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.     

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.     

微生物燃料电池用于低品位锰矿浸提的研究

为提高低品位锰矿的利用,实现有机废水对锰矿物粉的浸提,通过改造微生物燃料电池(MFC),在阴极反应池中增加电解室及矿物质室,构建用于锰矿湿法浸提的MFC反应器,实现有机废水与锰矿物粉的还原氧化反应的分离。结果显示,以乙酸钠为碳源,以低品位锰矿粉为阴极的MFC输出电压最高可达0.81 V,是以K₃[Fe(CN)₆]为阴极液(0.631 V)的1.23倍。在相同条件下,矿物浸提MFC对COD的去除率可达90.9%,高于对照组(87.5%),而降解时间为3 d,显著少于对照组(5.2 d)。在降解COD能力的提升上,可实现对低品位锰矿粉中MnO₂的还原,其锰含量由原矿粉的23%降至0.98%,浸提率可达95.7%。进一步通过高通量测序对阳极端菌群结构进行分析发现,其主要菌群为地杆菌属(Geobacter),相对于对照组的85%,矿物浸提MFC中该属比例占总菌群的95%。结果表明,矿物浸提MFC可有效地将有机降解与矿物浸提耦合,避免两者直接混合反应带来的二次废水污染及浸提产物硫酸锰的净化问题,在提高MFC产电效率、处理废水的同时,实现对低品位锰矿的浸提。     

Direct electrodeposition of ionic liquid-based template-free SnCo alloy nanowires as an anode for Li-ion batteries

SnCo alloy nanowires were successfully electrodeposited from SnCl₂-CoCl₂-1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid without a template. The nanowires were obtained from the molar ratio of 5:40:60 for SnCl₂:CoCl₂:EMIC at -0.55 V and showed a minimum diameter of about 50 nm and lengths of over 20 μm. The as-fabricated SnCo nanowires were about 70 nm in diameter and featured a Sn/Co weight ratio of 3.85:1, when used as an anode for a Li-ion battery, they presented respective specific capacities of 687 and 678 mAh·g-1 after the first charge and discharge cycle and maintained capacities of about 654 mAh·g-1 after 60 cycles and 539 mAh·g-1 after 80 cycles at a current density of 300 mA·g-1. Both the nanowire structure and presence of elemental Co helped buffer large volume changes in the Sn anode during charging and discharging to a certain extent, thereby improving the cycling performance of the Sn anode.     

An improved implementable process for the synthesis of zeolite 4A from bauxite tailings and its Cr<Superscript>3+</Superscript> removal capacity

A simple and practical method for the synthesis of zeolite 4A from bauxite tailings is presented in this paper. Systematic investigations were carried out regarding the capacity of zeolite 4A to remove Cr(Ⅲ) from aqueous solutions with relatively low initial concentrations of Cr(Ⅲ) (5–100 mg·L-1). It is found that the new method is extremely cost-effective and can significantly contribute in decreasing environmental pollution caused by the dumping of bauxite tailings. The Cr(Ⅲ) removal capacity highly depends on the initial pH value and concentration of Cr(Ⅲ) in the solution. The maximum removal capacity of Cr(Ⅲ) was evaluated to be 85.1 mg·g-1 for zeolite 4A, measured at an initial pH value of 4 and an initial Cr(Ⅲ) concentration of 5 mg·L-1. This approach enables a higher removal capacity at lower concentrations of Cr(Ⅲ), which is a clear advantage over the chemical precipitation method. The removal mechanism of Cr(Ⅲ) by zeolite 4A was examined. The results suggest that both ion exchange and the surface adsorption-crystallization reaction are critical steps. These two steps collectively resulted in the high removal capacity of zeolite 4A to remove Cr(Ⅲ).     

广西伊岭岩岩石(CaCO3)晶体结构、德拜温度以及硬度研究

本文从微观角度研究碳酸钙矿石的晶体结构与物理性能,为碳酸钙矿石的应用提供理论依据。利用X射线衍射(XRD)技术分析广西伊岭岩岩石2个样品(A_1、A_2)的相组成及其晶体结构,并利用带能谱仪的电子显微镜(SEM/EDS)测试这2个样品的各相成分。结果表明:广西伊岭岩岩石的主要成分为CaCO_3,其中A_1样品含有少量的K~+,A_2样品含有少量Na~+。通过Rietveld全谱图拟合晶体结构精修可知,K~+替代样品A_1主要物相CaCO_3中的Ca~(2+),使其点阵参数变大,单胞体积变大。同样A_2样品中的Na~+替代了样品中CaCO_3的Ca~(2+)位置,造成A_2中的CaCO_3点阵参数变小,单胞体积变小。德拜温度近似模型计算出2个样品的德拜温度分别为318.86K、324.82K。维氏硬度测试法测试出2个样品的硬度大小分别为132.6HV、148.9HV。     

用钛钌阳极从氯化锰溶液电解二氧化锰的研究

为了研究在氯盐溶液中用钛钌阳极电解二氧化锰的新技术,运用恒流水溶液电解方法考察了电解温度、电流密度和电解液组成对二氧化锰电流效率、槽电压及产品质量的影响.试验结果表明,在电解温度75℃、电流密度100 A/m2、锰离子质量浓度50 g/L、盐酸质量浓度10 g/L的条件下,二氧化锰的电流效率达96%,槽电压为2.0 V,产品中二氧化锰的含量为92.32%,电解二氧化锰晶型为γ型.通过在氯盐溶液中用钛钌阳极电解二氧化锰,不仅产品质量能达到电池用电解二氧化锰标准,而且电解温度低(75℃),优于硫酸盐溶液体系(95℃).     

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO₃2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO₃2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO₃2- (HCO₃-) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.     

Improving the sulfidation-flotation of fine cuprite by hydrophobic flocculation pretreatment

Hydrophobic flocculation pretreatment was performed to assess its effect on the recovery of fine cuprite in sulfidation-flotation. The results of the micro-flotation experiment showed that cuprite recovery is related to the particle size, and that an excessive content of fine particles (<18 μm) impacted the recovery of coarse particles. When hydrophobic flocculation pretreatment was used, the recovery of fine cuprite in sulfidation-flotation increased from 60.3% to 86.3% under optimum conditions (pH 9.5; sodium oleate concentration, 2×10-4 mol·L-1; stirring time, 6 min; stirring speed, 1600 r·min-1). The laser particle size analysis and optical microscopy results indicate that hydrophobic flocculation pretreatment effectively reduces the content of fine cuprite, and augments the apparent particle size in the pulp. We performed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and extended DLVO theory calculations to further support the interpretation of the results.     

Effect of exogenous lanthanum on accumulation of cadmium and its chemical form in Tomatoes

In the condition that soil is polluted by Cd(20 mg·L-1),two varieties of tomato(Lycopersicon esculintum Mill.)(plant high Cd-enriched variety(Yufen109)and plant low Cd-enriched variety(4641))treated with LaCl3 of different concentration(0,10 and 20mg·L-1)were determined for their effect on plant dry weight,anti-oxidase activity(CAT,SOD and POD),tomato fruit Cd chemical form and Cd accumulation.The results show that 10 mg?L-1LaCl3 can increase dry weight of plant at various positions and can reduce the concentration of Cd of different forms.Spraying with LaCl3(10,20 mg·L-1)can reduce Cd concentration in leaves,stems,roots and fruits of tomato plants with lowering rates of 13.7%-31.9%,9.5%-30.6%,10.8%-44.5%and 19.4%-37.0%,respectively.Suitable amount of lanthanum(10 mg·L-1 LaCl3)can increase yield of tomatoes,reduce Cd accumulation in the fruit.In the two tomato varieties,Lanthanum and Cadmium react interactively,expressing to be coexisting of both synergism and antagonistic.     

Discovery of the superlarge gallium ore deposit in Jungar, Inner Mongolia, North China

Gallium, Ge, V, and U are the associated valuable elements in coal. From the 1950s to the 1970s, some researchers in the departments of coal industry and mineral resources of China investigated these elements in coal during geological explorations. The enrichment mechanism and the environmental influence of trace elements in coal have been deeply studied in recent twenty years. With respect to the ore-forming theories and practical utilizations of metals in coal, germanium was furthest studi…     

Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore: gold flotation–gold concentrate leaching–lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concentrate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue—preferential flotation of lead and zinc and bulk flotation of lead and zinc—were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead–zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.     

Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

Carbon-coated LiFePO₄ hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller specific surface area analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO₄ hollow nanofibers have good long-term cycling performance and good rate capability: at a current density of 0.2C (1.0C = 170 mA·g-1) in the voltage range of 2.5–4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g-1 with a first charge–discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99% after 10 cycles; moreover, the materials can retain a specific capacity of 135.68 mAh·g-1, even at 2C.     

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.     

沉淀法对聚合醇钻井液使用中的消泡研究

通过对所用聚合醇防塌钻井液进行消泡研究,在基浆中添加无水碳酸钠,向一定量的聚硅氧烷消泡剂X-4050中加入氯化镁溶液,用仅占HEL-40用量的2％即可迅速消泡,11 000 r·min-1×5 min后起泡率仅为6％,应用于实际井浆中11 000 r· min-1×20 min后起泡率为0％,大大降低消泡剂的用量.     

共沉淀法制备镁锰双金属氢氧化物及表征

以氯化镁、氯化锰、氢氧化钠及碳酸钠为原料,采用共沉淀法合成镁锰双金属氢氧化物(Mg-Mn-LDH).探讨镁锰摩尔比、反应温度、反应时间等条件对镁锰双金属氢氧化物(Mg-Mn-LDH)结晶性的影响.通过XRD和SEM对产物结晶性、组成结构等进行表征.实验结果表明,在镁锰摩尔比3∶1、反应温度40℃、反应3h、长陈化时间和反应体系pH 13下,制备出的产物的结晶性最好,层状结构也最清晰.     

人工栽培金银花的生物量和元素含量测定及其经济效益估算

采集广西忻城县红渡镇金银花(Lonicera quaponica)种植示范区人工栽培3年生的金银花样品,测定生物量及各器官的主要元素含量,并估算金银花的经济效益.结果表明,金银花的生物生产力是藤茎(0.79t·hm-2·a-1)＞叶子(0.40t·hm-2·a-1)＞根(0.33 t·hm-2·a-1)＞花(0.30 t·hm-2·a-1);金银花的主要元素(N、P、K)平均含量显示花(5.68 kg·hm-2)＞叶子(4.60kg·hm-2)＞藤茎(3.06kg·hm-2)＞根(2.93 t·hm-2);金银花年均产干花1.78 t·hm-2,年均经济收入每公顷35600元.     

两种芳胺基团修饰的螺二芴衍生物在有机电致发光材料及荧光探针中的应用

通过在螺二芴上引入芳胺基团制备出两种全新的螺二芴衍生物SPF-1和SPF-2.化合物SPF-1能够通过荧光强度检测有机溶剂中的含水量.其中,SPF-1在1,4-二氧六环中对水的检测限达到0.018％,在四氢呋喃（THF）中对水的检测限达到0.049％,结果优于大多数文献的报道.另外,SPF-1和SPF-2都可用作有机电致发光（EL）器件的发射层材料.SPF-1制备的器件在506 nm附近有强的发射峰,色度坐标为（0.24,0.48）;SPF-2制备的器件在471 nm和502 nm处有较强发射,色度坐标为（0.31,0.54）.两个器件都具有低开启电压、高热稳定性等优异性能.其中SPF-1的最大亮度、最大电流效率和最大功率效率分别为1 653 cd·m^-2,2.55 cd·A^-1和1.23 lm·W^-1,SPF-2的最大亮度、最大电流效率和最大功率效率为是1 660 cd·m^-2,2.1 cd·A^-1和1.28 lm·W^-1.     

Carrier transport characteristics of H-terminated diamond films prepared using molecular hydrogen and atomic hydrogen

The H-terminated diamond films, which exhibit high surface conductivity, have been used in high-frequency and high-power electronic devices. In this paper, the surface conductive channel on specimens from the same diamond film was obtained by hydrogen plasma treatment and by heating under a hydrogen atmosphere, respectively, and the surface carrier transport characteristics of both samples were compared and evaluated. The results show that the carrier mobility and carrier density of the sample treated by hydrogen plasma are 15 cm2·V-1·s-1 and greater than 5×1012 cm-2, respectively, and that the carrier mobilities measured at five different areas are similar. Compared to the hydrogen-plasma-treated specimen, the thermally hydrogenated specimen exhibits a lower surface conductivity, a carrier density one order of magnitude lower, and a carrier mobility that varies from 2 to 33 cm2·V-1·s-1. The activated hydrogen atoms restructure the diamond surface, remove the scratches, and passivate the surface states via the etching effect during the hydrogen plasma treatment process, which maintains a higher carrier density and a more stable carrier mobility.     

Synergistic interaction and gelation in cationic guar gum-sodium alginate system

The synergistic interaction between the cationic guar gum (the ammonium hydroxy-propyl-trimethyl chloride of guar gum) and sodium algirmte has been studied. The effects of the mass ratio of them, mixed temperature, balk salt ion concentration, incubation time and pH value on gelation were investigated. It has been observed that there was a gel strength maximum when the mass ratio was 0. 6, the mixed temperature was 70 ~C, the balk salt ion concentration was 1.0 mol ~ L-1 , the incubation time was 30 rain and the pH value was 8. Interaction between molecules of these two polysaccharides was investigated by FT-IR spectrometry.