Heavy metals in the environment. Part I: Removal of cobalt from dilute effluent streams by fluidised bed electrolysis

The fluidised bed cell is an electrolytic reactor which is designed to provide higher ion-transfer conditions during electrolysis by breaking up the barrier layer at the cathode, thus enabling metals to be removed efficiently from dilute solutions. The effectiveness of the method as a means of removing metals from effluent to meet discharge consent levels is studied for the in-situ removal of cobalt from dilute solution. The effects of cathode density, pH, reaction time, buffer solution composition, buffer concentration and agitation on the removal of cobalt are reported and expressed in terms of the percentage removal of cobalt (α_Co), the efficiency for cobalt deposition (∞_Co), and the energy consumption (W_Co) for 1 kg of cobalt deposited. The results show that cobalt can, under optimised conditions, be removed from dilute solutions to a residual level of 0.2 ppm.     

Removal of copper and cadmium from hydrometallurgical leach solutions by fluidised bed electrolysis

A fluidised bed cell which consists of a bed of inert glass beads, in which are immersed expanded mesh electrodes, is used to provide high ion transfer conditions making it possible to recover metals efficiently from dilute solutions. The use of the cell in the removal of Cu and Cd from dilute solutions is described, and the effects of cathode density, pH, time, type of electrode, distance between the electrodes and presence of other ions in solutions studied. These investigations are then extended to examine the electrolysis of solutions obtained by leaching a copper—zinc calcine.     

Removal of cadmium from dilute aqueous solutions with a rotating cylinder electrode of expanded metal

The removal of cadmium from dilute solutions using a continuous undivided electrochemical reactor with a rotating cylinder cathode of expanded metal is analysed. The effects of cathodic applied potential, size and orientation of expanded metal meshes and inlet cadmium concentration were ascertained. The results show that cadmium can be removed from dilute solutions (inlet concentration range 5–50 mg dm⁻³) with a high fractional conversion of between 35 and 40% depending on the operating conditions. Thus a minimal residual cadmium concentration of 3 mg dm⁻³ was achieved. The specific energy consumption increases from 0.6 to 2 kWh mol⁻¹ as the cadmium concentration decreases. Copyright © 2003 Society of Chemical Industry     

Electrochemical dissolution of tin in methanesulphonic acid solutions

High-rate electroplating of tin on a moving steel strip is generally carried out in cells with dimensionally stable anodes. To obtain a matt tin deposit a concentrated acidic tin methanesulphonate solution containing a small concentration of sulphuric acid is used. The concentrated tin methanesulphonate solution is prepared by dissolution of tin particles with oxygen in a special column. To describe this dissolution process electrode reactions (namely, reduction of oxygen, hydrogen peroxide and hydrogen ions on a tin electrode and oxidation of tin) were studied using electrochemical techniques. It was concluded that on tin, oxygen is almost entirely reduced to water and that H₂O₂ cannot corrode tin directly, but its decomposition products, for instance oxygen, can. The exchange current density and the charge transfer coefficient for the investigated electrode reactions are estimated. The dissolution of tin by oxygen is determined by the kinetic parameters of the oxygen reduction reaction and by the mass transfer of (i) dissolved oxygen to and (ii) Sn²⁺ ions from the tin electrode surface. Hydrogen evolution can be neglected during the dissolution of tin in the presence of oxygen. Moreover, it was found that the rate of tin corrosion increases with (i) increasing H⁺ concentration, (ii) oxygen concentration, (iii) convection intensity and (iv) temperature. It is likely that the tin surface is not covered with oxygen during corrosion in pure methanesulphonic acid solutions, but an oxide layer may be present on the tin surface during oxygen corrosion in pure sulphuric acid solutions. This oxide layer may hinder the oxygen corrosion of tin.     

Separation of the protease enzymes of Bacillus licheniformis from the fermentation medium by crossflow ultrafiltration

The separation from fermentation medium of extracellular serine alkaline protease (SAP) enzyme produced by Bacillus licheniformis was investigated using a crossflow ultrafiltration system. SAP was separated from the high molecular weight neutral protease (NP) and amylase (AMY) enzymes and from the low molecular weight organic acids and amino acids in a crossflow ultrafiltration system with 30 000 Da and 10 000 Da MWCO polysulfone membranes, respectively. The effects of transmembrane pressure (TMP), recirculation velocity (v), and initial enzyme concentration (C_E) on the permeate flux, on the activities of SAP, NP and AMY enzymes, and on the recovery of SAP were investigated. High permeate flux was obtained at high recirculation velocity and TMP, but at low initial enzyme concentration. SAP enzyme recovery and activity measured in the system also showed alterations with hydrodynamic conditions. The best operation conditions for the separation of SAP from NP and AMY were TMP = 20 kPa, v = 0.50 ms⁻¹ and C_E = 0.28 gdm⁻³. The separation of SAP from the organic and amino acids was best performed at TMP = 100 kPa, v = 0.33 ms⁻¹ and C_E = 0.40 gdm⁻³. © 2000 Society of Chemical Industry     

Selective removal of copper ions from multi‐component aqueous solutions using modified silica impregnated with LIX 84

A silica support impregnated with 2‐hydroxy‐5‐nonylacetophenone oxime (LIX 84) was prepared after surface modification by ‐aminopropyltriethoxysilane. Fixed‐bed tests were conducted to investigate the capabilities of the prepared adsorbent with respect to the selective removal of copper ions from multi‐metal solutions. Break‐through curves were obtained using the modified silica for a solution containing Cu²⁺, Cd²⁺, Ni²⁺, Co²⁺ and Zn²⁺, as well as an industrial electronics wastewater sample. The copper adsorption capacities for the multi‐metal solution and the wastewater were 0.175 and 0.198 mmolg⁻¹, respectively under the conditions used in this study. The copper recovery ratios for the modified silica treated with the multi‐metal solution and the wastewater were 86 and 91%, respectively after treating with 0.1 moldm⁻³ HNO₃. The results show that the modified silica, prepared here, has potential value for the selective removal of copper ions from multi‐component aqueous solutions containing multi‐metals using a fixed‐bed reactor. © 2000 Society of Chemical Industry     

Corrosion of tin in aqueous solutions of mono-, Di- and trichloroacetic acids

The corrosion behaviour of tin in stagnant mono-, di- and trichloroacetic acids solutions in the pH range 1–6 and at concentrations 4.0 to 5 × 10^?4 M was investigated. The results indicate behaviour that is generally the same but there is some dependence on the acid concentration and the pH value. In 4.0 to 10^?2 M solutions, the corrosion rate (W) increased with increasing acid concentration and decreasing pH value from 1 to 4 as follows: log W=a+b log C, where b=0.70, 0.42 and 0.35 for tri-, di- and mono-chloroacetic acids respectively. At high concentrations 4.0 to 10^?2 M and in the pH range 1–6, the steady state corrosion potential shifted in the negative direction with increase of acid concentration accompanied by an increase in the corrosion rate, indicating that the corrosion process becomes anodically controlled by the complexing of Sn²⁺ ions with organic acid anions and that the order of aggressiveness is mono-<di-<trichloroacetic acids. In dilute solutions (10^?2 to 5.10^?4 M) in the pH range 1–6 the steady state potential shifted in the noble direction with increase of acid concentration (accompanied by a remarkable decrease in the corrosion rate). Corrosion inhibition in dilute solutions was attributed to film formation on the surface of tin which may result from the hydrolysis of tin species.     

Stannous chloride—an effective reducing agent for the removal of selenium(IV) from acidic solution

BACKGROUND: Selenium removal from aqueous solutions can be a significant industrial problem, particularly in the metallurgical industry. In order to evaluate new reducing agents for this application, the reduction of selenious acid (H₂SeO₃) species with stannous ions (Sn²⁺) from weakly acidic sulfate solutions containing 300 mg L^?1 of selenium at 23 °C was studied. RESULTS: At initial pH values < 1.3 and molar ratio ≥ 2, less than 0.5 µg L^?1 of selenium(IV) remained in solution after reduction. The reductive precipitation reaction started as soon as the stannous ions were added to the selenium‐bearing solution and was completed in less than 5 min. The reaction products, characterized using X‐ray diffraction, electron microscopy, particle and surface area measurements, X‐ray photoelectron spectroscopy and chemical analysis, were composed of approximately equal amounts of tin selenide and tin dioxide. In addition to tin selenide a minor amount of selenium(IV) was found to be removed via adsorption on the tin dioxide formed in situ. Tests with a complex industrial solution also resulted in full and stable selenium precipitation. CONCLUSION: Stannous ions were found to be very effective in removing selenious ions from synthetic and industrial solutions, producing very stable precipitates. Copyright © 2012 Society of Chemical Industry     

Electrodeionisation 3: The removal of nickel ions from dilute solutions

The removal of nickel ions from dilute solutions using a process that combines an ion-exchange bed with electrodialysis has been studied. The main aspects include: the concentration of nickel ions in the diluate, the voltage over the cell and the current density distribution along the ion-exchange bed. The current density distribution provides insight into the state of the bed as it is simultaneously loaded with Ni²⁺ and regenerated with an electric potential difference applied perpendicular to it. A simple model is used to describe the state of the bed and the quantity of nickel removed from it as a function of time. Under specific conditions the precipitation of metal hydroxides is observed in the compartment containing the ion-exchange bed. The results show that hydroxide precipitation is related to the nickel concentration in solution and the electric potential gradient across the bed.     

The role of sulfate as a competitive inhibitor of enzymatically‐mediated heavy metal uptake by Citrobacter sp: implications in the bioremediation of acid mine drainage water using biogenic phosphate precipitant

Heavy metals can be removed from solution via biocrystallization with enzymatically‐liberated inorganic phosphate, according to Michaelis–Menten kinetics, in free whole cells and cells immobilized within polyacrylamide gel in a flow‐through reactor. Sulfate is a competitive inhibitor of phosphate release and a predictive model was developed and shown to describe the effect of sulfate on the efficiency of phosphate release by flow‐through columns. The inhibitory effect was substantially less than anticipated in the case of metal removal by the columns. In the case of lanthanum removal metal removal efficiency was restored by increasing the substrate concentration in accordance with model predictions. In the case of uranyl ion its removal with an equivalent substrate supplement increased the activity by 20% over the initial value at a limiting flow rate. Since the initial loss in activity in the presence of 40 mmol dm⁻³ SO₄²⁻ (approximately twice the K_i value) was only approximately 20% with both metals this was considered to be a minor problem for bioprocess application. In confirmation, calculations made from a published ‘case history’ of application of the system to the bioremediation of acid mine drainage water (AMD) containing 0.22 mmol dm⁻³ of uranyl ion and 35 mmol dm⁻³ of SO showed that the benchscale model is a good representation of performance under actual load conditions. © 1999 Society of Chemical Industry     

Reduction of chromate in dilute solution using hydrogen in a GBC-cell

Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. Hydrogen gas is a very attractive reductant, since its use gives no additional pollution. In this paper the reduction of chromate in a sulphuric acid medium has been studied. A new electrochemical cell, a GBC-cell, which is a combination of a gas-diffusion electrode in direct contact with a packed bed of carbon particles, is introduced. Hydrogen gas flows along the hydrophobic side of the gas-diffusion electrode and a chromate solution is pumped upwards through the bed. Experiments were carried out with H₂SO₄ solutions initially containing 70 mol m^–3 chromate at various temperatures, solution flow rates, H₂SO₄ concentrations and bed thicknesses. Experimental results for the chromate reduction are described by an empirical relation. It has been found that the reduction of chromate is a first-order reaction in chromate and the apparent rate constant for the chromate reduction increases with decreasing chromate concentration and increasing temperature, H₂SO₄ concentration and bed thicknesses and is practically independent of the flow rate of the solution. It is concluded that the new GBC-cell is very attractive for the reduction of chromate in dilute solutions and for industrial abnlication on a large scale.     

Performance evaluation of the anaerobic fluidised bed system: I. Substrate utilisation and gas production

COD removal efficiencies in the range 75 to 98% were achieved in an anaerobic fluidised bed system designed for the recovery of methane from liquid wastes, when evaluated at COD loadings of between 5.8 to 108 kg m^?3 day^?1, hydraulic retention times of between 4.45 to 8 h, and feed COD concentrations of beween 480 to 9 000 mg dm^?3. More than 90% of feed COD could be removed up to COD loadings of about 40 kg m^?3 day^?1. Up to around 300 dm² of methane were produced per kg COD removed and this methane production rate was independent of the COD loadings applied in this investigation. Volatile acid concentration in the reactor increased sharply at a COD loading of about 40 kg m^?3 day^?1 and therefore, sufficient alkalinity should be provided to prevent pH from dropping to the undesirable level. The anaerobic fluidised bed system can be operated at a significantly higher liquid throughputs while maintaining its excellent efficiency.     

Water softening using packed bed of polypyrrole from flowing solutions

Packed bed of polypyrrole/polystyrene sulfonate (PPy/PSS) electrodeposited porous carbon electrode was prepared and used for continuous water softening from flowing artificial hard water solutions. Careful preparation of the packed bed was performed in order to obtain the greatest possible degree of uniformity of the PPy/PSS-within the porous carbon matrix. The porous carbon electrode was of the type, reticulated vitreous carbon (RVC) of grades 20, 45 and 80 PPI. Cyclic voltammetry and scanning electronmicroscopy (SEM) were used to characterize the prepared electrodes. The porous electrode was used in removal of Ca²⁺ ions from flowing 0.0125 M CaCl₂ solution at different conditions. Removal efficiencies of about 10% were obtained at some conditions. This low conversion per pass calls for using multi-electrode systems or recirculation of the solution (filters) to obtain the desired Ca²⁺ and water softening levels. The energy consumption and coulombic efficiency of the overall removal process was determined at a given set of experimental conditions. Regeneration of the PPy bed was affected by the presence of dissolved oxygen in the flowing solutions.     

The two-electron exchange between the <Emphasis Type="Italic">U</Emphasis><Superscript>–</Superscript> tin centers in crystal and glass-like chalcogenide semiconductors

The two-electron exchange between neutral and doubly ionized U ^– tin centers in the partially compensated Pb_0.96Sn_0.02Na_0.01Tl_0.01S hole solid solutions in the temperature range of 80–900 K and in the partially compensated Pb_0.965Sn_0.015Na_0.01Tl_0.01Se hole solid solutions in the temperature range of 80–600 K was studied by ^119mm Sn(^119m Sn) Mössbauer spectroscopy. The activation energy of this process for the Pb_0.96Sn_0.02Na_0.01Tl_0.01S solid solutions is comparable with the depth of the tin energy levels in the PbS band gap and amounts to 0.11(2) eV, while in the Pb_0.965Sn_0.015Na_0.01Tl_0.01Se solid solutions it is comparable with the correlation energy of the donor U ^– tin centers in PbSe and amounts to 0.05(1) eV. It is established that the exchange is implemented by the simultaneous transfer of two electrons with the valence band states involved. In the glass-like (As₂Se₃)_0.3(GeSe)_0.6(SnSe)_0.1 alloy containing quadruply charged six-coordinated tin (singly ionized donor center) and doubly charged three-coordinated tin (singly ionized acceptor center), no traces of the electronic exchange between differently charged tin states was observed up to a temperature of 480 K, which is explained by the fact that the doubly charged and quadruply charged tin centers are in different coordination states.     

A study on the removal of urea from aqueous solution with immobilized urease and electrodialysis

A five-compartment electrodialyzer with immobilized urease was developed for the removal of urea from aqueous solution. The immobilized urease, supported on polyurethane foam, was placed in the central (dilute) compartment, where urea was hydrolyzed and the products NH₄⁺ and CO₃^2-/HCO₃^? were removed simultaneously by electrodialysis. The system was studied both under constant current and under constant voltage. The effects of urea concentration and applied current or voltage on the removal of urea and ammonium ions from the dilute solution were investigated. The variations of the pH of dilute solution, the current or voltage of system, and current efficiency were also examined during reaction-electrodialysis. The removal of urea by enzymic reaction was not affected significantly by the applied electric field. The current effieiencies for removing ammonium ions from dilute solution were mostly within 40-80%, and the removal percentage of ammonium ions was dependent on current density and current efficiency.     

Structural studies of electrodeposited tin—cobalt alloys

The cast tin—cobalt alloys γ′Co₃Sn₂ (hexagonal) and CoSn₂ (tetragonal) were prepared and studied using Mössbauer and X-ray measurements. These results were used in the indentification of the components of electrodeposited tin—cobalt alloys obtained from mildly alkaline sulphate baths. γ′Co₃Sn₂ (hexagonal), CoSn (cubic) and metallic tin were detected as components of the electrodeposited alloys. The relative amounts of the components is highly dependent on the bath operation conditions, and no γ′Co₃Sn₂ was observed when the concentration of electroactive tin in the plating bath was high. The Mössbauer parameters of all the studied alloys are given and are well within the observed values for binary tin alloys.     

Improvement of water quality using alginate/montmorillonite composite beads

The aim of this study is to explore naturally occurring sorbents that have high affinity for heavy metal treatment. In this respect, series of polymer‐clay composite beads that consists of Na‐alginate and montmorillonite clay were prepared using CaCl₂ as crosslinker. The prepared composite bead was characterized by scanning electron microscope (SEM). Removal of lead from aqueous solution using this bead was then studied in batch adsorption experiments. The amount of lead removed was found to increase as the percent of Na‐alginate increase in the composite beads. The experimental results also showed that the equilibrium contact time was obtained within ∼ 100 min with (t_1/2) of 50% adsorption in less than 10 min. Lead adsorption was found to be strongly pH‐dependent and display a maximum uptake capacity (244.6 mg/g) at pH 6 and minimum uptake (76.6 mg/g) at pH 1. Maximum lead adsorption was found to increase with increasing initial lead concentration in the feed solution and with decreasing temperature of experiment. Based on alginate‐montmorillonite beads packed columns, a highly efficient method for Pb(II) removal from aqueous solution was developed. The effect of flow rate on adsorption of 100 mg/L Pb(II) in the packed‐bed column was investigated by changing the flow rate between 0.5 and 2.5 mL min⁻¹. The recovery of 100 mg/L Pb(II) in the packed‐bed column was found to be 100% at flow rates 0.5 and 1 mL min⁻¹ then lowered to be 93% and 84% at flow rates 1.5 and 2.5 mL min⁻¹, respectively. The effect of Pb(II) flow concentration ranging from 10 to 1000 mg/L on the adsorption of lead ions at constant flow rate 1.0 mL min⁻¹ was also studied using column procedure. Technical feasibility for the uses of the prepared composite beads for the treatment of actual polluted wastewater samples collected from some industrial cities in Egypt was investigated. The evaluation of the system was performed by a complete analysis of heavy metals in the wastewater samples before and after the treatment process. The results showed a promising possibility for producing wastewater of better quality using such prepared beads. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ionic conductivity of Mn2+ doped dense tin pyrophosphate electrolytes synthesized by a new co-precipitation method

Mn²⁺-doped Sn_1−xMn_xP₂O₇ (x = 0–0.2) are synthesized by a new co-precipitation method using tin(II)oxalate as tin(IV) precursor, which gives pure tin pyrophosphate at 300 °C, as all the reaction by-products are vaporizable at <150 °C. The dopant Mn²⁺ acts as a sintering aid and leads to dense Sn_1−xMn_xP₂O₇ samples on sintering at 1100 °C. Though conductivity of Sn_1−xMn_xP₂O₇ samples in the ambient atmosphere is 10⁻⁹–10⁻⁶ S cm⁻¹ in 300–550 °C range, it increases significantly in humidified (water vapor pressure, pH₂O = 0.12 atm) atmosphere and reaches >10⁻³ S cm⁻¹ in 100–200 °C range. The maximum conductivity is shown by Sn_0.88Mn_0.12P₂O₇ with 9.79 × 10⁻⁶ S cm⁻¹ at 550 °C in ambient air and 2.29 × 10⁻³ S cm⁻¹ at 190 °C in humidified air. It is observed that the humidification of Sn_1−xMn_xP₂O₇ samples is a slow process and its rate increases at higher temperature. The stability of Sn_1−xMn_xP₂O₇ samples is analyzed.     

Magnetic Properties of Mn‐doped SnO2 Thin Films Prepared by the Sol–Gel Dip Coating Method for Dilute Magnetic Semiconductors

Manganese‐doped tin oxide (SnO₂:Mn) thin films were deposited on glass substrates by the sol–gel dip coating technique. The effect on structural, morphological, magnetic, electrical, and optical properties in the films with different Mn concentrations (0–5 mol%) were investigated. X‐ray diffraction patterns (XRD) showed the deterioration of crystallinity with increase in Mn‐doping concentration. Scanning electron microscopy (SEM) studies showed an inhibition of grain growth with an increase in Mn concentration. X ray photoelectron spectroscopy (XPS) revealed the presence of Sn⁴⁺ and Mn³⁺ in SnO₂: Mn films. SnO₂: Mn films show ferromagnetic and paramagnetic behavior. These SnO₂:Mn films acquire n‐type conductivity for 0–3 mol% (SnO₂ ‐ Sn_0.97Mn_0.03O_{2) ‐}doping concentration and p type for 5 mol% Mn‐doping concentration(Sn_0.95Mn_0.05O₂) in SnO₂ films. An average transmittance of > 75% (in UV‐Vis region) was observed for all the SnO₂:Mn films. Optical band gap energy of SnO₂: Mn films were found to vary in the range 3.55 to 3.71 eV with the increase in Mn‐doping concentration. Photoluminescence (PL) spectra of the films exhibited an increase in the emission intensity with increase in Mn‐doping concentration which may be due to structural defects or luminescent centers, such as nanocrystals and defects in the SnO₂. Such SnO₂:Mn films with structural, magnetic and optical properties can be used as dilute magnetic semiconductors.     

Dehydrating Effect of Concentrated Aqueous Alkaline Solutions in Aliphatic Nucleophilic Substitutions Carried out in Aqueous-Organic Two-Phase Systems. The Different Behavior of Various Phase-Transfer Catalysts: Quaternary Salts,Crown Ethers and Cryptands

Concentrated aqueous NaOH and KOH solutions affect the hydration and hence the reactivity of anions (Cl⁻, Br⁻, I⁻, SCN⁻, N⁻₃) in aliphatic nucleophilic substitutions catalyzed by lipophilic quaternary onium salts, cryptands and crown ethers under phase-transfer (PTC) condtions. In the presence of aqueous 50% NaOH or 53% KOH non-hydrated anions are transferred from the aqueous into the organic phase by quaternary salts. The anionic reactivity thus becomes identical to that found under anhydrous homogeneous conditions in non-polar organic media. Unlike quaternary salts, in the presence of cryptates water is not completely removed even at the highest KOH concentration, i.e. conditions in which aH₂O ∼ 0. Residual hydration depends on the nature of the anion and is the highest for anions with localized and/or less polarizable charge, such as Cl⁻, Br⁻ and N⁻₃. As a consequence, rate constants noticeably increase in comparison with those found under conventional PTC conditions, but don't reach those of anhydrous solutions. Behavior of crown ethers is in between that of quaternary salts and cryptates, since residual hydration in the presence of 53% aqueous KOH is lower than that of cryptates, whereas anionic reactivity become practically identical to that found under anhydrous conditions. A comparison of the catalytic efficiency of lipophilic quaternary salts, cryptands and crown ethers under various reaction conditions is also included.