Selective and direct sorption of zirconium from acidic leach liquor of zircon concentrate by rice bran

A new method for extraction of zirconium from leach liquor of zircon concentrate is proposed. The procedure is based on the adsorption of Zr(IV) ions on rice bran. The sorption capacity of the biomass for zirconium is 50 mg g^?1. Adsorption equilibrium was achieved in less than 1 min and slightly affected by solution acidity. In the optimum conditions, the adsorption efficiencies of other associated metal ions such as Ti⁴⁺, Fe³⁺, Al³⁺, La³⁺, Ce³⁺ were significantly lower than Zr(IV) ion and this biomass is excellent sorbent for the selective uptake of zirconium from acidic aqueous solutions.     

Application of ocean manganese nodules for the adsorption of potassium ions from seawater

Extracting potassium from seawater has great economic potential, although conventional methods offer low separation capacity and selectivity. In this study, a series of novel potassium ionic sieves (PISs) were synthesized using ocean manganese nodules (OMN) as raw materials. The PISs were characterized by XRD, SEM, and nitrogen adsorption–desorption. The potassium adsorption capacities and separation factors of PISs and OMN in KCl solution and sea brine showed that KMnO₄ treatment will result in the highest adsorption and separation performance. The resulted sample OMN-C exhibit major composition of birnessite-type potassium manganese oxides and high micropore volumes. The adsorption capacities of OMN-C to K⁺ in KCl solution and sea brine were 35.2 mg g⁻¹ and 22.1 mg g⁻¹, respectively. The separation factor of OMN-C was α(K⁺/Na⁺) = 108.6 and the sieve did not adsorb Mg²⁺, indicating its relatively high separation selectivity to K⁺. Therefore, OMN-C can selectively extract potassium from sea brine effectively. This study not only utilized the abundant OMN resources, but also prepared effective PISs, which showed great potential in the utilization of seawater.     

Froth zone characterization of an industrial flotation column in rougher circuit

In this investigation the froth zone of an industrial column (4 m “diameter” × 12 m “height”) in rougher circuit was characterized. Experiments were carried out at Miduk copper concentrator, Iran. Miduk is a unique copper processing plant which utilizes columns in rougher circuit. Cleaning and selectivity actions in the rougher froth were illustrated using solids and grade profiles along with RTD data. The impact of froth depth (FD) on overall rate constant (k) and k–S_b relationship was evaluated. Dependency of overall flotation kinetics on froth depth and gas velocity (J_g) was modeled by k = 4.97(FD)^?0.87(J_g)^0.80. Froth recovery (R_f) was estimated and modeled in terms of froth residence time of slurry (FRT_Slurry) as R_f = R_f,maxexp(?k × FRT_Slurry). Finally, the correlation between k, S_b (indicative of the collection zone performance) and FRT_Slurry (indicative of the froth zone performance) was modeled by k = 0.02 (FRT_Slurry)^?0.62(S_b)^0.82.     

Biological treatment of wastewater produced during recycling of spent lithium primary battery

Wastewater produced during recycling of spent lithium primary battery was biologically treated with Acidithiobacillus ferrooxidans to decrease the pH and metal concentration. Since the wastewater contains high concentrations of Cr, Ni, and Li, the effects of these metals on the bacterial activity in a 9 K medium were also investigated. Samples of the medium with different metal concentrations were treated, and the oxidation ratio of Fe²⁺ ions was measured to examine the activity of bacteria. In the treatment of simulated wastewater, the presence of Cr and Ni ions with concentrations of 8000 g m^?3 and 13,000 g m^?3, respectively, did not inhibit the bacterial activity, whereas the oxidation ratio of Fe²⁺ ions was observed to be low in the medium when Li ion was present with a concentration at 5000 g m^?3. This observation suggested that at this concentration, Li ion suppressed the bacterial activity. In the case of treatment of real wastewater containing Cr, Ni, and Li, the oxidation ratio of Fe²⁺ to Fe³⁺ was observed to be low while the Fe concentration and pH decreased to 21,633 g m^?3 and 1.8, respectively. Thus, the wastewater produced during the recycling of spent lithium primary batteries can be effectively treated biologically for re-circulating in the recycling process.     

Zinc precipitation by heavy-metal tolerant sulfate-reducing bacteria enriched on phosphogypsum as a sulfate source

In the present study, heavy-metal tolerance and precipitation by a mixed culture of sulfate-reducing bacteria (SRB) were evaluated. These bacteria have been enriched during a previous study from a sewage sludge using phosphogypsum as sulfate source. Taking into account that both sulfate and zinc are naturally occurring in phosphogypsum, zinc tolerance of SRB was tested in synthetic media containing 20 mM sulfate and zinc chloride at concentrations ranging from 0 to 200 mg L⁻¹. Zinc tolerance was determined by bacterial growth susceptibility and zinc removal monitoring. Bacterial growth and sulfate reduction were possible between 10 and 150 mg L⁻¹ of initial zinc concentration. Zinc concentrations more than 150 mg L⁻¹ were lethal to SRB. Zinc was removed effectively by SRB to less than 5% from medium containing 150 mg L⁻¹ initial zinc concentrations or less. Energy-dispersive X-ray analysis showed that precipitation of zinc occurred in the form of sulfide. The results presented in this paper have shown that this mixed culture might be of use for bioremediation of sulfate and heavy-metals containing wastewaters.     

Biosorptive removal of Cd and Zn from liquid streams with a Rhodococcus opacus strain

The biosorption abilities of Rhodococcus opacus were studied for cadmium and zinc removal for liquid aqueous streams. The influence of pH, initial metal concentration and time removal were evaluated on the biosorption studies, in a batch scale basis. The Cd²⁺ and Zn²⁺ species uptake capacity by R. opacus has been also compared using Langmuir and Freundlich models. At pH 7.0 and 26 °C C, Cd²⁺ removal achieved a value around 60% from an initial concentration of 15 ppm. On the other hand, Zn removal achieved a value around 88% from an initial concentration of 5 ppm. Kinetics studies revealed that the biosorption process followed a pseudo-second order model for the two metal species (Cd²⁺ and Zn²⁺) and the kinetic constants were 3.90 and 3.37 g mg⁻¹ min⁻¹, for an initial concentration of 15 and 5 ppm for cadmium and zinc, respectively. The results showed that the R. opacus is a potential engineering biosorbent for environmental and extractive metallurgy sustainable applications.     

Simultaneous determination of iron and copper in pregnant liquid solutions

A new method for the determination of Fe_Total and Cu is proposed. The method is based on the formation of the iron and copper complexes with 5-sulfosalicylic acid (SSA), the optimal conditions were found, using SSA 5.1 g L⁻¹ in the presence of ammonia 7.5 g L⁻¹ (pH = 10). Under these conditions the selected analytical wavelengths were 488.5 and 423.5 nm for the determination of iron and copper, respectively, by using the zero crossing approach. The detection and quantification limits were 0.02 mg L⁻¹ and 0.07 mg L⁻¹ for iron and 1.14 mg L⁻¹ and 3.80 mg L⁻¹ for copper. The proposed method was applied to the determination of both analytes in pregnant liquid solutions and the recovery was between 98% and 100% and in all cases the relative standard deviation was minor to 2%.     

Heavy metals removal from solution by palygorskite clay

The possible use of palygorskite clay, mined in the Dwaalboom area of the Northern Province of South Africa, as an adsorbent for the removal of metal ions such as lead, nickel, chromium and copper from aqueous solution, was investigated. In this work, adsorption of these metals onto palygorskite has been studied by using a batch method at room temperature. The results of adsorption were fitted to both the Langmuir and Freundlich models. Satisfactory agreement between experimental data and the model-predicted values was expressed by the correlation coefficient (R²). The Langmuir model represented the sorption process better than the Freundlich one, with correlation coefficient (R²) values ranging from 0.953 to 0.994. The adsorption capacity (Q₀) calculated from the Langmuir isotherm was 62.1 mg Pb(II) g⁻¹, 33.4 mg Ni(II) g⁻¹, 58.5 mg Cr(VI) g⁻¹ and 30.7 mg Cu(II) g⁻¹ at a pH of 7.0 at 25 ± 1 °C for a clay particle size of 125 μm. Kinetic investigations were performed to investigate the rate of adsorption of metal ions. The Lagergren’s first-order rate constants were calculated for different initial concentrations of metal ions. In batch mode adsorption studies, removal increased with an increase of contact time, adsorbent amount and solution pH. Adsorption of metals from the single-metal solutions was in the order: Pb > Cr > Ni > Cu. Data from this study proved that metal cations from aqueous solution can be adsorbed successfully in significant amounts by palygorskite. This opens up new possibilities and potential commercial uses in the palygorskite market.     

Removal of Mn2+ from aqueous solution by manganese oxide coated zeolite

The preparation, characterization, and adsorption properties of Mn²⁺ by manganese oxide coated zeolite (MOCZ) and its ability in removing Mn²⁺ by adsorption were investigated. Characterization analyses were used to monitor the surface properties (and their changes) of the coated layer and metal adsorption sites on the surface of MOCZ. The adsorption experiments were carried out as a function of solution pH, adsorbent concentration and contact time. Binding of Mn²⁺ ions onto MOCZ was highly pH dependent with an increase in the extent of adsorption with the pH of the media investigated. After the Mn²⁺ adsorption by MOCZ, the medium pH decreased and enhanced with increasing adsorbent concentration. The pseudo-second-order model fitted better among all the kinetic models suggesting that the adsorption mechanism might be a chemisorption process. The equilibrium data showed excellent correlation for both Langmuir and Freundlich isotherm model and this implies both monolayer adsorption and a heterogeneous surface existence in MOCZ. At pH = 6, the Mn²⁺ uptake by MOCZ attained as high as 1.1 meq Mn²⁺ g^?1 at equilibrium. The results suggested that MOCZ presents a fairly good potential as an adsorbent for an efficient removal of Mn²⁺ ions from aqueous solution.     

A simple spectrophotometric method for determination of gold (III) in aqueous samples

A simple method for rapid determination of trace Au in natural water was presented by using UV–vis spectrophotometry after reaction of gold (III) with 3,3′, 5,5′-tetramethylbenzidine hydrochloride (TMBH) in acidic solution. Under the optimum conditions, in a concentration range of 100–2000 μg L^?1 of Au (III) a good linear calibration graph was obtained (r = 0.9969, n = 7). The percent relative standard deviation (RSD) for determination of 1000 μg L^?1 Au was 10% (n = 3) and limit of detection based on a signal-to-noise ratio (S/N) of 3 (3S_bl) was 50 μg L^?1. The proposed method has been successfully applied to the determination of gold spiked and real aqueous samples.     

Solvent extraction of tetravalent hafnium from acidic chloride solutions using 2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (PC-88A)

Solvent extraction of Hf(IV) from acidic chloride solutions has been carried out with PC-88A as an extractant. Increase of acid concentration decreases the percentage extraction of metal indicating the ion exchange type mechanism. The plot of logD vs log[extractant], M is linear with slope 1.8 indicating the association of two moles of extractant with the extracted metal species. Plot of logD vs log[H⁺] gave a straight line with a negative slope of ∼2 indicating the exchange of two moles of hydrogen ions for every mole of Hf(IV). The effect of Cl⁻ ion concentration at constant concentration of [H⁺] did not show any change in D values. Addition of sodium salts enhanced the percentage extraction of metal and follows the order NaSCN > NaCl > NaNO₃ ∼ Na₂SO₄. Stripping of metal from the loaded organic (LO) with different acids indicated sulphuric acid as the best stripping agent. Regeneration and recycling capacity of PC-88A, temperature, extraction behavior of associated elements was studied.     

Hydrodynamic and kinetic characterization of industrial columns in rougher circuit

In the present investigation the relationship between collection zone rate constant (k_c) and gas dispersion parameters, viz. bubble size (d_b), superficial gas velocity (J_g), gas hold-up (ε_g) and bubble surface area flux (S_b) was evaluated. Experiments were conducted in an industrial (4 m in diameter and 12 m high) and a pilot (0.1 m in diameter and 4 m high) flotation column in rougher circuit at Miduk copper concentrator in Iran. Gas hold-up was measured using pressure difference technique and mean bubble sizes were estimated from a drift flux analysis. It was found that the collection zone rate constant was not correlated with d_b and J_g solely but was linearly dependent on ε_g and S_b for the range of interest. Collection efficiency (E_k) and floatability factor (P) in the industrial columns were quantified (E_k = 3.1%; P = 7.7 × 10^?3). The influence of operating parameters comprising superficial gas velocity, slurry solids% and frother dosage/type on S_b and flotation kinetics was discussed. Analysis of available industrial data suggested that S_b and ε_g were related by S_b = 4.46ε_g over the range 30 < S_b < 60 s^?1 and 7% < ε_g < 14%.     

Zinc removal in anaerobic sulphate-reducing liquid substrate process

Zinc and sulphate removal from synthetic wastewater was investigated by using four laboratory parallel upflow-mode reactors (referred as R1 to R4; R1 contained carriers to retain biomass, whereas R2–R4 were operated as suspended reactors). All reactors were inoculated with anaerobically digested cow manure. R1 and R2 were first fed with glucose- and sulphate-containing feed for 48 days after which all four reactors were fed with wastewater containing 50 mg l⁻¹ of zinc in R1–R3 and 200 mg l⁻¹ in R4 and operated for 96 days. In all reactors, hydraulic retention time, organic loading rate, and sulphate load were 5–6 d, 0.2–0.4 kg COD m⁻³ d⁻¹ and 3.3–3.8 g SO₄ l⁻¹ d⁻¹, respectively, whereas the zinc load in R1–R3 was 0.074–0.077 and in R4 0.282 g Zn l⁻¹ d⁻¹. During the runs, 30–40% of sulphate and over 98% of zinc was removed, and up to 150–200 mg H₂S was produced in all reactors. Effluent pH dropped in all reactors (feed pH 6.5) to 3–5 by the end of the experiment. No significant effects on zinc removal were observed, despite differences in operating conditions and feed. It was only in the latter part of the runs (i.e. between experiment days 120–142) that zinc removal began to fluctuate, showing a negligible decrease in R3 and R4, whereas in R1 and R2 zinc was removed below the limit of detection (<0.01 mg Zn l⁻¹). Qualitative X-ray diffraction analysis of the reactor sludge at the end of the runs indicated that the compounds precipitated were most probably ZnS (Code 05-0566 Sphalerite), suggesting metal removal through sulphide precipitation; this was supported by the fact that sulphate was reduced and zinc removed simultaneously.     

Mathematical modeling of thermophilic bioleaching of chalcopyrite

Previous studies have shown that the different preferences of thermophiles to oxidize S⁰ or Fe²⁺ is reflected by different [Fe³⁺]/[Fe²⁺] levels in solution. In those studies it was concluded that [Fe³⁺]/[Fe²⁺] governs the thermophilic bioleaching of chalcopyrite rather than temperature or pH. Therefore, the proposed model is mainly based on the finding that thermophilic bioleaching of chalcopyrite is governed by [Fe³⁺]/[Fe²⁺] that result from the activity of thermophiles. A direct interaction between chalcopyrite and thermophiles is neglected because it has been reported that this is not a general behavior for all thermophiles. The case of constant temperature, initial pH 1.5–2.5, and chalcopyrite concentrates is considered. The main assumption is that chalcopyrite can be anodically oxidized or cathodically reduced depending on [Fe³⁺]/[Fe²⁺] in solution. When chalcopyrite is oxidized at high [Fe³⁺]/[Fe²⁺] levels, Cu²⁺ is formed directly at low rates: CuFeS₂ + 4Fe³⁺ → Cu²⁺ + 5Fe²⁺ + S⁰. Whereas, when chalcopyrite is reduced at low [Fe³⁺]/[Fe²⁺] levels, an intermediate (Cu₂S) is formed at higher rates: CuFeS₂ + Fe²⁺ + Cu²⁺ + 2H⁺ → Cu₂S + 2Fe³⁺ + H₂S. Because the oxidation of Cu₂S is relatively fast: Cu₂S + 4Fe³⁺ → 2Cu²⁺ + S⁰ + 4Fe²⁺, its accumulation is assumed to be negligible. To take into account the possibility of chalcopyrite being oxidized or reduced depending on [Fe³⁺]/[Fe²⁺] in solution, the principle of mixed potentials is used. The model is validated by comparing the calculated and measured values of copper extraction, total iron in solution, and pH.     

Impact of organic carbon on the leachability of vanadium,manganese, iron and molybdenum from shale residues

From 1942 to the 1966, oil was produced by pyrolysis of shale, in Kvarntorp, Sweden. This generated some 40 million m³ of metal rich pyrolyzed shale and discarded fines that were piled on site with its original metal content almost intact. The present study focuses on the leaching of vanadium, manganese, iron and molybdenum from fines after addition of wood chips and steel slag, in outdoor 1 m³ reactor systems at low liquid to solid ratio, in order to evaluate the potential environmental impact and recovery of the elements from the leachates. Seasonal variations were observed, with increased leaching during peak summer. For vanadium and molybdenum, high addition of wood chips decreased the leaching, probably due to adsorption. Manganese showed the opposite behavior while leaching of iron was almost independent of the amount of wood chips. Depending on the systems, up to 2200 μg L⁻¹ vanadium, 90 μg L⁻¹ molybdenum, 25 mg L⁻¹ manganese and 500 mg L⁻¹ iron was found in the aqueous phase. Applied to the 40 million m³ pile, the annual leaching of those elements may reach 14 ton, 0.6 ton, 200 ton and 2400 ton, respectively.     

Oxidation of cyanide in effluents by Caro’s Acid

Caro’s Acid (peroxymonosulphuric acid: H₂SO₅) is a powerful liquid oxidant made from hydrogen peroxide that has been adopted for the detoxification of effluents containing cyanides in gold extraction plants in recent years.The present work reports the findings of a study on the kinetics of aqueous cyanide oxidation with Caro’s Acid. Experiments were conducted in batch mode using synthetic solutions of free cyanide. The experimental methodology employed involved a sequence of two 2³ factorial designs using three factors: initial [CN⁻]: 100–400 mg/L; H₂SO₅:CN⁻ molar ratio: 1–1.5–3–4.5; pH: 9–11; each one conducted at one level of Caro’s Acid strength which is obtained with the H₂SO₄:H₂O₂ molar ratio used in Caro’s Acid preparation of 3:1 and 1:1. The objective was the evaluation of the effect of those factors on the reaction kinetics at room temperature. Statistical analysis showed that the three investigated variables were found to be significant, with the variables which affected the most being the initial [CN⁻] and the H₂SO₅:CN⁻ molar ratio. The highest reaction rates were obtained for the following conditions: H₂SO₅:CN⁻ molar ratio = 4.5:1; pH = 9; and Caro’s Acid strength produced from the mixture of 3 mol of H₂SO₄ with 1 mol of H₂O₂. These conditions led to a reduction of [CN⁻] from an initial value of 400 mg/L to [CN⁻] = 1.0 mg/L after 10 min of batch reaction time at room temperature. An empirical kinetic model incorporating the weight of the contributions and the interrelation of the relevant process variables has been derived as: −d[CN⁻]/dt = k [CN⁻]^1.8 [H₂SO₅]^1.1 [H⁺]^0.06, with k = 3.8 (±2.7) × 10⁻⁶ L/mg min, at 25 °C.     

Solvent extraction and separation of palladium(II) and platinum(IV) from hydrochloric acid medium with dibutyl sulfoxide

The solvent extraction and separation performances of Pd(II) and Pt(IV) from hydrochloric acid solutions were investigated using dibutyl sulfoxide (DBSO) diluted in kerosene. Pd(II) was strongly extracted by a lower concentration DBSO in a lower concentration hydrochloric acid solution while the reverse was obtained for Pt(IV) extraction. Based on independent extraction and separation experiments of Pd(II) and Pt(IV), the separation parameters of Pd(II) and Pt(IV), including dibutyl sulfoxide concentration, contact time of aqueous and organic phases, organic/aqueous (O/A) phase ratio and H⁺ concentration of aqueous phase, were studied in detail, and the optimal separation parameters were obtained and summarized as the following: dibutyl sulfoxide concentration 0.6–1.2 mol dm^?3, organic/aqueous (O/A) phase ratio 0.6–1.0, H⁺ concentration of aqueous phase 1.0–1.5 mol dm^?3 and contact time of two phases 5 min. The as-prepared separation parameters were corroborated by the extraction and separation from a synthetic stock solution containing Pd(II), Pt(IV) as well as several common impurities like Fe(II), Cu(II) and Ni(II). The results revealed that Pd(II) could be separated efficiently from Pt(IV) with a high separation coefficient of Pd(II) an Pt(IV) (2.7 × 10⁴) by predominantly controlling dibutyl sulfoxide and hydrochloric acid concentrations. The extraction saturation capacity of Pd(II) was determined from 1.0 mol dm^?3 HCl solution with 3 mol dm^?3 dibutyl sulfoxide and its experimental value exceeded 14 g dm^?3 under the experimental conditions.Stripping of Pd(II) from loaded organic phase was performed using a mixed aqueous solution containing NH₄Cl and ammonia solutes. Pd(II) (99.2%) was stripped using the stripping solution containing 3% (m/v) NH₄Cl and 5 mol dm^?3 ammonia, respectively.     

Simultaneous oxidation and immobilization of arsenite from refinery waste water by thermoacidophilic iron-oxidizing archaeon,Acidianus brierleyi

The use of a thermophilic acidophilic iron-oxidizing archaeon, Acidianus brierleyi, was investigated for oxidation and immobilization of As(III) from acidic refinery waste water. Some As(III) oxidation was measured in all Ac. brierleyi cultures independently of the presence or concentration of Fe(II) in bulk solution; the exception was at initial Fe(II) concentration ([Fe(II)]_ini) of 1000 mg l⁻¹ where As(III) oxidation became markedly facilitated and consequently approximately 70% of As was immobilized as amorphous ferric arsenate. Providing 1000 mg l⁻¹ Fe(III) instead of Fe(II) did not show the same effect, implying the importance of Fe(III) be microbially-produced and complexed in the archaeal EPS (extracellular polymeric substances) region for effective As(III) oxidation. The reaction towards secondary mineral formation shifted from ferric arsenate to jarosite at [Fe(II)]_ini of >1000 mg l⁻¹. Furthermore addition of jarosite seed crystals retarded the As(III) oxidation rate at [Fe(II)]_ini of 1000 mg l⁻¹. The observations indicate that by setting the appropriate bulk Fe(II)/As(III) ratio in Ac. brierleyi culture to achieve a certain concentration of Fe(III) within the EPS region, but at the same time to avoid jarosite formation, it is possible to maximize the As(III) oxidation rate and thus As immobilization efficiency. This study describes for the first time microbially-mediated simultaneous oxidation and immobilization of As(III) as ferric arsenate, using a thermoacidophilic iron-oxidizing archaeon, Ac. brierleyi.