铁矿石流化还原的气体利用率

通过试验求得铁矿石流化还原的开始失流温度及气体流速对它的影响。通过计算模型及试验数据得到了还原温度及气体流速对气体利用率的影响。结合两方面的工作分析了提高气体利用率的途径,讨论了降低熔融还原工艺总能耗的条件。

脉石对矿粉气基流化还原过程中粘结性能的影响

以智利粉矿为原料,通过磁选去除和添加惰性组分以及球磨等方法,研究并分析了原矿中脉石的含量和分布对其流化还原过程中粘结性能的影响。实验结果表明脉石组分的含量对矿粉高温气基流化还原过程中的粘结性能影响很小,而脉石组分的分布影响较大,矿粉颗粒表面的脉石组分可以很好地抑制粘结失流的发生。力平衡模型分析表明当脉石组分在矿粉颗粒表面的覆盖面积超过一定温度下的临界值时,矿粉就可以实现稳定的流化还原了。进行流化还原及采取适当的措施预防粘结,提供一定的理论依据。

还原条件下煤中硫的转化

在小型流化床实验台上对还原条件下硫化物的生成进行了研究。实验结果表明,还原态条件下燃料中的硫首先生成H2S,以及少量的SO2。作者认为SO2主要是由硫酸盐的分解形成的。H2S产生速率受还原性气氛、有机硫比例以及含氧量的影响很大,还原性越强,有机硫比例越大,含氧量越低产生的H2S越多;H2S产生的速率还与煤中挥发份含量和有机硫含量有关,挥发份含量越高,有机硫含量越低,H2S产生越早;低按发份和低有机硫含量的煤在强还原性气氛下容易生成单质硫。因此,循环流化床的脱硫过程中必须采取有效措施去除燃烧过程中产生的H2S,特别对于燃烧高硫煤种。

Characterization of fluidized reduction roasting of nickel laterite ore under CO/CO_(2)atmosphere

Fluidized reduction roasting is an efficient metallurgical technique.However,its application to nickel laterite ore has rarely been reported.In this paper,the effects of reduction temperature,reduction time,CO concentration,and material particle size on the roasting characteristics of ferronickel fluidization reduction were investigated.Combined with X-ray diffraction,scanning electron microscopy-energy dispersive spectrometry(SEM-EDS)characterization,the mineral phases and microscopic morphology of nickel laterite ore and its roasted ores were analyzed in depth.The results indicated that under the condition of a CO/CO_(2)ratio of 1:1,a reduction temperature of 800℃,and a reduction roasting time of 60 min,a nickel-iron concentrate with a nickel grade of 2.10%and an iron content of 45.96%was produced from a raw material with a nickel grade of 1.45%,achieving a remarkable nickel recovery rate of 46.26%.XRD and SEM-EDS analysis indicated that nickel in the concentrate mainly exists in the form of[Fe,Ni],while the unrecovered nickel in the tailings is primarily present in the form of[Fe,Ni]and Ni_(2)SiO_(4)in forsterite.This study established a theoretical foundation for further exploration of fluidized reduction roasting technology.

过程工程所流化床直接还原技术研究进展

“双碳”背景下,钢铁工业亟待低碳重塑,氢气直接还原(常称为“氢冶金”)是国内外竞相研发的重要方向。流态化直接还原是过程工程所六十多年来一直坚持的研究方向。值此叶渚沛先生诞辰120周年之际,本综述回顾并概述了过程工程所在流态化直接还原基础理论和工业应用两方面所取得的一系列重要成果。基础理论方面包括颗粒间黏着力与分离力相互竞争黏结机制、聚团流化和慢速失流的发现、不同铁形貌析出机理和黏结特性,以及降低颗粒间黏结力(颗粒包覆改性、调控铁析出形貌)和增大颗粒间分离力(增强颗粒运动、增大颗粒尺寸、施加外场力)等一系列抑制黏结失流方法;工业应用方面包括100公斤/天流化床氢气直接还原、1吨/天钒钛磁铁矿流化床直接还原和千吨级钒钛磁铁矿直接还原-电炉熔分等中间试验,目前正在与鞍钢集团等单位合作开展全球首套1万吨直接还原铁/年流化床绿氢直接还原工程示范。谨以此文缅怀叶渚沛先生、郭慕孙先生等老一辈科学家,以期推动流化床直接还原基础理论和技术研发的进步,为钢铁工业低碳重塑贡献智慧和力量。

Boosting catalytic activities of carbon felt electrode towards redox reactions of vanadium ions by defect engineering

Vanadium redox flow batteries(VRFBs)are one of the most promising energy storage systems owing to their safety,efficiency,flexibility and scalability.However,the commercial viability of VRFBs is still hindered by the low electrochemical performance of the available carbon-based electrodes.Defect engineering is a powerful strategy to enhance the redox catalytic activity of carbon-based electrodes for VRFBs.In this paper,uniform carbon defects are introduced on the surfaces of carbon felt(CF)electrode by Ar plasma etching.Together with a higher specific surface area,the Ar plasma treated CF offers additional catalytic sites,allowing faster and more reversible oxidation/reduction reactions of vanadium ions.As a result,the VRFB using plasma treated electrode shows a power density of 1018.3 mW/cm^(2),an energy efficiency(EE)of 84.5%,and the EE remains stable over 1000 cycles.

Evaluation of metal-doped manganese oxide octahedral molecular sieves in catalytic reduction of NO_x from cigarette mainstream smoke

A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NOx from cigarette mainstream smoke.The catalysis and reduction of NO in laboratory were studied.A mechanism for NOx catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described.The catalysts show excellent catalytic activity for NOx removal,especially the Ag-doped OMS-2 catalyst.0.5%(mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NOx from cigarette mainstream smoke.The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.

Effect of Return Sludge Pre-concentration on Biological Phosphorus Removal in a Novel Oxidation Ditch

A pilot-scale,pre-anoxic-anaerobic oxidation ditch was used in this study to treat municipal wastewater with limited carbon source.A novel return activated sludge(RAS) pre-concentration tank was adopted for improv-ing the phosphorus removal efficiency and the effects of RAS pre-concentration ratio were studied.Under the opti-mal operational condition,the suspended total phosphorus(STP) and the total phosphorus(TP) removal efficiencies were around 58.9% and 63.9% respectively and the effluent-P was lower than 0.8 mg·L-1.The reason is that with the optimal RAS pre-concentration ratio,nitrate is completely removed with endogenous carbon source and the secondary phosphorus release is strictly restrained in the pre-anoxic tank.Therefore,the anaerobic phosphorus release and the carbon source uptake by phosphorus accumulation organisms(PAOs) in the sludge,which are ex-tremely important to the phosphorus removal process,can be fully satisfied.Furthermore,the oxidation-reduction potential is proved to be suitable for controlling the RAS pre-concentration ratio due to influent fluctuation and varied conditions.The novel modified system is also beneficial for PAO accumulation.

Separation of alumina and silica from metakaolinite by reduction roasting-alkaline leaching process: Effect of CaSO_(4) and CaO

Limestone(CaCO3),which could promote sulfur fixation,was added to coal gangue during roasting in a circulating fluidized bed(CFB)boiler.CaO and CaSO_(4) were the main Ca-bearing minerals while metakaolinite was the major Al-bearing mineral in CFB slag.The effect of CaSO_(4) and CaO on the separation of alumina and silica from metakaolinite by reduction roasting−alkaline leaching process was studied.Results showed that metakaolinite was completely converted into hercynite and silica solid solutions(i.e.,quartz and cristobalite solid solutions)by reduction roasting with hematite.More than 95%of silica in the reduced specimen was removed by alkaline leaching.The addition of CaSO_(4) and CaO remarkably decreased the separation efficiency of alumina and silica in metakaolinite,which could be attributed to the formation of Si-bearing minerals:(1)Fayalite and anorthite were formed during the reduction roasting process;(2)Fayalite was stable while anorthite was converted into sodalite and wollastonite during the alkaline leaching process.This study demonstrates that sulfur in coal gangue should be fixed by treating the exhaust gas instead of controlling the combustion process of CFB to achieve the comprehensive recovery of silica and alumina from the CFB slag.

Effect of Percolation Pattern on Yields and Accumulation of Copper and Cadmium in the Rice Plants with Soil Dressing Models

A greenhouse experiment was conducted using stratified paddy field models, which were prepared by polluted soil with 12.5 cm soil dressing. The paddy models were assembled with open and closed percolation system to focus the effect of percolation pattern on accumulation of cupper （Cu） and cadmium （Cd） in rice plants in contaminated paddy filed with soil dressing models. Percolation pattern has significant effect on soil environment, especially redox potential that may influence mobilization of Cd, Cu and other elements. In open system percolation models, the plowsole and subsoil were in oxidative condition （600 mV）, whereas reduction condition （-200 mV） was measured in closed system percolation models. Accumulations of Cu and Cd in all parts of rice plants （roots, grains, stems and leaves） were found higher in an open system percolation with the paddy field model comparatively than in a closed system percolation. The soil redox （Eh） condition influenced by the percolation pattern might be one of the main factors for uptake and accumulation of Cu and Cd in rice plants. The plant height and stem number were found lower in open system percolation comparatively to closed system percolation. In the yields section, the average panicle length, number of panicle and rice grain/hill and weight of grain/hill were lower in open system percolation than the closed system percolation.

Ozonation of Sulfur Dioxide in Sulphuric Acid Solution

In this study, the oxidation rates of sulfur dioxide （SO2） in sulphuric acid solution by ozone and oxygen were compared, and the oxidation mechanism of ozone on SO2 was investigated. The results showed that the oxidation-reduction potential of the acidic solution was enhanced, the transformation rate of sulfuric acid to sulphuric acid was increased and the absorption driving force was improved in the presence of ozone. By comparing the amount of sulfate ions measured in the experiments and the theoretical amount of sulfate ions calculated from the amount of ozone consumed in the reaction, it can be confirmed that oxygen free radicals from dissociation of ozone are reactive as an efficient oxidant and oxygen from ozone generator participates in the reaction with SO2. 0.602 mol of effective oxygen was introduced into the reaction by one mole of ozone in 10.15 rain at sulphuric acid concentration of 3% （by mass）, SO2 concentration of 1.33% （by volume） and oxygen flow rate of 1.5 L.min^-1 from ozone generator.

Nitrite Accumulation during the Denitrification Process in SBR for the Treatment of Pre-treated Landfill Leachate

The nitrite accumulation in the denitrification process is investigated with sequencing batch reactor （SBR） treating pre-treated landfill leachate in anoxic/anaerobic up-flow anaerobic sludge bed I（UASB）. Nitrite accumulates obviously at different initial nitrate concentrations （64.9,54.8,49.3 and 29.5 mg·L^-1 ） and low temperatures, and the two break points on the oxidation-reduction potential （ORP） profile indicate the completion of nitrate and nitrite reduction. Usually, the nitrate reduction rate is used as the sole parameter to characterize the denitrification rate, and nitrite is not even measured. For accuracy, the total oxidized nitrogen （nitrate ＋ nitrite） is used as a measure, though details characterizing the process may be overlooked. Additionally, batch tests are conducted to investigate the effects of C/N ratios and types of carbon sources on the nitrite accumulation during the denitrification. It is observed that carbon source is sufficient for the reduction of nitrate to nitrite, but for further reduction of nitrite to nitrogen gas, is deficient when C/N is below the theoretical critical level of 3.75 based on the stoichiometry of denitrification. Five carbon sources used in this work, except for glucose, may cause the nitrite accumulation. From experimental results and cited literature, it is concluded that Alcaligene species may be contained in the SBR activated-sludge system.

Verification of Levich Law-Determination of Hydrogen Currents during Calcareous Deposition

The complexity of calcareous deposits processes in a marine environment results in simultaneous effects of the following parameters： temperature, polarization potential, interfacial pH, chemical composition, etc.. The comprehension of these processes implies studies in artificial seawater and a follow-up of the parameters by voltarnperometry and chronoamperometry. Calcareous deposits electrochemically are very often used to follow up the evolution of scale deposition in desalination circuits. Again, the scale formation is brought about by electrochemical reduction of dissolved oxygen. The hydroxyl ions formed on the metallic surface engender a rise of interfacial pH which causes calcareous deposition （CaCOs and Mg（OH）2）. This reaction goes with reaction of hydrogen evolution which could disrupt the formed deposit, A study is carried out in a solution of seawater ASTM without calcium and without magnesium （so that the deposit will not be formed） on a titanium rotating disk electrode monitored between 300 and 1000 rpm. Study shows that Levich criterion is checked for the four values of selected potential on the diffusion plateau and a very cathodic polarization potential and a high temperature favors hydrogen current rate.

“Electron collector”Bi_(19)S_(27)Br_(3)nanorod‐enclosed BiOBr nanosheet for efficient CO_(2) photoconversion

Although CO_(2)photoreduction is a promising method for solar‐to‐fuel conversion,it suffers from low charge transfer efficiency of the photocatalysts.To improve the CO_(2)photoreduction performance,introduction of electron‐accumulated materials on the photocatalyst surface is considered an effective method.In this study,the Bi_(19)S_(27)Br_(3)/BiOBr composites were designed and synthesized.The Bi19S27Br3 nanorod in this photocatalytic system acts as an electron‐accumulated active site for extracting the photogenerated electrons on the BiOBr surface and for effectively activating the CO2 molecules.As a result,Bi_(19)S_(27)Br_(3)/BiOBr composites exhibit the higher charge carrier transfer efficiency and further improves the CO_(2)photoreduction performance relative to that of pure Bi_(19)S_(27)Br_(3)and BiOBr.The rate of CO formation using Bi_(19)S_(27)Br_(3)/BiOBr‐5 is about 8.74 and 2.40 times that using Bi_(19)S_(27)Br_(3)and BiOBr,respectively.This work provides new insights for the application of Bi_(19)S_(27)Br_(3)as an electron‐accumulating site for achieving high photocatalytic CO2 reduction performance in the future.

Electrochemical Energy Storage Technologies and Applications

The current need to fasten the implementation of renewable energies greatly depends on the development of competitive storage devices, and while there is not a single technology which is likely capable to competitively cover the wide range of possible demands, electrochemical technologies are one of the most promising for many of them. For the realization of this promise, new materials fulfilling criteria such as high energy density, high power density, competitive cost, reliability, and environmental compatibility need to be developed in the near future. Electrochemical energy storage devices can be classified into two main technologies： supercapacitors and batteries （including redox flow batteries）. Materials and applications for these technologies are discussed and compared, listing current status, technical and strategic challenges.

铁矿粉预还原强化实验研究

考察了600℃下50vol.%CO^50vol.%CO2中铁氧化物还原和CaO碳酸化耦合后的流化反应性能,并通过对比实验分析了耦合反应的优越性,得到如下结论:CaO/MgO粉末在流化床内600℃下50vol.%CO^50vol.%CO2气氛中可以很好地吸收CO2,CaO/MgO可以通过原位吸收流化气和产物气中的CO2来提高矿粉中Fe3O4到FeO的还原速率,CaO/MgO的强化作用优于其他方法,且可以通过热磁选循环利用。

添加纳米二氧化硅对氧化铁颗粒表观黏度的影响

借鉴流体黏性的表征方式,引入粉体颗粒表观黏度的概念表征粉体颗粒间的相互作用力,基于能量耗散原理,利用旋转黏度计测定了含SiO2纳米添加剂的Fe2O3颗粒在不同温度条件下的表观黏度.实验结果表明,Fe2O3颗粒表观黏度随温度升高而增大,纳米SiO2的加入使颗粒表观黏度明显降低,主要原因是纳米SiO2对Fe2O3颗粒形成了包覆,抑制了颗粒间的团聚和烧结.此外,本研究利用微型流化床研究了含纳米SiO2的Fe2O3颗粒在流化还原过程中发生黏结失流的过程,进一步验证了纳米SiO2对Fe2O3颗粒表观黏度的影响.结果表明,加入纳米SiO2显著提高了还原样品的金属化率,延长了还原过程中的黏结时间;扫描电镜分析表明纳米SiO2有效包覆在Fe2O3颗粒表面,降低了铁原子的扩散活性,并充分阻隔新鲜铁之间的接触,抑制新鲜铁的烧结,从而导致Fe2O3颗粒之间难以形成黏结点,由此证明纳米SiO2对流化床内Fe2O3颗粒的还原过程中的黏结失流具有明显抑制作用.

In-situ electropolymerized bipolar organic cathode for stable and high-rate lithium-ion batteries

To address the dissolution issue and enhance the electrochemical performance of organic electrode materials,herein, a bipolar organic cathode was prepared by in-situ electropolymerization of amino-phenyl carbazole naphthalene diimide(APCNDI). APCNDI is composed of n-type 1,4,5,8-naphthalene tetracarboxylic diimide that stores Li cations and p-type carbazole groups which react with anions and serve as polymerization sites. Electropolymerization completely eliminated the dissolution problem of APCNDI, and the electropolymerized cathode demonstrated a bipolar reaction with excellent electrochemical performance, stable cycling performance with a capacity retention of 92 mA h g;after1000 cycles, and a superior rate performance of 72 mA h g;at 10 A g;. The bipolar feature and reactions of APCNDI were systematically investigated and verified by multiple characterization techniques. Our findings provide a novel strategy for the design and fabrication of electrodes for high-performance organic batteries.

Coherent Mn3O4-carbon nanocomposites with enhanced energy-storage capacitance

Nanostructured Mn3O4 was introduced to activated C （AC） by a novel sonochemical reaction, and the resulting nanocomposites were examined as supercapacitor electrodes. The sonication not only catalyzed the redox reaction but also promoted the diffusion of the precursors, causing the formation of coherent nanocomposites with Mn3O4 nanoparticles grown and uniformly distributed inside the mesopores of the AC. In addition, the extreme local condition in the sonochemical synthesis yielded an excessive amount of divalent manganese ions and oxygen vacancies. This novel microstructure endowed the sample with a superior performance, including a specific capacitance of 150 F/g compared with the value of 93 F/g for AC at a charge/discharge rate of 100 mA/g. A Li-ion capacitor delivered an energy density of 68 Wh/kg, compared with 41 Wh/kg for the AC capacitor at a power density of 210 W/kg.