粉煤灰酸浸物制备氢氧化铝产品工艺优化研究

固原六盘山热电厂粉煤灰酸浸制得铝酸盐溶液,以Na OH溶液为调整剂制备氢氧化铝产品,考察了反应温度、Na OH用量(实用量/理论量)、Na OH浓度、反应时间等因素影响。结果表明,最优条件为:Na OH用量(实用量/理论量)2.0倍,Na OH浓度35%,反应温度75℃,反应时间1.5 h。在该条件下,氢氧化铝平均产率97.83%。SEM、XRD及化学成分分析表明,氢氧化铝为球状颗粒,晶相为β'-三水铝石,性能指标达到了GB/T 4294—2010的要求。研究将为该地区粉煤灰高附加值资源化奠定理论基础。

煤矸石中和渣酸浸物的溶出

采用浸提法提取煤矸石中和渣酸浸物中的有价元素,考察了溶出温度、溶出时间和溶出液固质量比对酸浸物溶出过程的影响;以单因素实验为基础,进行正交实验,优化溶出工艺条件,用X射线衍射(XRD)和扫描电镜(SEM)表征煤矸石中和渣酸浸物、酸化产物及滤渣的物相和微观形貌。结果表明,酸浸物溶出最优工艺条件为液固质量比3:1、溶出时间40 min、溶出温度80℃,此时有价元素氧化物的溶出率分别为TiO282.63%,Fe2O396.48%,Al2O398.33%,CaO 87.72%,MgO 95.31%。提取后滤渣中只有SiO2和少量TiO2及CaSO4存在,表明煤矸石中和渣酸浸物中的有价元素通过该溶出工艺可充分溶出。

Leaching kinetics of bastnaesite concentrate in HCl solution

The leaching kinetics of bastnaesite concentrate in HCl solution was investigated with respect to the effects of HCl concentration by changing HCl concentration,leaching temperature,liquid to solid ratio,and particle size.A particle size of 25 μm was required to leach 89.6% RE2（CO3）3 and 1.5%REF3 at 90 ℃ for 90 min,when HCl concentration was 6 mol/L and liquid to solid ratio was 15：1.The leaching kinetics of bastnaesite concentrate is represented by shrinking core model with diffusion through a porous product layer.The activation energies for the dissolution reaction of RE2（CO3）3 and REF3 were calculated to be 59.39 kJ/mol and 66.13 kJ/mol respectively.

Effect of pyrite, elemental sulfur and ferrous ions on EPS production by metal sulfide bioleaching microbes

Extracellular polymeric substances （EPS） produced by acidophilic bioleaching microorganisms play an important role in the production of acid mine drainage and metal sulfide bioleaching. EPS mediate the contact between microbial cells and growth substrates, having a pivotal role in organic film formation and bacterium-substratum interactions. The production and chemical composition of EPS produced by seven bioleaching strains grown with different substrates were studied. Analysis of the EPS extracted from these strains indicated that the EPS consisted of carbohydrates, proteins and galacturonic acid. The contents of EPS, carbohydrates, proteins and galacturonic acid of EPS were largely related to the kind of strain used and culture condition. The results show that EPS productions of microbes grown with pyrite were significantly higher than those of microbes grown with sulfur or FeSO4·7H2O. The highest EPS production of the seven acidiphilic strains was （159.43±3.93） mg/g, which was produced by Leptospirillum ferriphilum CBCBSUCSU208015 when cultivated with pyrite.

Effect of initial pH on chalcopyrite oxidation dissolution in the presence of extreme thermophile Acidianus manzaensis

The influence of initial pH on the chalcopyrite oxidation dissolution at 65 ℃ was investigated by bioleaching and cyclic voltammetiy experiments,and the oxidation products were investigated by XRD and Raman spectroscopy.Bioleaching results show that chalcopyrite dissolution rate increases with the decrease of the initial pH in chemical leaching,while the influence of initial pH on bioleaching is on the contrary.The presence of Acidianus manzaensis does not promote chalcopyrite dissolution under initial pH1.0,which mainly results from serious inhibition of high acidity to the growth of Acidianus manzaensis.Electrochemical experiments results show that anodic oxidation currents of electrolyte with or without Acidianus manzaensis both increase with the increase of initial pH,and covellite and sulfur are detected on the electrode surface.The results confirm that chalcopyrite dissolution in chemical leaching is under the combined action of oxidation and non-oxidation of proton,with conversion of chalcopyrite to covellite and elemental sulfur.

Decomposition mechanism of pentlandite during electrochemical bio-oxidation process

Electrochemical measurements were carried out to elucidate decomposition mechanism of pentlandite using modified powder microelectrode with Acidithiobacillus ferrooxidans attached or without on the mineral powder surface.Cyclic voltammetry（CV） results show that at a low potential of about-0.2 V（vs SCE）,the pentlandite was transformed to an intermediated phase like Fe4.5-yNi4.5-xS8-z when Fe and Ni ions were evacuated from mineral lattice;when the potential was changed from-0.2 V to 0.2 V,the unstable violarite（Fe3Ni3S4） and FeNi2S4 were formed which was accompanied by element sulfur formed on the mineral surface;when the potential increased over 0.2 V,the unstable intermediated phase decomposed entirely;at a higher potential of 0.7 V,the evacuated ferrous ion was oxidized to ferric ion.The presence of Acidithiobacillus ferrooxidans made the oxidation peak current increase with initial peak potential negatively moving,and the bacteria also contributed to the sulfur removing from mineral surface,which was demonstrated by the reduction characteristic at potential ranging from-0.75 to-0.5 V.Leaching experiments and electrochemical results show that the solution acidity increasing when pH2 may impede the oxidation process slightly.

Preparation of titanium mineral from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching

Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction degree.The phase compositions of the reduced materials and the leached residues were analyzed by XRD to identify the effect of reduction degree on the leaching mechanisms.The results showed that the concentrates were reduced to iron metal and titanomagnetite at 800-1000°C for 0.5 h,and the above elements of Fe and impurities were easily leached.Deeper reduction led to the formation of ilmenite and Mg-Al spinel,which hindered leaching.Mg-bearing anosovite appeared in the further reduced materials,and the leaching rates of impurities became much lower.An upgraded titanium mineral with a normalized TiO_(2) grade of 70.3%was achieved by H_(2) reduction at 850°C for 0.5 h and acid leaching,which is a satisfactory Ti resource for the preparation of titanium oxide by sulfate process.

Extraction of germanium(IV) from acid leaching solution with mixtures of P204 and TBP

Solvent extraction experiments were conducted from acidic solutions containing germanium（IV） and other metal ions, such as Ga3＋, Fe3＋, Zn2＋ and Fe2＋ in hydrometallurgical process of zinc. The purpose of this work was to enhance the efficiency of the extraction and stripping processes and the selectivity of germanium and other metals, while making the method as simple as possible. Germanium was recovered from sulfuric acid, using di-（2-ethylhexyl） phosphoric acid （P2O4） as an extractant, tributyl phosphate （TBP） as modifier diluted in sulfonate kerosene and stripped by NaOH aqueous solution. Extraction studies were carried out under different acid concentrations and solvent concentrations, and optimized conditions were determined. The numbers of stages required for extraction and stripping of metal ions were determined from the McCabe-Thiele plot. The results show that the extracting and stripping efficiencies are 94.3% and 100%, respectively, through two-stage extraction and two-stage strip. Moreover, the synergistic effect of TBP on the system P2O4/kerosense/Ge4＋ is revealed with respect to the extraction of germanium.

Heavy Metals in a Sulfldic Minespoil: Fractions and Column Leaching

Fractions of various heavy metals in a sulfidic minespoil were investigated. Column leaching experimentwas also conducted to simulate 'acid mine drainage' (AMD) from the minespoil. The results show thatleaching of heavy metals from the minespoil was extremely significant during the initial water flushing.The amounts of heavy metals leached out dramatically reduced after leaching twice. It is worthwhile tonote that in this study, Zn, Mn, Fe, As and Ni in the first leachate exceeded the total amount of eachcorresponding water-extractable (1:5, soil:water) metal contained in the minespoil sample. This appears tosuggest that 1:5 water extraction did not allow accurate estimation of water-leachable concentrations of theabove heavy metals. This work has implications for the management of sulfidic minespoils. Acid drainageof great environmental concerns is likely to occur only during heavy rainfall events after substantial solubleand readily exchangeable acid and metals are accumulated in the minespoils. The slow-reacting fractionsother than water-soluble and readily exchangeable fractions may pose little environmental hazards. This isparticularly true for Pb, As and Ni.

Improving zinc recovery by thermoacidophilic archaeon Acidianus copahuensis using tetrathionate

The attachment and bioleaching experiments were conducted to evaluate the zinc recovery from Hualilan ore by thethermoacidophilic archaeon Acidianus copahuensis. Cells of this species pregrown on tetrathionate showed higher capability ofattachment to the ore than cells pregrown on other energy sources and such attachment seemed to be mediated by the product ofextracellular polymeric substances. A. copahuensis achieved a successful bioleaching of the ore reaching 100% of zinc recoverywhen tetrathionate was added. Simultaneous addition of yeast extract and tetrathionate maintained the zinc extraction at higher rate.Zinc dissolution kinetics was controlled by chemical reaction in cultures with the external addition of tetrathionate but by thediffusion through a product layer of jarosite in the other cultures.

Synthesis of intracellular cobalt ferrite nanocrystals by extreme acidophilic archaea Ferroplasma thermophilum

Ferroplasma thermophilum,a sort of extreme acidophilic archaea,which can synthesize intracellular cobalt ferrite nanocrystals,is investigated in this study.The nanocrystals were analyzed with ultrathin sections and transmission electron microscope,with the size of 20−60 nm,the number of more than 30 in each cell at average,which indicated that F.thermophilum can synthesize intracellular nanocrystals and also belongs to high-yield nanocrystals-producing strain.Intriguingly,the nanocrystals contain ferrite and cobalt characterized by EDS X-ray analysis,suggesting that both cobalt and ferrite are potentially contributed to the formation of nanocrystals.Moreover,under the different energy source culture conditions of FeSO4 and CuFeS2,the size and the morphology of the nanocrystals are different.It was also found that the higher initial Fe availability leads to an induced synthesis of larger nanocrystals and the lower oxidation-reduction potential(ORP)leads to an induced effect on the synthesis of nanocrystals with abnormal unhomogeneous size,which suggested that the higher initial Fe availability and the lower oxidation-reduction potential lead to a higher uptake efficiency of iron ions of F.thermophilum by iron and ORP gradient culture.

Really active form of fluorine toxicity affecting Acidithiobacillus ferrooxidans activity in bioleaching uranium

In order to determine the mechanism of bacterial tolerance to fluorine,Acidithiobacillus ferrooxidans ATCC 23270 was domesticated and studied under the conditions of different fluorine concentrations and pH values with or without treatment by Proteinase K.The bacterial activities were observed through measuring the changes of solution potentials by platinum electrode with Ag/AgCl reference electrode and the intracellular fluorine was determined by-uorine ion-selective electrode.The results indicated that the tolerance of Acidithiobacillus ferrooxidans ATCC 23270 to fluorine could be obviously improved by domestication,HF was the effective form of fluorine to affect the bacterial activity,and pH increase or concentration change of ions of strong complex ability with fluorine ions in solution could result in false appearance of high fluorine-resistant strain.Some proteins located in cell wall or cell membrane were intimately relative with the bacterial fluorine tolerance.

Formation of jarosite and its effect on important ions for Acidithiobacillus ferrooxidans bacteria

The precipitation of jarosite adversely affects the bio-leaching of copper sulfides in the Sarcheshmeh heap bio-leaching process. The variables of the initial concentration of ferrous iron in the growth medium, pH, and temperature were examined in the laboratory to determine how they affect the precipitation of jarosite in the presence of Acidithiobacillus ferrooxidans bacteria. It was found that the maximum ferric precipitate occurred at a ferrous sulfate concentration of 50 g/L, a temperature of 32 ℃, and an initial pH value of 2.2. The effects of the precipitation of ferric iron on the quantities of ions that are important for A. ferrooxidans bacteria in aqueous phase, i.e., ferric, sulfate, potassium, phosphate, and magnesium ions, also were assessed. The results showed relatively similar patterns for the ferric and potassium ions, and then reason might have been the co-precipitation of these ions as constituent elements of jarosite mineral. At pH values greater than 1.6, the solubility of phosphate ions decreased dramatically due to the co-precipitation of phosphate ions with the jarosite precipitate and due to the significant growth rate of A. ferrooxidans bacteria in this pH range. Due to the dissolution of a gangue constituent in the ore, the magnesium levels increased in the first few days of the bio-leaching process;thereafter, it decreased slightly.

Catalytic effect of visible light and Cd^2+on chalcopyrite bioleaching

The effects of visible light and Cd^2+ion on chalcopyrite bioleaching in the presence of Acidithiobacillus ferrooxidans(A.ferrooxidans)were studied by scanning electron microscopy(SEM),synchrotron radiation X-ray diffraction(SR-XRD),and X-ray photoelectron spectroscopy(XPS).The results of bioleaching after 28 days showed that the copper dissolution increased by 4.96%with only visible light,the presence of Cd2+alone exerted slight inhibition effect on chalcopyrite dissolution and the concentration of dissolved copper increased by 14.70%with visible light and 50 mg/L Cd^2+.The results of chemical leaching showed that visible light can promote the circulation of iron.SEM results showed that Cd^2+promoted the attachment of A.ferrooxidans on chalcopyrite surface under visible light.SR-XRD and XPS results indicated that visible light and Cd^2+promoted chalcopyrite dissolution,but did not inhibit the formation of passivation.Finally,a model of synergistic catalysis mechanism of visible light and Cd2+on chalcopyrite bioleaching was proposed.

Electrochemical synthesis of Nb C-Sn composite powder in molten chloride

NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating electrochemicalexperiments for various durations.The influence of carbon on the final products was considered.NbC particles were obtained byleaching the composite with acid.The results showed that the aggregated NbC-Sn composite powdev contained NbC particles about50-100nm and Sn particles about200nm.SnO2was reduced to Sn in the sintering process.Nb2O5was electrochemically reduced toNb in molten salt,experiencing some intermediate products of calcium niobates and niobium suboxides.Nb metal obtained wasconverted to NbC with assistance of carbon.The reduction of Nb oxides may be incomplete and Nb3Sn would be formed if carbon isinsufficient in the cathodic pellet.NbC with good dispersity is produced by leaching NbC-Sn with HCl.

Extraction of cobalt from laterite ores by citric acid in presence of ammonium bifluoride

Citric acid was used to selectively extract cobalt from limonite-type laterite ores in the presence of ammonium bifluoride.The results show that ammonium bifluoride enhances the leaching of cobalt by citric acid,and 84.5% cobalt is extracted from a laterite ore containing 0.13% Co when leached at ambient temperature for 2 h with 30 g/L citric acid and 10 g/L ammonium bifluoride.Pyrolusite is reduced by citric acid during leaching,cobalt intergrown with which is liberated and subsequently chelated by the citric acid.The extraction of cobalt is enhanced in the presence of ammonium bifluoride because the matrix of silicate minerals is destroyed by ammonium bifluoride and the adsorbed cobalt is subsequently liberated.

Effect of L-cysteine on bioleaching of Ni-Cu sulphide by A. manzaensis

The effect of L-cysteine in different concentrations on the bioleaching of Ni-Cu sulfide was studied with an extremely thermophilic archaea,Acidianus manzaensis. It is found that adding certain amounts of L-cysteine to the bioleaching system of Ni-Cu sulfide largely enhances the leaching rate. X-ray diffraction (XRD) patterns show the change of bioleached solid residues and the effect of L-cysteine on the surface charges of minerals. Zeta potential and IR spectra of mineral surface show that the interaction between L-cysteine and mineral leads to the formation of metal complex,which is propitious to the bioleaching of Ni-Cu sulfide by Acidianus manzaensis.

Pressure leaching of zinc silicate ore in sulfuric acid medium

Zinc silicate ore was characterized mineralogically and the results showed that zinc exists mainly as hemimorphite and smithsonite in the sample.Sulfuric acid pressure leaching of zinc silicate ore was carried out to assess the effect of particle size,sulfuric acid concentration,pressure,reaction time and temperature on the extraction of zinc and the dissolution of silica.Under the optimum conditions employed,up to 99.25% of zinc extraction and 0.20% silica dissolution are obtained.The main minerals in leaching residue are quartz and small amounts of undissolved oxide minerals of iron,lead and aluminum are associated with quartz.

Bioleaching of chalcocite by mixed microorganisms subjected to mutation

Mixed microorganisms with elevated activity of chalcocite-leaching were screened by mutation methods. The original microorganisms collected from acid mine drainage of different sites were mixed and then treated with mutagens NO2^- , diethyl sulfate （DES）, UV and their combinations, respectively. Five groups of mixed microorganisms with much stronger ore-leaching ability were obtained by screening on the leaching media. Among them, group E of mixed microorganisms （treated with 1% DES for 60 min） with the best perfonnance on chalcocite-leaching, increases the content of Cu^2＋ by 101.4% in 20 d of leaching compared with the control culture. In addition, group E is more tolerant to Cu^2＋ in media than the control without mutation treatment. Analysis for the diversity of microbial clones indicates that half of operational taxonomic units （OTUs） in group E are Acidithiobacillus ferrooxidans. These observations suggest that group E might have potentials for industrial application.

Molybdenum removal from copper ore concentrate by sodium hypochlorite leaching

The removal of molybdenum from a copper ore concentrate by sodium hypochlorite leaching was investigated. The results show that leaching time,liquid to solid ratio,leaching temperature,agitation speed,and sodium hypochlorite and sodium hydroxide concentrations all have a significant effect on the removal of molybdenum.The optimum process operating parameters were found to be：time,4 h;sodium hydroxide concentration,10%;sodium hypochlorite concentration,8%;liquid to solid ratio,10：1;temperature,50℃;and, agitation speed,500 r/min.Under these conditions the extraction of molybdenum is greater than 99,9%and the extraction of copper is less than 0.01%.A shrinking particle model could be used to describe the leaching process.The apparent activation energy of the dissolution reaction was found to be approximately 8.8 kJ/mol.