mother liquor is >=200g/l, agitating and washing the obtained filter cake at 60-70°C, adjusting pH value of the clear solution obtained by pressure-filtering and separating to 2-4, adding manganese sulfide under agitation at 25-95 °C, and filtering and removing impurities, continuing agitating, pressure-filtering and separating, vaporizing the obtained clear filtrate, and obtaining manganese sulfate monohydrate after drying in the air stream. Desulfurizing efficiency is improved, the production cost of manganese sulfate is reduced, the recycling rate of total manganese is improved, and the valuable metals are recycled in high efficiency.

摘要翻译： 提供了一种用于通过脱硫烟与中等低级二氧化锰矿，包括制备一水合硫酸锰的方法：通过使用中等低级二氧化锰粉矿，第一推杆含硫烟气在吸收装置和控制制备浆料 气体速度和气体 - 液体比，再加入二氧化锰浆液和控制浆料倒流相对于含硫硅粉，排出从吸收设备，压力过滤脱硫烟和分离从吸收装置中排出的淤浆 ，将母液再循环而到吸收装置，并继续循环操作，直到硫酸锰在母液中是> = 200克/升，搅拌并洗涤，在60-70℃下获得的滤饼，调整清晰的pH值 溶液通过加压过滤获得和分离至2-4，在25-95℃下添加在搅拌下的硫化锰，和过滤和除去IMPU rities，持续搅拌，压力过滤和分离，蒸发获得澄清的滤液，并在空气流中干燥后，获得一水合硫酸锰。 脱硫效率提高，硫酸锰的生产成本降低，总锰的再循环率提高，有价值的金属循环到高效率。

公开(公告)号：EP2487137B1

公开(公告)日：2015-03-25

申请号：EP10821565.8

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  WU, Fei

IPC分类号： C01G45/10 ,  B01D53/80 ,  B01D53/50

CPC分类号： C01G45/10 ,  B01D53/50 ,  B01D53/80 ,  B01D2251/60

公开(公告)号：EP2557067A1

公开(公告)日：2013-02-13

申请号：EP10848733.1

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong

IPC分类号： C01G45/10

CPC分类号： C01G45/10

摘要： Provided is a method for preparing manganese sulfate monohydrate, which comprises the following steps: (1) reacting MnO with (NH 4 ) 2 SO 4 solution under heat, and separating solid from liquid after reaction; 2) determining the concentration of MnSO 4 in the resulting solution of step 1), adding equimolar ammonium sulfide solution thereto to carry out reaction under agitation, separating solid from liquid after reaction, and then washing solid phase; 3) dissolving the solid phase with concentrated sulfuric acid, adding hydrogen peroxide to the obtained solution, heating to boiling, adjusting the pH value of the solution to 5-6, removing the solid phase through precise filtration, evaporating and oven drying the filtrate to obtain MnSO 4 •H 2 O product. The impurities are separated away and the amount of byproducts is reduced by this method, and the yield of manganese sulfate monohydrate is improved.

摘要翻译： 本发明提供一种制备硫酸锰一水合物的方法，包括以下步骤：（1）将MnO与（NH4）2SO4溶液加热反应，反应后将固体与液体分离; 2）测定步骤1）所得溶液中MnSO4的浓度，加入等摩尔硫化铵溶液搅拌反应，反应后将固体与液体分离，然后洗涤固相; 3）用浓硫酸溶解固相，向得到的溶液中加入过氧化氢，加热至沸腾，调节溶液的pH值至5-6，精密过滤除去固相，蒸发并烘干滤液至 获得MnSO4•H2O产品。 通过该方法杂质被分离并且副产物的量被减少，并且硫酸锰一水合物的产率得到改善。

公开(公告)号：EP2554519B1

公开(公告)日：2014-05-21

申请号：EP10848732.3

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd. ,  Beijing Maxqueen Technology Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong

IPC分类号： C01G45/10

CPC分类号： C01G45/10 ,  C01P2006/80

公开(公告)号：EP2554519A1

公开(公告)日：2013-02-06

申请号：EP10848732.3

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd. ,  Beijing Maxqueen Technology Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong

IPC分类号： C01G45/10

CPC分类号： C01G45/10 ,  C01P2006/80

摘要： Provided is a method for preparing manganese sulfate monohydrate, which comprises the following steps: (1) adding equimolar BaS or SrS solution into manganese sulfate solution to carry out reaction fully, and separating and washing the obtained solid; (2) mixing the solid with deionized water to prepare a slurry, dissolving the slurry with concentrated sulfuric acid, and separating solid from liquid to obtain MnSO 4 solution; (3) adding proper amount of hydrogen peroxide to the MnSO 4 solution, heating to boiling, adjusting the pH value of the solution within 5-6, evaporation the filtrate after a precise filtration, and crystallizing and drying to obtain MnSO 4 H 2 O product. Manganese sulfate monohydrate can be produced at high yield in a cost-efficient manner by this method.

摘要翻译： 提供了一种制备硫酸锰一水合物的方法，其包括以下步骤：（1）将等摩尔BaS或SrS溶液加入硫酸锰溶液中进行充分反应，分离和洗涤所得固体; （2）将固体与去离子水混合以制备浆料，用浓硫酸溶解浆料，并从液体中分离固体得到MnSO 4溶液; （3）向MnSO 4溶液中加入适量的过氧化氢，加热至沸腾，将溶液的pH值调节至5-6，精确过滤后蒸发滤液，结晶并干燥得到MnSO 4 H 2 O 产品。 通过该方法，可以高成本高效率地生产硫酸锰一水合物。

公开(公告)号：EP2557067B1

公开(公告)日：2014-04-16

申请号：EP10848733.1

申请日：2010-07-20

申请人： Guizhou Redstar Developing Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong

IPC分类号： C01G45/10

CPC分类号： C01G45/10

公开(公告)号：EP2455341A1

公开(公告)日：2012-05-23

申请号：EP10799405.5

申请日：2010-06-13

申请人： Guizhou Redstar Developing Co., Ltd. ,  Shenzhen Haoyitong Investment And Development Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong

IPC分类号： C01G45/10

CPC分类号： C01G45/10 ,  C01G45/02 ,  C01P2006/80

摘要： Provided is a method for preparing manganese sulfate, which comprises the following steps: adding sulfide with reducing ability to manganese dioxide ore by quantification according to the reaction molar ratio to fully react, determining the end-point of reaction, and then separating and washing solid product; reacting the solid product with 9-12mol/L H 2 SO 4 , controlling the end-point of reaction to pH 3-5, keeping the MnSO 4 concentration in the reaction liquid within the range of 300 - 400g/L, and then separating solid from liquid after reaction; and using H 2 SO 4 to acidify the separated solution until the pH value of the solution is 2-3, adding hydrogen peroxide and heating, finely filtering to remove solid phase, and then vaporizing, condensing, crystallizing and dewatering the filtered liquid to obtain manganese sulfate. The method enables a plurality of heavy metals to be converted into indissoluble sulfides while obtaining manganous compounds that are dissoluble in acid. At the same time, manganese sulfate low in calcium, magnesium and heavy metals is obtained.

摘要翻译： 本发明提供硫酸锰的制备方法，其特征在于，通过根据反应摩尔比定量添加二氧化锰矿还原能的硫化物进行充分反应，确定反应终点，然后分离洗涤固体 产品; 使固体产物与9-12mol / LH 2 SO 4反应，控制反应终点为pH 3-5，使反应液中的MnSO 4浓度保持在300-400g / L范围内，然后分离固体 反应后液体; 并使用H 2 SO 4将分离的溶液酸化直至溶液的pH值为2-3，加入过氧化氢并加热，精细过滤除去固相，然后蒸发，冷凝，结晶和脱水过滤液体，得到 硫酸锰。 该方法能够将多种重金属转化为不溶性硫化物，同时获得可溶于酸的二价锰化合物。 同时，获得了低钙，镁和重金属的硫酸锰。

公开(公告)号：EP2679543A3

公开(公告)日：2016-03-23

申请号：EP13165123.4

申请日：2013-04-24

申请人： Guizhou Redstar Developing Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  LIU, Zhengtao ,  ZENG, Kaiwen

IPC分类号： C01G45/00 ,  C01G45/02

CPC分类号： C01G45/02 ,  C01G45/00 ,  C01P2002/72 ,  C01P2004/03 ,  C01P2004/51 ,  C01P2004/61 ,  C01P2004/62 ,  C01P2006/12 ,  C01P2006/80 ,  C30B7/14 ,  C30B29/16 ,  Y02E60/122 ,  Y10T428/2982

摘要： The present invention provides methods for preparing trimanganese tetroxide with low BET specific surface area and methods for controlling particle size of trimanganese tetroxide and trimanganese tetroxide product. The preparation methods and the methods for controlling particle size comprise following processes: (1) Purifying air by spraying dilute aqueous ammonia; (2) Pretreating of removing impurities from MnSO 4 solution with concentration in a range of 150~200g/L; (3) Process for preparing seed crystal: Cooling MnSO 4 solution to a temperature of less than 40°C, and introducing liquid NH 3 into the cooled MnSO 4 solution until pH value reaches 10.5-11.0, and then separating the mixture by solid-liquid separation to obtain filtrate and solid; adding NH 4 HCO 3 to the filtrate to recovery Mn element, and then forming slurry, introducing the purified air, and oxidizing the slurry into Mn 3 O 4 ; (4) Process for obtaining the final product by controlling oxidization: adding Mn 3 O 4 seed crystal to the MnSO 4 solution, Al containing salt is optionally added, turning on the recycle pump, controlling the temperature of the system in the range of 25 ± 5°C, and controlling pH value of the reaction system in a range of 6.5-7.5, which makes the MnSO 4 solution circulate more than 6 times per hour, not stopping the reaction until MnSO 4 content of the reaction solution is ≤1.5g/L, so as to obtain Mn 3 O 4 product.The trimanganese tetroxide product has properties that the particle is spherical, impurities content is low, the crystalline phase is pure, particle size distribution is narrow, which meets the international requirements for trimanganese tetroxide used for preparation manganese cathode materials for lithium ion secondary battery. The trimanganese tetroxide product has properties that BET specific surface area is less than 1m 2 /g, D 50 is 10-12µm or 14-16µm, weight content of Fe is less than 10ppm, and weight content of Cu, Zn, Pb and Cd are less than 0.1ppm.

公开(公告)号：EP2679543A2

公开(公告)日：2014-01-01

申请号：EP13165123.4

申请日：2013-04-24

申请人： Guizhou Redstar Developing Co., Ltd. ,  Shenzhen Haoyitong Investment And Development Co., Ltd.

发明人： JIANG, Zhiguang ,  HUA, Dong ,  LIU, Zhengtao ,  ZENG, Kaiwen

IPC分类号： C01G45/00 ,  C01G45/02

CPC分类号： C01G45/02 ,  C01G45/00 ,  C01P2002/72 ,  C01P2004/03 ,  C01P2004/51 ,  C01P2004/61 ,  C01P2004/62 ,  C01P2006/12 ,  C01P2006/80 ,  C30B7/14 ,  C30B29/16 ,  Y02E60/122 ,  Y10T428/2982

摘要： The present invention provides methods for preparing trimanganese tetroxide with low BET specific surface area and methods for controlling particle size of trimanganese tetroxide and trimanganese tetroxide product. The preparation methods and the methods for controlling particle size comprise following processes: (1) Purifying air by spraying dilute aqueous ammonia; (2) Pretreating of removing impurities from MnSO 4 solution with concentration in a range of 150~200g/L; (3) Process for preparing seed crystal: Cooling MnSO 4 solution to a temperature of less than 40°C, and introducing liquid NH 3 into the cooled MnSO 4 solution until pH value reaches 10.5-11.0, and then separating the mixture by solid-liquid separation to obtain filtrate and solid; adding NH 4 HCO 3 to the filtrate to recovery Mn element, and then forming slurry, introducing the purified air, and oxidizing the slurry into Mn 3 O 4 ; (4) Process for obtaining the final product by controlling oxidization: adding Mn 3 O 4 seed crystal to the MnSO 4 solution, Al containing salt is optionally added, turning on the recycle pump, controlling the temperature of the system in the range of 25 ± 5°C, and controlling pH value of the reaction system in a range of 6.5-7.5, which makes the MnSO 4 solution circulate more than 6 times per hour, not stopping the reaction until MnSO 4 content of the reaction solution is ≤1.5g/L, so as to obtain Mn 3 O 4 product.The trimanganese tetroxide product has properties that the particle is spherical, impurities content is low, the crystalline phase is pure, particle size distribution is narrow, which meets the international requirements for trimanganese tetroxide used for preparation manganese cathode materials for lithium ion secondary battery. The trimanganese tetroxide product has properties that BET specific surface area is less than 1m 2 /g, D 50 is 10-12µm or 14-16µm, weight content of Fe is less than 10ppm, and weight content of Cu, Zn, Pb and Cd are less than 0.1ppm.

摘要翻译： 本发明提供了用于制备具有低的BET比表面积和用于控制四氧化三锰和四氧化三锰产品的颗粒尺寸的方法四氧化三锰的方法。 的制备方法和用于控制粒径的方法包括以下过程：（1）通过喷雾稀氨水wässrige净化空气; （2）从硫酸锰溶液同浓度的范围为150〜200克/ L中除去杂质的前处理; 冷却硫酸锰溶液到低于40℃的温度，并引入液体NH 3到冷却的硫酸锰溶液直至pH值达到10.5-11.0，然后由固分离混合物：（3）用于制备晶种的方法 液分离，得到滤液和固体; 加入NH 4 HCO 3向滤液中回收的Mn元素，然后形成用浆料，将精制的空气，并将该浆料氧化成的Mn 3 O 4; （4），用于通过控制氧化获得最终产物的方法：添加Mn 3 O 4晶种到硫酸锰溶液，含Al盐可任选地加入，接通循环泵，控制系统的温度在25的范围内 ±5℃，并且控制在范围6.5-7.5，这使得该溶液硫酸锰循环6次以上每小时，不停止，直到反应溶液的反应硫酸锰含量为‰¤反应体系的pH值 1.5克/ L，从而获得的Mn 3 O 4产物。四氧化三锰产品具有属性做的颗粒是球形的，杂质含量低，结晶相是纯的，粒径分布窄，符合国际要求 用于制备锰正极材料的锂离子二次电池四氧化三锰。 的四氧化三锰产品具有属性确实BET比表面积小于1米2 /克，D 50是10-12μm或14-16μm，铁的重量含量低于10ppm的，和重量含量铜，锌，铅和镉的 小于的0.1ppm。