Three-dimensional computational fluid dynamics analysis of an electric submerged arc furnace.

A computational fluid dynamics (CFD) method is proposed to analyze the operation of a submerged electric arc furnace (SAF) used in ferronickel production. A three-dimensional mathematical model was used for the time-dependent solution of the fluid flow, heat transfer and electromagnetic phenomena. The slag's physical properties, which play a crucial role in the SAF operation, were previously determined using classical molecular dynamics simulations and empirical relationships. The analysis revealed that the main slag properties affecting SAF operation are density, viscosity and electrical conductivity-the latter two being mutually dependent. The high electrical conductivity values of the slag favor melting via the high Joule heat produced within the slag region. Calculation of the dimensionless Péclet and Reynolds numbers revealed that the slag velocities play a decisive role in heat transfer and further indicate that the slag flow is laminar. The average slag velocity calculated 0.0001 m/s with maxima in the vicinity of the electrodes.

Continuous Flow Process for Cr(VI) Removal from Aqueous Solutions Using Resin Supported Zero-Valent Iron.

The objective of the present study was to evaluate the performance of a nanocomposite material consisting of nano zero valent iron and a cation exchange resin, for the reduction of chromate, by conducting column tests. A cationic resin, Amberlyst 15, was selected as porous host material. The synthesis of the nanocomposite material (R-nFe) was carried out using Green Tea extract to obtain the reduction of adsorbed Fe(III) to the elemental state Fe(0). Three column tests were implemented with different dimensions, corresponding to variable contact times between the aqueous solution and the resin beads loaded with Fe(0), namely 168, 744 and 1260 s respectively for columns I, II and III. The results indicated that the removal of Cr(VI) follows a first order kinetic law with a chemical constant equal to 0.0526 min-1 (8.8 × 10-4 s-1).

Pragmatic analysis of the electric submerged arc furnace continuum.

A transient mathematical model was developed for the description of fluid flow, heat transfer and electromagnetic phenomena involved in the production of ferronickel in electric arc furnaces. The key operating variables considered were the thermal and electrical conductivity of the slag and the shape, immersion depth and applied electric potential of the electrodes. It was established that the principal stimuli of the velocities in the slag bath were the electric potential and immersion depth of the electrodes and the thermal and electrical conductivities of the slag. Additionally, it was determined that, under the set of operating conditions examined, the maximum slag temperature ranged between 1756 and 1825 K, which is in accordance with industrial measurements. Moreover, it was affirmed that contributions to slag stirring due to Lorentz forces and momentum forces due to the release of carbon monoxide bubbles from the electrode surface were negligible.

Comparative evaluation of five plant extracts and juices for nanoiron synthesis and application for hexavalent chromium reduction.

The effectiveness of five plant extracts and juices, i.e. extracts of Camellia sinensis (green tea, GT), Syzygium aromaticum (clove, CL), Mentha spicata (spearmint, SM), Punica granatum juice (pomegranate, PG) and Red Wine (RW), for the production of nanoiron suspensions and their application for Cr(VI) reduction was investigated. Polyphenols contained in extracts act as reducing agents for iron ions in aqueous solutions, forming thus iron nanoparticles, and stabilize the nanoparticles produced from further oxidation and agglomeration. The maximum amount of polyphenols extracted per g of herbs was obtained at herb mass to water volume ratio varying from 10 to 20g/L. Suspensions of nanoparticles with sizes below 60nm were produced by mixing iron chloride solution with the plant extracts and juices investigated. The maximum concentration of nanoiron in suspensions was estimated to 22mM, obtained using RW and PG at a mixing ratio of iron solution to extract equal to 2. Lower concentrations, up to 18mM, were achieved using GT and CL extracts. Therefore, PG juice and RW were considered as more effective for nanoiron production, and, together with GT extracts, they were selected for the production of nanoiron suspensions, which have been proven effective for Cr(VI) reduction, reaching removal capacity as high as 500mg Cr(VI) per g of iron in nanoparticles.

Incineration of tannery sludge under oxic and anoxic conditions: study of chromium speciation.

A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of oxygen. Incineration in oxic conditions was performed at the temperature range from 300°C to 1200°C for duration of 2h, while in anoxic conditions at the temperature range from 400°C to 600°C and varying durations. Incineration under oxic conditions at 500°C resulted in almost total oxidation of Cr(III) to Cr(VI), with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was reduced, mainly due to the formation of MgCr2O4. At 1200°C approximately 30% of Cr(VI) was reduced to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no chromium containing crystalline phase was detected.

Forensic investigation of a chromium(VI) groundwater plume in Thiva, Greece.

A forensic investigation was conducted with the aim of decoupling the contribution of geogenic and anthropogenic Cr(VI) sources in the wider area of Thiva. Groundwater and topsoil samples were collected from two Cr(VI) groundwater plumes of 160 µg/L and 75 µg/L. A series of evidence support the view that the origin of Cr(VI) detected in groundwater is mainly geogenic. These are: (a) the presence of Cr in topsoil of the wider area, (b) the moderate Cr(VI) groundwater concentrations, (c) the high Ni levels within the Cr(VI) plumes, (d) the predominance of Mn(IV), which is a prerequisite for Cr(III) oxidation to Cr(VI), and (e) the absence of co-contaminants. The present study also revealed that, although both Cr(VI) plumes are clearly of geogenic origin, the plume with the elevated Cr(VI) values, in the north of Thiva town, exhibits also an anthropogenic component, which can potentially be attributed to the alkaline environment associated with the old uncontrolled landfill of Thiva and the industrial cluster located in this area.

Assessment of polyphenol coated nano zero valent iron for hexavalent chromium removal from contaminated waters.

Alternative plant extracts were examined as raw materials for the synthesis of nZVI from ferric solutions. Four plants were selected for evaluation, i.e. Camellia sinensis (green tea, GT), Syzygium aromaticum (clove, CL), Mentha spicata (spearmint, SM) and Punica granatum (pomegranate, PG). Based on the results obtained, it was concluded that the reduction of Fe(III) with the herb extracts is not complete. Using the GT extract, approximately 28 mM of the initial 66 mM of Fe (42.4 %) are reduced to the elemental state Fe(0). The highest reduction of Fe(III), about 53 %, was achieved with PG and the lowest, only 15.6 %, with the SM extract. Additional batch experiments have been carried out to evaluate the effectiveness of nZVI, synthesized with GT, CL, SM and PG, for the removal of hexavalent chromium from a 0.96 mM solution. The highest reduction of Cr(VI) (96 %) was obtained using the nZVI suspension produced with PG juice. The other three nZVI suspensions, i.e. CL-nZVI, GT-nZVI, and SM-nZVI, had a comparable effectiveness corresponding to 70 % reduction of chromate.

Column study for the evaluation of the transport properties of polyphenol-coated nanoiron.

Injection of a nano zero valent iron (nZVI) suspension in the subsurface is a remedial option for obtaining the in situ reduction and immobilization of hexavalent chromium in contaminated aquifers. Prerequisite for the successful implementation of this technology is that the nanoparticles form a stable colloidal suspension with good transport properties when delivered in the subsurface. In this study we produced stable suspensions of polyphenol-coated nZVI (GT-nZVI) and we evaluated their transport behavior through representative porous media. Two types of porous materials were tested: (a) silica sand as a typical inert medium and (b) a mixture of calcareous soil and sand. The transport of GT-nZVI through the sand column was effectively described using a classic 1-D convection-dispersion flow equation (CDE) in combination with the colloid filtration theory (CFT). The calculations indicate that nZVI travel distance will be limited in the range 2.5-25cm for low Darcy velocities (0.1-1m/d) and in the order of 2.5m at higher velocities (10m/d). The mobility of GT-nZVI suspension in the soil-sand column is lower and is directly related to the progress of the neutralization reactions between the acidic GT-nZVI suspension and soil calcite.

A XAFS study of plain and composite iron(III) and chromium(III) hydroxides.

Reduction of hexavalent Cr(VI) to the trivalent state is the common strategy for remediation of Cr(VI) contaminated waters and soils. In the presence of Fe the resulting compounds are usually mixed Fe(III)-Cr(III) phases, while, under iron-free conditions, reduction leads to formation of plain Cr(III) hydroxides. Environmental stability of these compounds depends on their structure and is important to understand how different precipitation conditions affect the local atomic order of resulting compounds and thus their long term stability. In current study, typical Cr(VI) environmental remediation products, i.e. plain and mixed Fe(III)-Cr(III) hydroxides, were synthesized by hydrolysis and redox reactions and their structure was studied by X ray diffraction and X ray absorption fine structure techniques. Plain Cr(III) hydroxide was found to correspond to the molecular formula Cr(OH)3·3H2O and was identified as crystalline in XRD. However, the same compound when examined by EXAFS did not exhibit any clear local order in the range of EXAFS detectable distances, i.e. between 0 and 5Å. Namely, EXAFS spectroscopy detected only contribution from the first nearest neighboring (Cr-O) shell, suggesting that CrO6 octahedra interconnection is loose, in accordance with the suggested anti-bayerite structure of this compound. Mixed Fe(III)-Cr(III) systems resembled 2-line ferrihydrite irrespective of the synthesis route. Analysis of Fe-K-EXAFS and Cr-K-EXAFS spectra indicated that FeO6 octahedra are bonded by sharing both edges and corners, while CrO6 octahedra seem to prefer edge sharing linkage. EXAFS data also suggest that Fe-Cr hydroxide produced by hydrolysis presents a better arrangement of CrO6 octahedra compared to the redox product.

Atomic order and cluster energetics of a 17 wt% Si-based glass versus the liquid phase.

Aerodynamic levitation of a multicomponent 17 wt% Si glass formed by rapid quenching of the melt phase was studied by high resolution x-ray diffraction (XRD) and reverse Monte Carlo (RMC) modelling. The main local atomic order features comprised interactions between Si, Fe and Mg polyhedra, the stereochemistry of which was on a par with the literature. Both the glass and the liquid state appeared to consist of the same fundamental Si-O, Fe-O and Mg-O clusters, with only the relative number of each varying between the two. Transition from liquid to glass involved a three-fold decrease in uncoordinated O (to within the first minimum of the total g(r)) and a marked increase of Fe-Si-Mg polyhedra bridging O. Octahedral Fe coordination was not suggested by the RMC data. All-electron open-shell density functional theory (DFT) calculations of the most prominent clusters suggested independence between the Fe oxidation state and its polyhedra O-coordination. Of secondary thermodynamic importance were indications of network-forming Fe(2+) and Fe(3+) distorted trigonal and tetrahedral polyhedra. In all occasions, the Fe ferrous and ferric states involved comparable binding energies within similar clusters which indicate a dynamic equilibrium between the two.

The effectiveness of municipal sewage sludge application on the stabilization of Pb, Zn, and Cd in a soil contaminated from mining activities.

The effectiveness of municipal sewage sludge for the stabilisation of Pb, Zn and Cd in a heavily contaminated soil was evaluated by performing pot experiments on soil-sludge mixtures. The soil sample originated from the Montevecchio mining district, Sardinia, Italy, and presented high Pb, Zn and Cd content, as well as US EPA TCLP solubility values for Pb and Cd, which exceeded the respective regulatory limits. Sewage sludge application increased the soil pH. Stabilisation experiments showed that 10% w/w sewage sludge addition effectively reduced Pb and Cd solubilities below the TCLP regulatory limits. At the same addition rate, the EDTA extractable fraction of Pb, Zn, Cd in the treated soil was reduced by 12, 47 and 50% respectively compared with the untreated sample. The five-stage sequential extraction procedure applied on the untreated and treated soil samples, showed a remarkable shift of the metals towards more stable forms. The reducible fractions of Zn and Cd and the residual fraction of Pb were increased by 12, 20 and 18% respectively, while a corresponding decrease in the mobile fractions (exchangeable and carbonate) occurred which accounted for 14, 23 and 25% respectively.

The use of municipal sewage sludge for the stabilization of soil contaminated by mining activities.

The ability of municipal sewage sludge to immobilize Pb, Zn and Cd contained in contaminated soil originating from a former mining area in Lavrion, Greece was investigated. The soil was cured with sewage sludge in various proportions. The stabilization was evaluated primarily by applying chemical tests and complemented by the performance of additional biological tests. Application of the U.S. EPA Toxicity Characteristic Leaching Procedure (TCLP) on the stabilized mixtures proved that Pb, Zn and Cd solubility was reduced by 84%, 64% and 76%, respectively, at 15% w/w sludge addition, while a 10% w/w addition was sufficient to reduce Pb solubility below the U.S. EPA TCLP regulatory limit. The results of the extraction using EDTA solution showed the same trend, resulting in 26%, 36% and 53% reduction in the Pb, Zn and Cd extractable fractions, respectively. Speciation analysis of the treated soils revealed a significant decrease in the mobile fractions of heavy metals, which was attributed to their retention in sewage sludge by adsorption and organic complexation mechanisms. For the assessment of possible phytotoxicity, experiments including growing dwarf beans in the treated soil was carried out. It was found that sewage sludge addition had a positive effect on plant growth. Furthermore, the Pb and Zn uptake of plant leaves and roots was reduced, while Cd uptake was unaffected by the sludge treatment. The results of this study support the hypothesis that municipal sewage sludge is a potential effective stabilizing agent for contaminated soil containing Pb, Zn and Cd.