Electrochemical reduction process of Co(Ⅱ) in citrate solution

Effects of citrate concentration and pH on the electrochemical reduction process of Co（Ⅱ） were investigated by cyclic voltammetry（CV） and electrochemical impedance spectroscopy（EIS）. The results show that Co（Ⅱ） is reduced into two species which are free Co2＋ and [Co（C6H607）] in the solution composed of 0.05 mol/L CoS04·5H2O, 0.20 mol/L Na2SO4 and 0-0.40 mol/L C6H5O7Na3·2H2O in the pH range of 3-9. The reduction behavior depends on the pH of the solution. Co（H） is mainly reduced into the form of free Co^2＋ at pH 3 and into the form of [Co（C6H6O7）] at the pH range of 4-6 in citrate solution. The [Co（C6H6O7）] is first reduced to an intermediate state and then to Co°. Adsorption of the intermediate state exists on the surface of the electrode. Co（Ⅱ） is difficult to be reduced in the solution with the pH above 7, because the existing Co（Ⅱ）-citrate complex species [Co（C6H5O7）]- and [Co（C6H4O7）]2- are more difficult to be reduced than the hydrogen ion.

Microwave enhanced chemical reduction process for nitrite-containing wastewater treatment using sulfaminic acid

High-concentration nitrite-containing wastewater that presents extreme toxicity to human health and organisms is difficult to be treated using traditional biological process. In this study, a novel microwave-enhanced chemical reduction process （MECRP） using sulfarninic acid （SA） was proposed as a new manner to treat such type of wastewater. Based on lab-scale experiments, it was shown that 75%-80% nitrite （NO2-） could be removed within time as short as 4 min under 50 W microwave irradiation in pH range 5-10 when molar ratio of SA to nitrite （SA/NO2-） was 0.8. Pilot-scale investigations demonstrated that MECRP was able to achieve nitrite and chemical oxygen demand （COD） removal with efficiency up to 80% and 20%, respectively under operating conditions of SA concentration 80 kg/m3, SA/NO2- ratio 0.8, microwave power 3.4 kW, and stirring time 3 min. Five-day biological oxygen demand （BODs）/COD value of treated effluent after MECRP was increased from 0.05 to 0.36 （by 620%）, which clearly suggested a considerable improvement of biodegradability for subsequent biological treatment. This study provided a demonstration of using microwave irradiation to enhance reaction between SA and nitrite in a short time, in which nitrite in wastewater was completely converted into nitrogen gas without leaving any sludge and secondary pollutants.

Mathematical simulation of direct reduction process in zinc-bearing pellets

A one-dimensional unsteady mathematical model was established to describe direct reduction in a composite pellet made of metallurgical dust. The model considered heat transfer, mass transfer, and chemical reactions including iron oxide reductions, zinc oxide reduction and carbon gasification, and it was numerically solved by the tridiagonal matrix algorithm （TDMA）. In order to verify the model, an experiment was performed, in which the profiles of temperature and zinc removal rate were measured during the reduction process. Results calculated by the mathematical model were in fairly good agreement with experimental data. Finally, the effects of furnace temperature, pellet size, and carbon content were investigated by model calculations. It is found that the pellet temperature curve can be divided into four parts according to heating rate. Also, the zinc removal rate increases with the increase of furnace temperature and the decrease of pellet size, and carbon content in the pellet has little influence on the zinc removal rate.

Research on Development of Dolomite-Ferrosilicon Thermal Reduction Process of Magnesium Production

Up to now, the Pedgion magnesium reduction process is the dominating magnesium production process. In 2004, about 98% of raw magnesium is produced by Pedgion magnesium reduction process in China which equals to 60% of the global output. It shows that the dolomite-ferrosilicon thermal reduction process is the most important method to produce magnesium in the world. Limited by the disadvantage of dolomite-ferrosilicon thermal reduction process, the magnesium producing process always followed by relatively severe pollution, while the resource utilizing efficiency keeps very low. With the rapid development of dolomite-ferrosilicon thermal reduction process in China, many research works have been done aiming at the process technology and the reduction theory, and the magnesium producing process has got great evolution. The history of dolomite-ferrosilicon thermal reduction process was introduced; the process character, the merits and which defects were also discussed. Defects in dolomite-ferrosilicon thermal reduction process were expatiated, and feasible method and idea to upgrade the process was put forward. The main problems and the potential troubles hindering the development of magnesium industry were analyzed. Finally, the probability to further improve the thermal reduction process and the effective approaches to develop Chinese magnesium industry were discussed.

Application of coal-water slurry on the rotary calcining kiln of pedgion magnesium reduction process

Energy saving has been an important concept in modern industry especially to the countries and regions with energy shortage such as China and Japan. Utilization of Coal-Water Slurry （CWS） can improve the burning efficiency of coal and reduce the pollutions of soot, sulfide and the nitride by burning lump coal directly. The CWS is a promising energy saving technique and the effectual substitute of oil. The study on the preparation and application of the CWS has made progresses in many aspects. The present paper studied the basal problems for applying the CWS on the rotary kilns during the calcining-dolomite process in the magnesium factory, summarized the key points for the application process of the CWS and gave the corresponding solutions.

Influence of furnace temperature and non-uniform heat flux density on direct reduction process of newly designed carbon containing pellet

In this study,innovative ellipsoid pellet with craters on its surface was designed,and the direct reduction process was compared with ellipsoid(without craters)and sphere pellets.In addition,furnace temperature and uneven heat flux density effects on the pellet direct reduction process were also studied.The results show that ellipsoid pellet is better than that of spherical pellet on metallization ratio.However,under the condition of non-uniform heat flow,the ellipsoid pellet final metallization rate and zinc removal rate were lower.Although the heat transfer effect of ellipsoid pellet with craters was not improved significantly,the metallization rate and zinc removal rate were found improved,which will have a cumulative effect on the pellets direct reduction process in rotary hearth furnace.Under varying furnace temperature conditions,the pellet temperature was higher than that of the constant furnace temperature.After 1200 s,pellet Fe concentration increased to 123.6%,metallization rate and zinc removal rate increased to 113.7%and 102.2%,respectively.These results can provide references for the carbon-containing pellet design used in rotary hearth furnace.

Degradation of metoprolol by UV/sulfite as an advanced oxidation or reduction process:The significant role of oxygen

The degradation of metoprolol(MTP)by the UV/sulfite with oxygen as an advanced reduction process(ARP)and that without oxygen as an advanced oxidation process(AOP)was comparatively studied herein.The degradation of MTP by both processes followed the first-order rate law with comparable reaction rate constants of 1.50×10^(-3)sec^(−1)and 1.20×10^(-3)sec^(−1),respectively.Scavenging experiments demonstrated that both e^(−)_(aq)and H·played a crucial role in MTP degradation by the UV/sulfite as an ARP,while SO_(4)^(·−)was the dominant oxidant in the UV/sulfite AOP.The degradation kinetics of MTP by the UV/sulfite as an ARP and AOP shared a similar pH dependence with a minimum rate obtained around pH 8.The results could be well explained by the pH impacts on the MTP speciation and sulfite species.Totally six transformation products(TPs)were identified from MTP degradation by the UV/sulfite ARP,and two additional ones were detected in the UV/sulfite AOP.The benzene ring and ether groups of MTP were proposed as the major reactive sites for both processes based on molecular orbital calculations by density functional theory(DFT).The similar degradation products of MTP by the UV/sulfite process as an ARP and AOP indicated that e^(−)_(aq)/H·and SO_(4)^(·−)might share similar reaction mechanisms,primarily including hydroxylation,dealkylation,and H abstraction.The toxicity of MTP solution treated by the UV/sulfite AOP was calculated to be higher than that in the ARP by the Ecological Struc-ture Activity Relationships(ECOSAR)software,due to the accumulation of TPs with higher toxicity.

Comparative evaluation of energy and resource consumption for vacuum carbothermal reduction and Pidgeon process used in magnesium production

With the fast development of the application of magnesium based alloys,the demand for primary magnesium is increasing dramatically all over the world.The Pidgeon process is the most widely used process for producing magnesium in China,but suffers from problems such as high energy,resource consumption and environmental pollution.While the process of vacuum carbothermal reduction to produce magnesium(VCTRM)has attracted more and more attention as its advantages,but it has not been well-practiced in industrial applications and there also is no comprehensive and quantitative analysis of this process.This study quantified the flows of resource and energy for the Pidgeon process and the VCTRM process,then compared and analyzed these two processes with each other from three aspects.The VCTRM process results in 63.14%and 69.16%lower of non-renewable mineral resources and energy consumptions when compared to the Pidgeon process,respectively.Moreover,the low energy consumption(2.675 tce vs.8.681 tce)and material to magnesium ratio(2.953:1 vs.6.429:1)of the VCTRM process,which lead to lower greenhouse gas(GHG)emissions(8.777 t vs.26.337 t)and solid waste generation(0.522 t vs.5.465 t)with a decrease of 66.67%and 90.45%,respectively.Results indicate that the VCTRM process is a more environmentally friendly process for magnesium production with high efficiency but low cost and low pollution,and it shows a good potential to be industrialized in the future after solving the bottleneck problem of the reverse reaction.

Effect of scandia on tungsten oxide powder reduction process

Scandia doped tungsten powders were prepared by spray drying combined with two-step hydrogen reduction.The particle size of doped tungsten powder,powder morphology and doped tungsten matrix were characterized by scanning electron microscope,X-ray diffrac-tion and laser diffraction particle size analyzer,respectively.The reduction behavior of Sc2O3 doped tungsten oxide and the effect of Sc2O3 on the property of tungsten powder were studied by the temperature programmed reduction.The experimental results showed that the pre-cursor powders prepared by spray drying had spherical shape.The addition of Sc2O3 could decrease the reduction temperature of tungsten oxide.The scandia doped tungsten powder had sub-micrometer size in the range of 0.1 to1 μm and scandium distributed evenly in the powder.By using this kind powder,sub-microstructure cathode matrices with semispherical grains and homogenous distribution of scan-dium were obtained.

CFD simulation of effect of anode configuration on gas–liquid flow and alumina transport process in an aluminum reduction cell

Numerical simulations of gas–liquid two-phase flow and alumina transport process in an aluminum reduction cell were conducted to investigate the effects of anode configurations on the bath flow, gas volume fraction and alumina content distributions. An Euler–Euler two-fluid model was employed coupled with a species transport equation for alumina content. Three different anode configurations such as anode without a slot, anode with a longitudinal slot and anode with a transversal slot were studied in the simulation. The simulation results clearly show that the slots can reduce the bath velocity and promote the releasing of the anode gas, but can not contribute to the uniformity of the alumina content. Comparisons of the effects between the longitudinal and transversal slots indicate that the longitudinal slot is better in terms of gas–liquid flow but is disadvantageous for alumina mixing and transport process due to a decrease of anode gas under the anode bottom surface. It is demonstrated from the simulations that the mixing and transfer characteristics of alumina are controlled to great extent by the anode gas forces while the electromagnetic forces(EMFs) play the second role.

Solid-state reduction kinetics and mechanism of pre-oxidized vanadium-titanium magnetite concentrate

The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows： pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →（FenTi1-n）Ti2O5. M3O5-type（M can be Fe, Ti, Mg, Mn, etc） solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.

Simultaneous Degradation, Dehalogenation, and Detoxification of Halogenated Antibiotics by Carbon Dioxide Radical Anions

Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promising method for their regulation during water or wastewater treatment.

Development of Direct Reduced Iron in China:Challenges and Pathways

The steel industry is considered an important basic sector of the national economy,and its high energy consumption and carbon emissions make it a major contributor to climate change,especially in China.The majority of crude steel in China is produced via the energy-and carbon-intensive blast furnace–basic oxygen furnace(BF–BOF)route,which greatly relies on coking coal.In recent years,China’s steel sector has made significant progress in energy conservation and emission reduction,driven by decarbonization policies and regulations.However,due to the huge output of crude steel,the steel sector still produces 15%of the total national CO_(2) emissions.The direct reduced iron(DRI)plus scrap–electric arc furnace(EAF)process is currently considered a good alternative to the conventional route as a means of reducing CO_(2) emissions and the steel industry’s reliance on iron ore and coking coal,since the gas-based DRI plus scrap–EAF route is expected to be more promising than the coal-based one.Unfortunately,almost no DRI is produced in China,seriously restricting the development of the EAF route.Here,we highlight the challenges and pathways of the future development of DRI,with a focus on China.In the short term,replacing natural gas with coke oven gas(COG)and byproduct gas from the integrated refining and chemical sector is a more economically feasible and cleaner way to develop a gas-based route in China.As the energy revolution proceeds,using fossil fuels in combination with carbon capture,utilization,and storage(CCUS)and hydrogen will be a good alternative due to the relatively low cost.In the long term,DRI is expected to be produced using 100%hydrogen from renewable energy.Both the development of deep processing technologies and the invention of a novel binder are required to prepare high-quality pellets for direct reduction(DR),and further research on the one-step gas-based process is necessary.

Numerical simulation of the direct reduction of pellets in a rotary hearth furnace for zinc-containing metallurgical dust treatment

A mathematical model was established to describe the direct reduction of pellets in a rotary hearth furnace （RHF）. In the model, heat transfer, mass transfer, and gas-solid chemical reactions were taken into account. The behaviors of iron metallization and dezincification were analyzed by the numerical method, which was validated by experimental data of the direct reduction of pellets in a Si-Mo furnace. The simulation results show that if the production targets of iron metallization and dezincification are up to 80% and 90%, respectively, the furnace temperature for high-temperature sections must be set higher than 1300~ C. Moreover, an undersupply of secondary air by 20% will lead to a decline in iron metallization rate of discharged pellets by 10% and a decrease in dezincing rate by 13%. In addition, if the residence time of pellets in the furnace is over 20 min, its further extension will hardly lead to an obvious increase in production indexes under the same furnace temperature curve.

Basic properties of steel plant dust and technological properties of direct reduction

Basic physicochemical properties of the dust from Laiwu Iron and Steel Co. Ltd. were studied. It is found that C, Zn, K, Na, etc. exist in the fabric filter dust, off gas （OG） sludge, fine ash in converter, and electrical field dust in sinter. Among these, OG sludge gives the finest particle, more than 90% of which is less than 2.51 mm. The dust can lead to a serious negative influence on the production of sintering and blast furnaces （BF） if it is recycled in sintering. The briquette and reduction experimental results showed that the qualified strength could be obtained in the case of 8wt% molasses or 4wt% QT-10 added as binders. Also, more than 75% of metallization ratio, more than 95% of dezincing ratio, as well as more than 80% of K and Na removal rates were achieved for the briquettes kept at 1250℃ for 15 min during the direct reduction process. SEM observation indicated that the rates of indirect reduction and carbonization became dominating when the bri-quettes were kept at 1250℃ for 6 min.

Direct reduction of iron ore by biomass char

By using thermogravimetric analysis the process and mechanism of iron ore reduced by biomass char were investigated and compared with those reduced by coal and coke. It is found that biomass char has a higher reactivity. The increase of carbon-to-oxygen mole ratio （C/O） can lead to the enhancement of reaction rate and reduction fraction, but cannot change the temperature and trend of each reaction. The reaction temperature of hematite reduced by biomass char is at least 100 K lower than that reduced by coal and coke, the maximum reaction rate is 1.57 times as high as that of coal, and the final reaction fraction is much higher. Model calculation indicates that the use of burden composed of biomass char and iron ore for blast furnaces can probably decrease the temperature of the thermal reserve zone and reduce the CO equilibrium concentration.

Mathematical model of the direct reduction of dust composite pellets containing zinc and iron

Direct reduction of dust composite pellets containing zinc and iron was examined by simulating the conditions of actual production process of a rotary hearth furnace （RHF） in laboratory. A mathematical model was constructed to study the reduction kinetics of iron oxides and ZnO in the dust composite pellets. It was validated by comparing the calculated values with experimental results. The effects of furnace temperature, pellet radius, and pellet porosity on the reduction were investigated by the model. It is shown that furnace temperature has obvious influence on both of the reduction of iron oxides and ZnO, but the influence of pellet radius and porosity is much smaller. Model calculations suggest that both of the reduction of iron oxides and ZnO are under mixed control with interface reactions and Boudouard reaction in the early stage, but only with interface reactions in the later stage.

Nitrate reduction by·CO_(2)^(-) from UV-activated HCOOH

To address the environmental and health hazards of nitrate(NO_(3)^(-))in water,a denitrification advanced reduction process(ARP)using only formic acid(HCOOH)activated by ultraviolet(UV)light was proposed.The efficiency,influencing factors,mechanism,and kinetics of the reduction were investigated through component analysis and radical detection.Results show that,after 90 min of UV illumination,the reduction and gas conversion ratios of 50 mg/L NO_(3)^(-)-N reach 99.9%and 99.8%,respectively,under 9 mM of C_(0)(HCOOH),pH=3.0,and N_(2) aeration.Meanwhile,96.7%of HCOOH is consumed and converted into gas.The NO_(3)^(-)-N conversion process includes the transformation to NO_(2)^(-)-N,followed by a further reduction to gas and a direct conversion into gas,introducing small amounts of nitrite and ammonia.The carbon dioxide anion radical(·CO_(2)^(-))from HCOOH/HCOO^(-)is the principal cause of NO_(3)^(-)-N reduction by UV/HCOOH/N 2 ARP.In contrast,·CO_(2)^(-)production is caused by the hydroxyl radical(·OH).The NO_(3)^(-)-N reduction efficiency is enhanced by the increase in the light intensity,considerably affected by the initial pH,and less affected by inorganic anions,including Cl^(-),H_(2)PO_(4)^(-),and HCO_(3)^(-)/CO_(3)^(2-).The initial HCOOH concentration and light intensity are the main factors that influence the NO_(3)^(-)-N reduction rate.

Reduction and melting behavior of carbon composite lateritic bauxite pellets

Direct reduction of low-grade lateritic bauxite was studied at high temperature to recover Fe and beneficiate AlzO3 slag. The re- sults show that a metallization rate of 97.9% and a nugget recovery rate of 85.1% can be achieved when the reducing and melting tempera- tures are 1350 and 1480℃, respectively. Moreover, a higher-grade calcium aluminate slag （A1203 = 50.52wt%） can also be obtained, which is mainly composed of ct-A1203, hercynite （FeAI：O4）, and gehlenite （Ca2A12SiO7）. In addition, high-quality iron nuggets have been produced from low-grade lateritic bauxite. The nugget is mainly composed of iron （93.82wt%） and carbon （3.86wt%）, with almost no gangue （slag）.

Application of carbon composite iron ore hot briquette to innovative ironmaking process

As a new type of ironmaking raw materials,carbon composite iron ore hot briquette(CCB) is the product of fine iron ore and fine coal by hot briquetting process.On basis of experimental research on the manufacturing and metallurgical properties of CCB,this study focused on the application of CCB to blast furnace ironmaking and newly-developed shaft furnace smelting reduction processes.Firstly,the metallurgical properties of CCB are experimentally tested and compared with the common iron-bearing burdens.Then,the effects of charging CCB on blast furnace operation are numerically analyzed by means of multi-fluid blast furnace model,and the flowchart and pilot test of CCB-Shaft furnace smelting reduction process are briefly introduced.