利用生产钛白粉的废酸和低品位软锰矿生产硫酸锰

介绍用生产钛白粉的废酸和低品位软锰矿为原料生产应用广泛的硫酸锰的方法。该法对生产钛白粉的废酸和因杂质含量高难以开发利用的副产物硫酸亚铁的治理及低品位软锰矿的利用开辟了新路。     

Upgrading of low-grade manganese ore based on reduction roasting and magnetic separation technique

The selective reduction of low-grade manganese ore followed by magnetic separation was proposed to produce rich-manganese ore. The optimized parameters include a roasting temperature of 1050°C, a roasting time of 6 h, a manganese ore size of 8–13 mm, and an FC/O ratio of 2.5. The reduction roasting products of low-grade manganese ore, mainly comprising of MnO, metallic iron, and residual gangue, could be separated effectively to obtain rich-manganese ore and magnetic product. The RMn, RFe, and TMn can reach the peak values of 71.00%, 93.60%, and 56.20wt%, respectively, at a rational magnetic field strength of 100 mT. In particular, the Mn/Fe ratio is up to 10.85, which meets the requirements of ferromanganese alloy smelting.     

硫酸化焙烧从锰矿中回收钴—─I.硫酸化焙烧工艺

采用两段硫酸化焙烧工艺对从废弃菱锰矿中回收钴进行了实验研究．详细考查了酸比、焙烧温度、焙烧时间的影响以及硫酸钠在焙烧中的催化作用．实验结果表明，在适宜的工艺条件下，钴的提取率可达９５％，锰的提取率达１００％，而铁的溶出率则低于８％，取得了令人满意的结果．     

On the high‐gasification rate of Brazilian manganese ore in chemical‐looping combustion (CLC) for solid fuels

The high rate of char gasification observed when using a Brazilian manganese ore as compared to ilmenite is investigated in a batch fluidized‐bed reactor. Experiments were carried out at 970°C using petroleum coke, coal and wood char as fuel with a 50% H₂O in N₂ as fluidizing gas. A manufactured manganese oxygen carrier was also used, however, which presented a slower char conversion rate than the manganese ore. It is concluded that decrease in H₂ inhibition and oxygen release are unlikely to be the main responsible mechanisms for the ore's unexpected gasification rate. The ore was also mixed in different ratios with ilmenite and it was observed that the presence of even small amounts of ore in the bed resulted in increased gasification rate. Thus, the high‐gasification rate for the manganese ore could be due to a contribution from the impurities in the ore by catalyzing the gasification reaction. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4346–4354, 2013     

低品位氧化锰矿中锰的还原回收

锰矿是一种重要的战略矿产资源,在冶金、化工、电子等工业中被广泛地应用。但是,我国锰矿资源贫乏,锰矿石品位偏低,根本不能满足国内生产锰系产品的需要。对我国锰矿资源状况、资源特点以及资源需求等方面进行了介绍,着重综述了近期国内外从低品位氧化锰矿中还原回收锰的新工艺技术,并介绍了这方面的研究进展。     

Cobalt–manganese separation: The extraction of cobalt(II) from manganese sulphate solutions by cyanex 301

The extraction and stripping reactions of cobalt(II) by Cyanex 301 in Iberfluid diluent from aqueous manganese sulphate solutions has been investigated. The effect of different variables which should influence the extraction-stripping of cobalt was evaluated, including equilibration time, temperature, organic diluent, extractant concentration, aqueous pH, cobalt loading, strip solution concentration, etc. The number of stages required for the extraction and stripping of cobalt was also evaluated. The results were used to define the conditions for the purification of manganese sulphate solutions. © 1998 Society of Chemical Industry     

软锰矿浸出制备软磁铁氧体用碳酸锰的研究

研究了以低品位软锰矿石为原料,配入植物粉料,用硫酸直接浸出软锰矿制备软磁铁氧体用碳酸锰的新工艺方法。探讨了软锰矿直接酸浸、含锰浸出液净化除杂、锰净化液碳化结晶等工艺条件。所制备的产品经X 射线衍射、粒度分析及化学成分分析等测试,结果表明,产品质量达到GB10503 89Ⅰ型品的要求。在优惠工艺条件下,锰的回收率达90%以上。     

细粒嵌布锰银矿浸取中的超声强化作用

采用先锰后银两段浸出流程处理高锰银矿取得了较好的效果. 一段浸出以黄铁矿为还原剂浸出分解包裹银的锰矿物，暴露出新鲜的银矿物，锰分解率为96%，相应的工艺条件为：反应温度95℃，反应时间5 h，黄铁矿:锰银矿=0.20:1；当向反应器中输入频率为40 kHz的超声波时，比常规的锰浸出时间减少一半，黄铁矿用量也明显降低. 二段浸锰渣采用氰化法提银，银的浸出率可达95%，大大高于锰银矿直接氰化法的银浸出率28%.     

提钪废液制备高纯碳酸锰

本文研究了以钨渣提钪废液为原料,软锰矿为氧化剂,菱锰矿为中和剂,制备高纯碳酸锰的工艺方法。探讨了反应温度、菱锰矿用量与反应时间对锰浸出效果的影响,以及水合二氧化锰吸附法中过氧化氢用量对除硅效果的影响。硫酸锰溶液经过水解法除铁、铝,硫化铵法除重金属,水合二氧化锰吸附法除硅,氟化铵法除钙、镁、稀土元素,最后碳酸氢铵沉淀获得高纯碳酸锰。     

过硫酸铵容量法分析电解锰渣中锰含量的条件研究

对电解锰渣中准确测定锰的实验条件进行研究,测定方法是将电解锰渣用硫磷混酸分解,硝酸银为催化剂,用过硫酸铵将锰(Ⅱ)氧化为锰(Ⅶ),然后用硫酸亚铁铵进行滴定。研究了待测溶液的pH值、过硫酸铵的用量及煮沸时间对测定结果的影响。结果表明,电解锰渣的用量在0.2g,加过硫酸铵前的pH值为3,过硫酸铵的用量1.5～3.5g,煮沸时间为4min,测定准确度最高,加标回收率在99.6%～100.4%之间,在该条件下不同来源电解锰渣中锰含量测定结果与原子吸收分光光度计测定结果一致。     

不同催化剂光催化降解分散蓝56染料的效果

分析了锐钛晶型TiO2和锰矿光催化降解分散蓝56染料的效果。结果表明,锰矿对分散蓝56染料的降解效果与锐钛晶型TiO2对分散蓝56染料的降解效果相近。     

贫软锰矿直接酸浸生产高纯碳酸锰的工艺研究

介绍了含锰量18%～20%的贫软锰矿、硫铁矿与硫酸反应直接浸取制备硫酸锰溶液,经深度净化后,再与天然净化碱卤合成制备高纯碳酸锰的工艺过程和技术条件,产品质量符合标准要求,锰的浸出率达到95%,总合成收率达到90%以上。     

用闪锌矿(方铅矿)精矿催化还原软锰矿(大洋锰结核矿)制取硫酸锰

在稀硫酸(或稀盐酸)溶液中，用闪锌矿(或方铅矿)精矿作还原剂，用可溶性铁盐作催化剂，分解软锰矿(或大洋锰结核矿)，同时制取锰盐和锌盐。该工艺具有反应快速、彻底，工艺流程简单等特点，同时省去了软锰矿的还原焙烧和锌(铅)精矿的氧化焙烧，能够大幅度提高锰、锌(铅)矿的浸出率，对原料矿的品级没有严格要求。     

微波消解-硫酸亚铁铵容量法测定锰矿石中锰的含量

锰矿石试样加磷酸于消化罐中微波消解,溶样完全,不生成焦磷酸盐。加氧化剂后用微波加热氧化,用硫酸亚铁铵标准溶液滴定测定锰的含量。本方法溶样能力强,操作简便,条件易控制,结果准确。     

Simultaneous SO x /NO x removal in a fluidized bed reactor using natural manganese ore

In this experiment, the simultaneous removal of SO₂ and NO from flue gases was investigated through the use of natural manganese ore as a sorbent‐catalyst in a fluidized bed reactor. Selective catalytic reduction behavior was determined as a function of the sulfation degree within the temperature range from 100 °C to 500 °C. The natural manganese ore showed a high activity in the production of nitrogen and water by the reaction of nitric oxide with ammonia and oxygen up to around 200 °C. At higher temperatures, the nitric oxide removal efficiency decreased due to the oxidation of ammonia by oxygen. With the increase of sulfation degree, the temperature at which the maximum selective catalytic reduction of nitric oxide appears gradually increased, however the maximum nitric oxide removal efficiency decreased. Additionally, we investigated the removal efficiency of sulfur dioxide and nitric oxide with reaction time in a batch fluidized bed reactor within a temperature range of 350 °C to 500 °C. As the reaction temperature increased, the adsorption capacity of sulfur dioxide increased, but the nitric oxide removal efficiency decreased. © 2001 Society of Chemical Industry     

Manganese leaching in high concentration flue gas desulfurization process with semi-oxidized manganese ore

Manganese leaching during high concentration flue gas desulfurization process with semi-oxidized manganese ore was studied in this paper. It was found that there were different reaction pathways among which MnO_2,Mn_2O_3 and MnCO_3 in semi-oxidized manganese ore during flue gas desulphurization and manganese leaching.High SO_2 concentration facilitated redox reaction between MnO_2 and SO_2, and high concentration of H_2SO_4 accelerated MnCO_3/Mn_2O_3 leaching from semi-oxidized ore. Kinetics study showed that manganese leaching in flue gas desulfurization process with semi-oxidized ore was controlled by a mixed-control model, that is the surface chemical reaction and mass diffusion dominated both the oxidation of SO_2 and manganese leaching process. The apparent activation energy was 13.05 k J·mol~(-1) and the reaction orders with respect to SO_2 and H_2SO_4 concentration were 1.38 and 0.10, respectively. Finally, a semi-empirical rate equation based on shrinking core model was derived to describe the process.     

利用废锰矿制硫酸锰的研究

采用废锰矿湿法制硫酸锰、用SO2对废锰矿进行硫酸盐化处理，用硫铁矿对废锰矿进行硫酸盐化处理等工艺路线进行实验，利用废锰矿制取硫酸锰，取得了良好的效果。不但使有限的资源得到充分利用，为企业增加经济效益，而且减少了环境污染。     

水合肼法改性天然锰矿及其对苯酚的吸附性能

以广西大新锰矿出产的天然锰矿粉为原料，采取水合肼法进行改性，对工业废水中最常见的苯酚进行吸附实验，并检测其界面吸附能力。结果表明，水合肼法改性的最佳工艺为：5g天然锰矿粉，加入100mL 2mol／L硫酸溶液中，用3mL 2mol／L水合肼作还原剂，沸腾回流30min后，滴加5mL0．05mol／L高锰酸钾，过滤水洗干燥。得到的改性锰矿对苯酚的吸附效果优良，去除率可达75％，且吸附模式遵循Langmuir型吸附。     

铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺

结合电解锰生产工艺,以氧化锰矿为原料,以电解锰生产过程产生的电解阳极液废水配置烟气脱硫浆液,在其中添加FeSO₄强化电解锰阳极液体系下氧化锰矿烟气脱硫及浸锰能力,探讨铁强化氧化锰矿烟气脱硫和浸锰的工艺条件对烟气SO₂脱除和锰浸出的影响机制。研究发现FeSO₄的加入,通过FeSO₄与MnO₂之间的氧化还原反应以及产物三价铁离子和二价锰离子的协同催化作用,可同时提高锰矿烟气脱硫效率和锰的浸出率。锰矿粒径越小,脱硫及浸锰效率越高。温度升高,氧化锰矿浆液烟气脱硫率逐渐下降,浸锰率则先升高后下降,并在60℃时达到最大。浆液液固比和烟气流量的增大均会导致烟气脱硫率的下降,但会提高氧化锰矿浸锰率。进口SO₂浓度过高会导致脱硫率下降,但更有利于浸锰。采用5级逆流吸收对7%的烟气进行铁离子强化氧化锰浆脱硫,得到最终SO₂出口浓度293μL/L,溶液Mn²⁺浓度为44.72g/L,满足电解要求。铁强化电解锰阳极液体系有效回收利用了电解锰生产废水,不仅集脱硫浸锰工艺为一体,且可实现脱硫和浸锰效率的同时提升,为电解锰行业的清洁生产和资源综合利用提供理论依据和技术参考。     

Separation and recovery of iron and manganese from high-iron manganese oxide ores by reduction roasting and magnetic separation technique

Sodium salts were used in the reduction roasting and magnetic separation process to separate and recover iron and manganese from the high-iron manganese oxide ores to utilize the complex ores. Results showed that Na₂S₂O₃ was the most effective salt. A magnetic concentrate with 86.39 wt% TFe and 96.21 wt% Fe recovery as well as a nonmagnetic product with 54.84 wt% TMn and 85.96 wt% Mn recovery was obtained when the ore sample was reduced at 1100°C for 100 min in the presence of 7 wt% Na₂S₂O₃. In addition, the effects of roasting and separation parameters on the recovery of manganese and iron and the function mechanism of Na₂S₂O₃ were investigated.