生物质焦焙烧还原低品位软锰矿及其动力学

采用生物质焦和活性炭粉作还原剂,在管式炉中进行了低品位软锰矿焙烧还原对比试验.分别研究了焙烧温度、焙烧时间、生物质焦用量等条件对软锰矿还原率的影响,对焙烧产物进行了X射线衍射分析.结果表明,生物质焦在焙烧时间和还原效率上优于活性炭粉;软锰矿焙烧还原依次经历Mn O2→Mn2O3→Mn3O4→Mn O过程;在焙烧温度为800℃,焙烧时间为50 min,生物质焦用量为10%时,软锰矿还原率可达98%以上,在此基础上导出了还原动力学方程,并证实还原过程由界面化学反应控制,表观活化能为43.896 k J·mol-1.     

Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese (Mn) leaching and recovery from low-grade pyrolusite ore were studied using sulfuric acid (H₂SO₄) as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were investigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H₂SO₄ using a liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

低品位软锰矿流态化还原焙烧

采用流化床和马弗炉,进行了流态化还原焙烧与静态堆积焙烧对比实验,前者还原焙烧时间和还原效率明显优于后者．以CO和N2分别作为还原气体和流体介质进行了流态化还原焙烧实验,考察焙烧温度、焙烧时间和还原气氛等对还原效率的影响．在焙烧温度800℃、焙烧时间3min以及CO体积分数10％时,软锰矿中二氧化锰的还原效率大于97％．在此基础上导出了还原动力学方程,并证实还原过程由界面化学反应控制,求得表观活化能为38．817kJ·mol^-1.     

Effects of the mineral phase and valence of vanadium on vanadium extraction from stone coal

The influence of roasting on the leaching rate and valence of vanadium was evaluated during vanadium extraction from stone coal. Vanadium in stone coal is hard to be leached and the leaching rate is less than 10% when the raw ore is leached by 4 mol/L H₂SO₄ at 90℃ for 2 h. After the sample is roasted at 900℃ for 2 h, the leaching rate of vanadium reaches the maximum, and more than 70% of vanadium can be leached. The crystal of vanadium-bearing mica minerals decomposes and the content of V(V) increases with the rise of roasting temperature from 600 to 900℃, therefore the leaching rate of vanadium increases significantly with the decomposition of the mica minerals. Some new phases, anorthite for example, form when the roasting temperature reaches 1000℃. A part of vanadium may be enwrapped in the sintered materials and newly formed phases, which may impede the oxidation of low valent vanadium and make the leaching rate of vanadium drop dramatically. The leaching rate of vanadium is not only determined by the valence state of vanadium but also controlled by the decomposition of vanadium-bearing minerals and the existence state of vanadium to a large extent.     

碳质石煤与生物质混合焙烧过程的热分析研究

以湖北襄樊的碳质石煤为原料，通过热力学理论分析和热分析实验对石煤与生物质混合共焙烧过程进行研究。结果发现：混合焙烧过程中，各种物质反应的先后顺序为有机质的氧化反应→黄铁矿的氧化反应→钒的氧化反应；生物质的加入为打破石煤中的云母晶格提供了大量的热量，使石煤中的还原性物质反应温度降低且反应时间缩短，对石煤的脱碳与焙烧起相应的促进作用。     

Extraction of vanadium from high calcium vanadium slag using direct roasting and soda leaching

The extraction of vanadium from high calcium vanadium slag was attempted by direct roasting and soda leaching. The oxidation process of the vanadium slag at different temperatures was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The effects of roasting temperature, roasting time, Na₂CO₃ concentration, leaching temperature, leaching time, and liquid to solid ratio on the extraction of vanadium were studied. The results showed that olivine phases and spinel phases in the vanadium slag were completely decomposed at 500 and 800℃, respectively. Vanadium-rich phases were formed at above 850℃. The leaching rate of vanadium reached above 90% under the optimum conditions:roasting temperature of 850℃, roasting time of 60 min, Na₂CO₃ concentration of 160 g/L, leaching temperature of 95℃, leaching time of 150 min, and liquid to solid ratio of 10:1 mL/g. The main impurities were Si and P in the leach liquor.     

利用低品位软锰矿制备硫酸锰的工艺进展

介绍了目前利用低品位软锰矿制备硫酸锰的工艺现状以及目前正在开发的工艺,并且简述了它们的优缺点。对低品位软锰矿资源的开发利用具有一定的指导意义。     

含锌电炉粉尘配碳球团的冶金特性

以某钢铁公司含锌电炉粉尘为原料,配入适当的无烟煤制成含碳球团,焙烧球团通过还原煤保护冷却至室温后进行化学分析·研究了1150℃～1300℃的范围内,温度、时间和内配煤量对锌、铁的还原速率以及球团抗压强度的影响·研究结果表明:锌、铁的还原率均随焙烧温度、焙烧时间以及内配煤量的增加而提高;抗压强度随焙烧温度、焙烧时间的增加而增高,但随内配煤量的增加出现极值点·焙烧球团最佳的工艺参数:焙烧时间为15min,内配煤量为13 04%,焙烧温度为1250℃·此时锌的还原率为98 43%,金属化率为94 51%,抗压强度为800 6N/球·     

Recovery of valuable metals from a low-grade nickel ore using an ammonium sulfate roasting-leaching process

Metal leaching from a low-grade nickel ore was investigated using an ammonium sulfate roasting-water leaching process. The nickel ore was mixed with ammonium sulfate, followed by roasting and finally leaching with water. During the process the effects of the amount of ammonium sulfate, roasting temperature, and roasting time on the leaching recovery of metal elements were analyzed. The optimum technological parameters were determined as follows:ammonium sulfate/ore ratio, 0.8 g/g; roasting temperature, 400℃; and roasting time, 2 h. Under the optimum condition the leaching recoveries of Ni, Cu, Fe, and Mg were 83.48%, 76.24%, 56.43%, and 62.15%, respectively. Furthermore, the dissolution kinetics of Ni and Mg from the nickel ore was studied. The apparent activation energies for the leaching reaction of Ni and Mg were 18.782 and 10.038 kJ·mol-1, which were consistent with the values of diffusion control reactions. Therefore, the results demonstrated that the leaching recoveries of Ni and Mg were controlled by diffusion.     

用硫酸亚铁浸出同时沉淀铁矾法处理低品位锰矿

研究了用硫酸亚铁浸出同时沉淀黄钠铁矾的方法处理低品位软锰矿的过程．在该过程中,软锰矿中的ＭｎＯ２被还原成ＭｎＳＯ４同时ＦｅＳＯ４被氧化并以黄钠铁矾的形态沉淀．沉淀产生的酸可直接用于ＭｎＯ２浸出．考察了硫酸、硫酸亚铁和硫酸钠的加入量及温度等参数对锰浸出和沉铁效率的影响．讨论了过程动力学．实验结果表明,锰浸出率和沉铁效率（质量分数）在最佳条件下可分别达到９６％和９２％．     

Metalizing reduction and magnetic separation of vanadium titano-magnetite based on hot briquetting

To achieve high efficiency utilization of Panzhihua vanadium titano-magnetite, a new process of metalizing reduction and magnetic separation based on hot briquetting is proposed, and factors that affect the cold strength of the hot-briquetting products and the efficiency of reduction and magnetic separation are successively investigated through laboratory experiments. The relevant mechanisms are elucidated on the basis of microstructural observations. Experimental results show that the optimal process parameters for hot briquetting include a hot briquetting temperature of 475℃, a carbon ratio of 1.2, ore and coal particle sizes of less than 74 μm. Additionally, with respect to metalizing reduction and magnetic separation, the rational parameters include a magnetic field intensity of 50 mT, a reduction temperature of 1350℃, a reduction time of 60 min, and a carbon ratio of 1.2. Under these above conditions, the crushing strength of the hot-briquetting agglomerates is 1480 N, and the recovery ratios of iron, vanadium, and titanium are as high as 91.19%, 61.82%, and 85.31%, respectively. The new process of metalizing reduction and magnetic separation based on hot briquetting demonstrates the evident technological advantages of high efficiency separation of iron from other valuable elements in the vanadium titano-magnetite.     

生物质松木锯末中低温还原高铁拜耳法赤泥

对生物质松木锯末和烟煤还原焙烧高铁拜耳法赤泥进行对比试验研究,包括还原温度、还原时间、还原剂用量对还原效果的影响.生物质松木锯末还原高铁拜耳法赤泥所需还原温度低而且还原时间短最终还原效果较好.试验通过热分析和X射线衍射、动力学研究结果揭示出生物质松木锯末中低温还原高铁拜耳法赤泥机理.同时确定了生物质松木锯末中低温还原的最佳还原条件.研究表明生物质松木锯末为赤泥质量分数的20%,还原温度为650℃,还原时间为30 min可将赤泥完全磁化.生物质松木锯末热重试验分析表明250~375℃温度区间为锯末热解的主要阶段,350℃左右热解速率达到最大,450℃后热解反应趋于平缓;烟煤热重试验表明300~700℃温度区间为烟煤热解的主要阶段,450℃左右热解速率达到最大,650℃后热解反应趋于平缓.动力学研究表明锯末在300~400℃区间热解表观活化能比烟煤热解表观活化能要低很多,说明在此温度范围内锯末比烟煤更加容易发生热解反应.生物质能够中低温还原高铁拜耳法赤泥,还原温度比煤基还原的还原温度低200℃左右.     

Comprehensive recovery of lead,zinc, and iron from hazardous jarosite residues using direct reduction followed by magnetic separation

Lead, zinc, and iron were recovered from jarosite residues using direct reduction followed by magnetic separation. The influence of the coal dosage, reduction temperature, and reduction time on the volatilization rates of lead and zinc and the metallization rate of iron were investigated. The results show that the volatilization rates of lead and zinc were 96.97% and 99.89%, respectively, and the iron metallization rate was 91.97% under the optimal reduction roasting conditions of a coal dosage of 25.0wt% and reduction roasting at 1250℃ for 60 min. The magnetic concentrate with an iron content of 90.59wt% and an iron recovery rate of 50.87% was obtained under the optimum conditions in which 96.56% of the reduction product particles were smaller than 37 μm and the magnetic field strength was 24 kA/m. Therefore, the results of this study demonstrate that recovering valuable metals such as lead, zinc, and iron from jarosite residues is feasible using the developed approach.     

芦丁还原浸出低品位软锰矿的研究

为了研究糖蜜酒精废液中有机物还原浸出软锰矿的机理,采用芦丁为还原剂,在酸性介质中直接浸出低品位软锰矿。通过正交实验和单因素实验,研究了芦丁浓度、硫酸浓度、反应温度、浸出时间等因素对锰浸出率的影响,并对反应过程机理进行了初步探讨。实验结果表明,影响锰浸出率的主要因素依次为反应温度、硫酸浓度、浸出时间和芦丁浓度;当硫酸初始浓度2.35 mol/L,芦丁初始浓度0.041 mol/L,反应温度90℃,浸出时间90 m in时,锰浸出率达94.9%。     

赤铁矿石隧道窑直接还原助还原剂的作用及机理

对隧道窑直接还原焙烧--磁选法处理低品位难选赤铁矿石进行了探讨,重点研究助还原剂NCP的作用及机理.以煤作还原剂,质量分数为20%,CCO和NCP为助还原剂,质量分数分别为15%和5%,在焙烧温度为1200℃,焙烧时间为8 h的条件下,可以得到铁品位92.61%、铁回收率92.38%的铁精矿.利用X射线衍射和扫描电镜对助还原剂NCP的作用机理进行分析.结果表明NCP可以与原矿中石英发生反应,生成硅钠石和钠长石,破坏原矿结构,使还原性气体更易与赤铁矿接触发生还原反应生成金属铁.     

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

白云鄂博尾矿一步法焙烧实验研究

采用差热分析(TG-DTA)和X射线衍射(XRD)方法研究了C-Ca(OH)₂-NaOH体系焙烧白云鄂博尾矿的过程,考察了焙烧温度、焙烧时间、煤用量、Ca(OH)₂用量及NaOH用量对尾矿中稀土矿分解和赤铁矿还原的影响.结果表明:在焙烧温度为650℃,焙烧时间为60min,煤加入量为2%,Ca(OH)₂加入量为4%,NaOH加入量为2%的条件下,赤铁矿可以有效地还原为磁铁矿,还原磁化率为2.37;同时,稀土矿有效地分解成稀土氧化物,稀土浸出率达98.39%.     

两矿干法制取工业硫酸锰的实验研究

通过实验，探索利用软锰矿和硫铁矿经硫酸化焙烧、浸取等工序制取工业硫酸锰的生产工艺条件，并对 原料消耗定额、总锰利用率及产品质量等方面进行了分析研究。     

Reductive recovery of manganese from low-grade manganese dioxide ore using toxic nitrocellulose acid wastewater as reductant

The hydrometallurgical strategy of extracting Mn from low-grade Mn ores has attracted attention for the production of electrolytic manganese metal (EMM). In this work, the reductive dissolution of low-grade MnO₂ ores using toxic nitrocellulose acidic wastewater (NAW) as a reductant was investigated for the first time. Under the optimized conditions of an MnO₂ ore dosage of 100 g·L-1, an ore particle size of -200 mesh, concentrated H₂SO₄-to-NAW volume ratio of 0.12, reaction temperature of 90℃, stirring speed at 160 r·min-1, and a contact time of 120 min, the reductive leaching efficiency of Mn and the total organic carbon (TOC) removal efficiency of NAW reached 97.4% and 98.5%, respectively. The residual TOC of 31.6 mg·L-1 did not adversely affect the preparation of EMM. The current process offers a feasible route for the concurrent realization of the reductive leaching of Mn and the treatment of toxic wastewater via a simple one-step process.     

Utilization of waste polyethylene terephthalate as a reducing agent in the reduction of iron ore composite pellets

The increasing consumption of plastics inevitably results in increasing amounts of waste plastics. Because of their long degradation periods, these wastes negatively affect the natural environment. Numerous studies have been conducted to recycle and eliminate waste plastics. The potential for recycling waste plastics in the iron and steel industry has been underestimated; the high C and H contents of plastics may make them suitable as alternative reductants in the reduction process of iron ore. This study aims to substitute plastic wastes for coal in reduction melting process and to investigate their performance during reduction at high temperature. We used a common type of waste plastic, polyethylene terephthalate (PET), because of its high carbon and hydrogen contents. Composite pellets containing PET wastes, coke, and magnetite iron ore were reduced at selected temperatures of 1400 and 1450°C for reduction time from 2 to 10 min to investigate the reduction melting behavior of these pellets. The results showed that an increased temperature and reduction time increased the reduction ratio of the pellets. The optimum experimental conditions for obtaining metallic iron (iron nuggets) were reduction at 1450°C for 10 min using composite pellets containing 60% PET and 40% coke.