Precise regulation of the phase transformation for pyrolusite during the reduction roasting process

The mechanism involved in the phase transformation process of pyrolusite (MnO_(2)) during roasting in a reducing atmosphere was systematically elucidated in this study,with the aim of effectively using low-grade complex manganese ore resources.According to single-factor experiment results,the roasted product with a divalent manganese (Mn^(2+)) distribution rate of 95.30% was obtained at a roasting time of 25 min,a roasting temperature of 700℃,a CO concentration of 20at%,and a total gas volume of 500 mL·min^(-1),in which the manganese was mainly in the form of manganosite (MnO).Scanning electron microscopy and Brunauer–Emmett–Teller theory demonstrated the microstructural evolution of the roasted product and the gradual reduction in the pyrolusite ore from the surface to the core Thermodynamic calculations,X-ray photoelectron spectroscopy,and X-ray diffractometry analyses determined that the phase transformation of pyrolusite followed the order of MnO_(2)→Mn_(2)O_(3)→Mn_(3)O_(4)→MnO phase by phase,and the reduction of manganese oxides in each valence state proceeded simultaneously.

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.

Mechanism of phosphorus removal in beneficiation of high phosphorous oolitic hematite by direct reduction roasting with dephosphorization agent

High phosphorous oolitic hematite ore is one of typical intractable iron ores in China, and the conventional beneficiation methods are found to be impracticable to , remove phosphorus from the ore effectively. Better beneficiation index were gotten by direct reduction roasting with dephosphorization agent followed by two stages of grinding and magnetic separation. P content decreases from 0.82% in the raw ore to 0.06% in the magnetic concentrate, and the total iron grade increases from 43.65% to 90.23%, the recovery of iron can reach 87%. Mechanisms of phosphorus removal in the beneficiation of high phosphorous oolitic hematite ore by direct reduction roasting with dephosphorization agent were studied using XRD, SEM and EPMA. The results showed that about 20% of the apatite in the raw ore transferred into phosphorus and volatilized with the gas in the process of reduction roasting, while the rest 80% apatite was not involved in the reaction of generation of phosphorus, and remained as apatite in the roasted products, which was removed to tailings by grinding and magnetic separation. A small amount of phosphorus existed in the magnetic concentrate as apatite. The oolitic texture of raw ore was partly changed during roasting, resulting in the formation of nepheline in the reaction between the dephosphorization agent, SiO2 and Al2O3 in the raw ore, which greatly improved the liberation degree of minerals in the roasted products, and it was beneficial to the subsequent grinding and magnetic separation.

Response surface optimization of process parameters for reduction roasting of low-grade pyrolusite by bagasse

The reduction roasting processes for low-grade pyrolusite using bagasse as the reducing agent was statistically analyzed. The central composite rotatable design （CCD） was used to optimize this reduction roasting processes. The three process parameters studied were the mass ratio of bagasse to ore, the roasting temperature and the roasting time. Analysis of variance （ANOVA） was used to analyze the experimental results. The interactions between the process parameters were done by using the linear and quadratic model. The results revealed that the linear and quadratic effects as well as the interaction are statistically significant for the mass ratio and roasting temperature but insignificant for the roasting time. The optimal conditions of 0.9：10 of mass ratio, the roasting temperature of 450 ~C, the roasting time of 30 min were obtained. Under these conditions, the predicted leaching recovery rate for manganese was 98.1%. And the satisfied experimental result of 98.2% confirmed the validity of the model.

Reaction behavior of kaolinite with ferric oxide during reduction roasting

The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe2O3/Al2O3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.

Extraction of valuable metals from low-grade nickeliferous laterite ore by reduction roasting-ammonia leaching method

Nickel and cobalt were extracted from low-grade nickeliferous laterite ore using a reduction roasting-ammonia leaching method.The reduction roasting-ammonia leaching experimental tests were chiefly introduced,by which fine coal was used as a reductant.The results show that the optimum process conditions are confirmed as follows:in reduction roasting process,the mass fraction of reductant in the ore is 10%,roasting time is 120 min,roasting temperature is 1 023-1 073 K;in ammonia leaching process,the liquid-to-solid ratio is 4:1(mL/g),leaching temperature is 313 K,leaching time is 120 min,and concentration ratio of NH3 to CO2 is 90 g/L:60 g/L.Under the optimum conditions,leaching efficiencies of nickel and cobalt are 86.25% and 60.84%,respectively.Therefore,nickel and cobalt can be effectively reclaimed,and the leaching agent can be also recycled at room temperature and normal pressure.

Characteristics of the reduction behavior of zinc ferrite and ammonia leaching after roasting

A novel method for recovering zinc from zinc ferrite by reduction roasting–ammonia leaching was studied in this paper. The reduction thermodynamic of zinc ferrite by CO was analyzed. The effects of roasting parameters on the phase transformation and conversion rate of zinc ferrite, and the leaching behavior of zinc from the reductive roasted samples by ammonia leaching, were experimentally investigated. The mineralogical phase compositions and chemical compositions of the samples were characterized by X-ray diffraction and chemical titration methods, respectively. The results showed that most of the zinc ferrite was transformed to zinc oxide and magnetite after weak reduction roasting. 86.43% of the zinc ferrite was transformed to zinc oxide under the optimum conditions: CO partial pressure of 25%, roasting temperature of 750°C, and roasting duration of 45 min. Finally, under the optimal leaching conditions, 78.12% of zinc was leached into the solution from the roasted zinc ferrite while all iron-bearing materials were kept in the leaching residue. The leaching conditions are listed as follows: leaching duration of 90 min,ammonia solution with 6 mol/L concentration, leaching temperature of 50°C, solid-to-liquid ratio of 40 g/L, and stirring speed of 200 r/min.

Recovery of antimony from antimony-bearing dusts through reduction roasting process under CO–CO_2 mixture gas atmosphere after firstly oxidation roasted

This paper mainly investigated the antimony recovery from antimony-bearing dusts through reduction roasting process after the dust firstly oxidation roasted.CO–CO2 mixture gas was used as reducing agent,and the antimony-containing phase was reduced into Sb4O6,volatilized into smoke,and finally recovered through the cooling cylinder.The antimony recovery rate increased from 66.00 wt%to 73.81 wt%in temperature range of 650 to 800°C,and decreased with temperature increased further to 900°C due to the reduction of Sb4O6 to the nonvolatile Sb.Similarly,the CO partial pressure also played a double role in this test.Under optimized conditions of roasting temperature of 800°C,CO partial pressure of 7.5 vol%and roasting time of 120 min,98.40 wt%of arsenic removal rate and 80.40 wt%antimony recovery rate could be obtained.In addition,the“As2O3”product could be used for preparing ferric arsenate which realized the harmless treatment of it.

Feasibility of co-reduction roasting of a saprolitic laterite ore and waste red mud

Large scale utilization is still an urgent problem for waste red mud with a high content of alkaline metal component in the future.Laterite ores especially the saprolitic laterite ore are one refractory nickel resource,the nickel and iron of which can be effectively recovered by direct reduction and magnetic separation.Alkaline metal salts were usually added to enhance reduction of laterite ores.The feasibility of co-reduction roasting of a saprolitic laterite ore and red mud was investigated.Results show that the red mud addition promoted the reduction of the saprolitic laterite ore and the iron ores in the red mud were co-reduced and recovered.By adding 35wt%red mud,the nickel grade and recovery were 4.90wt%and 95.25wt%,and the corresponding iron grade and total recovery were 71.00wt%and 93.77wt%,respectively.The X-ray diffraction（XRD）,scanning electron microscopy,and energy dispersive spectroscopy（SEM-EDS）analysis results revealed that red mud addition was helpful to increase the liquid phase and ferronickel grain growth.The chemical compositions＂Ca O and Na_2O＂in the red mud replaced Fe O to react with Si O_2 and Mg Si O_3 to form augite.

Microwave-assisted reduction roasting–magnetic separation studies of two mineralogically different low-grade iron ores

The microwave-assisted reduction behaviours of two low-grade iron ores having a similar Fe content of 49wt%but distinctly different mineralogical and liberation characteristics were studied.Their performances in terms of the iron grade and recovery as obtained from statistically designed microwave(MW)roasting followed by low-intensity magnetic separation(LIMS)experiments were compared.At respective optimum conditions,the titano-magnetite ore(O1)could yield an iron concentrate of 62.57%Fe grade and 60.01%Fe recovery,while the goethitic ore(O2)could be upgraded to a concentrate of 64.4%Fe grade and 33.3%Fe recovery.Compared with the goethitic ore,the titanomagnetite ore responded better to MW heating.The characterization studies of the feed and roasted products obtained at different power and time conditions using X-ray diffraction,optical microscopy,vibrating-sample magnetometry,and electron-probe microanalysis explain the sequential reduction in the iron oxide phases.Finally,taking advantage of the MW absorbing character of the titano-magnetite ore,a blend of the same with the goethite-rich ore at a weight ratio of 60:40(O2:O1)was subjected to MW roasting that resulted in a concentrate of 61.57%Fe grade with a Fe recovery of 64.47%.

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.

Reaction behaviors of Pb and Zn sulfates during reduction roasting of Zn leaching residue and flotation of artificial sulfide minerals

To evaluate the feasibility of recovering Pb and Zn sulfides and Ag-containing minerals from Zn leaching residue by the process of reduction roasting followed by flotation,the reaction behaviors of Pb and Zn sulfates during this process were investigated.Chemical analysis showed that the transformation ratios of PbSO4 and ZnSO4 could reach 65.51%and 52.12%,respectively,after reduction roasting,and the introduction of a sulfidation agent could improve the transformation ratios of these sulfates.scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS)revealed that temperature obviously affects the particle size,crystal growth,and morphology of the artificial Pb and Zn sulfide minerals.Particle size analysis demonstrated that the particle size of the materials increases after roasting.Flotation tests revealed that a flotation concentrate composed of 12.01wt%Pb,27.78wt%Zn,and 6.975×10^(−2)wt%Ag with recoveries of 60.54%,29.24%,and 57.64%,respectively,could be obtained after roasting.

Manganese extraction from high-iron-content manganese oxide ores by selective reduction roasting-acid leaching process using black charcoal as reductant

Reduction roasting-acid leaching process was utilized to process high-iron-content manganese oxide ore using black charcoal as reductant. The results indicate that, compared with the traditional reductant of anthracite, higher manganese extraction efficiency is achieved at lower roasting temperature and shorter residence time. The effects of roasting parameters on the leaching efficiency of Mn and Fe were studied, and the optimal parameters are determined as follows: roasting temperature is 650 °C, residence time is 40 min, and black charcoal dosage is 10%(mass fraction). Under these conditions, the leaching efficiency of Mn reaches 82.37% while that of Fe is controlled below 7%. XRD results show that a majority of MnO2 and Fe2O3 in the raw ore are reduced to MnO and Fe3O4, respectively.

Recovery of Ferric Oxide from Bayer Red Mud by Reduction Roasting-Magnetic Separation Process

A great amount of red mud generated from alumina production by Bayer process was considered as a low-grade iron ore with a grade of 5wt% to 30wt% iron.We adopted the reduction roastingmagnetic separation process to recover ferric oxide from red mud.The red mud samples were processed by reduction roasting,grinding and magnetic separating respectively.The effects of different parameters on the recovery rate of iron were studied in detail.The optimum techqicalparameters were proposed with 700 ℃roasting for 20 min,as 50wt% carbon and 4wt% additive were added.The experimentalresults indicated that the iron recovery and the grade of totaliron were 91% and 60%,respectively.A novelprocess is applicable to recover ferric oxide from the red mud waste fines.

Pyrometallurgical recycling of spent lithium-ion batteries from conventional roasting to synergistic pyrolysis with organic wastes

The synergistic pyrolysis has been increasingly used for recycling spent lithium-ion batteries(LIBs)and organic wastes(hydrogen and carbon sources),which are in-situ transformed into various reducing agents such as H_(2),CO,and char via carbothermal and/or gas thermal reduction.Compared with the conventional roasting methods,this“killing two birds with one stone”strategy can not only reduce the cost and energy consumption,but also realize the valorization of organic wastes.This paper concluded the research progress in synergistic pyrolysis recycling of spent LIBs and organic wastes.On the one hand,valued metals such as Li,Co,Ni,and Mn can be recovered through the pyrolysis of the cathode materials with inherent organic materials(e.g.,separator,electrolyte)or graphite anode.During the pyrolysis process,the organic materials are decomposed into char and gases(e.g.,CO,H_(2),and CH_(4))as reducing agents,while the cathode material is decomposed and then converted into Li_(2)CO_(3) and low-valent transition metals or their oxides via in-situ thermal reduction.The formed Li_(2)CO_(3) can be easily recovered by the water leaching process,while the formed transition metals or their oxides(e.g.,Co,CoO,Ni,MnO,etc.)can be recovered by the reductant-free acid leaching or magnetic separation process.On the other hand,organic wastes(e.g.,biomass,plastics,etc.)as abundant hydrogen and carbon sources can be converted into gas(e.g.,H_(2),CO,etc.)and char via pyrolysis.The cathode materials are decomposed and subsequently reduced by the pyrolysis gas and char.In addition,the pyrolysis oil and gas can be upgraded by catalytic reforming with the active metals derived from cathode material.Finally,great challenges are proposed to promote this promising technology in the industrial applications.

Selective reduction process of zinc ferrite and its application in treatment of zinc leaching residues

The traditional zinc hydro-metallurgy generates a large amount of zinc ferrite residue rich in valuable metals. The separation of iron is crucial for resource recycling of valuable metals in zinc ferrite residue. A novel selective reduction roasting？leaching process was proposed to separate zinc and iron from zinc leaching residue which contains zinc ferrite. The thermodynamic analysis was employed to determine the predominant range of Fe3O4 and ZnO during reduction roasting process of zinc ferrite. Based on the result of thermodynamic calculation, we found thatV（CO）/V（CO＋CO2） ratio is a key factor determining the phase composition in the reduction roasting product of zinc ferrite. In the range ofV（CO）/V（CO＋CO2） ratio between 2.68% and 36.18%, zinc ferrite is preferentially decomposed into Fe3O4 and ZnO. Based on thermogravimetric （TG） analysis, the optimal conditions for reduction roasting of zinc ferrite are determined as follows： temperature 700？750 °C, volume fraction of CO 6% and V（CO）/V（CO＋CO2） ratio 30%. Based on the above results, zinc leaching residue rich in zinc ferrite was roasted and the roasted product was leached by acid solution. It is found that zinc extraction rate in zinc leaching residue reaches up to 70% and iron extraction rate is only 18.4%. The result indicates that zinc and iron can be effectively separated from zinc leaching residue.

Efficient separation of alumina and silica in reduction-roasted kaolin by alkali leaching

Alkali leaching was employed to investigate the separation of alumina and silica in roasted kaolin obtained by roasting kaolin alone in air at 1273 K for 60 min and in clinker prepared by roasting the mixed raw meal of kaolin,ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 in reducing atmosphere at 1373 K for 60 min.The thermodynamic analyses and alkali leaching results show that the composition of the Al-Si spinel in roasted kaolin is close to that of 3Al2O3·2SiO2 and the spinel is dissolved with increasing leaching time,resulting in difficulty in deeply separating alumina and silica in kaolin by the traditional roasting-leaching process.On the contrary,the efficient separation of alumina and silica in kaolin can be reached by fully converting kaolinite into insoluble hercynite and soluble free silica,namely quartz solid solution and cristobalite solid solution,during reduction roasting,followed by alkali leaching of the obtained clinker.Furthermore,experimental results from treating high-silica diasporic bauxite indicate that the reduction roasting-alkali leaching process is potential to separate silica and alumina in aluminosilicates.

Growth of metallic iron particles during reductive roasting of boron-bearing magnetite concentrate

The growing characteristics of metallic iron particles during reductive roasting of boron-bearing magnetite concentrate under different conditions were investigated.The size of the metallic iron particles was quantitatively measured via optical image analysis with consideration of size calibration and weighted ratio of image numbers in the core,middle and periphery zones of cross-section of pellets.In order to guarantee the measurement accuracy,54 images were captured in total for each specimen,with a weighted ratio of 1:7:19 with respect to the core,middle and periphery section of the cross-section of pellets.Increasing reduction temperature and time is favorable to the growth of metallic iron particles.Based on the modification of particle size measurement,in terms of time(t)and temperature(T)a predicting model of metallic iron particle size(D),was established as:D=125−0.112t−0.2352T−5.355×10^−4t^2+2.032×10^−4t∙T+1.134×10^−4T^2.

Thermodynamic and experimental study of high-temperature roasting of blast furnace gas ash for recovery of metallic zinc and iron

A high-temperature reduction roasting method was used to achieve metallic iron and zinc recovery from blast furnace gas ash(BFA).The reduction processes for Zn-containing and Fe-containing oxides were analyzed in detail by using ther-modynamic equilibrium calculation and the principle of minimum free energy.The results showed that the main reaction in the system is the reduction of ZnFe_(2)_(4)and iron oxides.Over the full temperature range,iron oxides were more easily reduced than zinc oxides.Regardless of the amount of CO contained in the system,the reduction of ZnO to Zn was difficult to proceed below the boiling point(906℃)of Zn.When the reduction temperature is below 906℃,the reduction process of zinc ferrate was ZnFe_(2)_(4)→ZnO;when the reduction temperature is above 906℃,its reduction process becomed ZnFe_(2)_(4)→ZnO→Zn(g).The metallization and dezincification rates of the BFA gradually increased with increasing reaction temperature.As the C/O ratio increased,the metallization and dezincification rates first increased and then decreased.The effect of reduction time on BFA reduction was similar to that of reaction temperature.

Recovery of Iron From High-Iron Red Mud by Reduction Roasting With Adding Sodium Salt

Red mud is the waste generated during aluminum production from bauxite, containing lots of iron and other valuable metals. In order to recover iron from red mud, the technology of adding sodium carbonate—reduction roasting—magnetic separation to treat high-iron red mud was developed. The effects of sodium carbonate dosage, reduction temperature and reduction time on the qualities of final product and the phase transformations in reduction process were discussed in detail. The results showed that the final product (mass percent), assaying Fe of 90.87% and Al2O3 of 0.95% and metallization degree of 94.28% was obtained at an overall iron recovery of 95.76% under the following conditions of adding 8% sodium carbonate, reduction roasting at 1 050 ℃ for 80 min and finally magnetic separation of the reduced pellets by grinding up to 90% passing 0.074 mm at magnetic field intensity of 0.08 T. The XRD (X-ray diffraction) results indicated that the iron oxides were transformed into metallic iron. Most of aluminum mineral and silica mineral reacted with sodium carbonate during the reduction roasting and formed nonmagnetic materials.