Modern hybrid sorbents – New ways of heavy metal removal from waters

The possibility of hybrid ion exchanger (HIX) application in the simultaneous removal of heavy metal ions such as Cr(VI), Cu(II) and Zn(II) as well as Cd(II) and Pb(II) was presented. The ion exchanger in question combines the unique properties of hydrated metal oxides with the mechanical and thermal stability of synthetic ion exchangers. The kinetics of the sorption process of Cr(VI), Cu(II) and Zn(II) as well as Cd(II) and Pb(II) in the presence of Cl⁻, NO₃⁻ and SO₄²⁻ as well as EDDS (ethylenediaminedisuccinic acid) was also analyzed. Additionally, the effect of initial concentration, phase contact time and pH was also studied. Taking into account the possibility of its application on a large scale, the parameters of the adsorption process were estimated based on the linear form of the Langmuir and Freundlich isotherms.     

The Extraction Ability and Sensitivity of Porphyrazine Derivatives Towards Some Transition Metal Cations

The synthesis of novel metal-free and magnesium porphyrazines, peripherally substituted with dithia-dioxa (S₂O₂) and tetrathia (S₄) 14-membered macrocycles were performed by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzo-dioxadithiacyclotetradecine-6,7-dicarbodinitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro 2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbodinitrile (5). The metal-free porphyrazines have been obtained by known route. The structure of compounds were characterized by elemental analysis and ¹H, ¹³C NMR, IR, UV-vis, and MS spectral data. The solvent extraction properties of the synthesized compounds towards some metal cations, such as Ag(I), Hg(II), Cu(II), Mn(II), Cr(III), Ni(II), Pb(II), and Zn(II) have been investigated. The effect of Cu²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Sr²⁺, Al³⁺, Zn²⁺, Ba²⁺, Cd²⁺, Co²⁺, Hg²⁺, and Ag⁺ ions on the absorption spectra of the compounds were investigated by means of spectrophotometric method. Magnesium porphyrazine with S₂O₂ (6) interacted within Hg²⁺ ion specifically of all the tested metal ions.     

Heavy metals removal from solution by polyaniline/palygorskite composite

Batch adsorption experiments were carried out to remove heavy metal ions such as Cu (II), Ni (II), Cd (II), and Cr (VI) from single‐metal solutions using a polyaniline/palygorskite (PP) composite. Different parameters affecting the adsorption capacity such as contact time and pH of the solution have been investigated. The structural characteristics of the PP composite were studied in this work. Atomic absorption spectroscopy was used for the measurement of heavy metal contents, and the adsorption capacity (q_e) calculated were 114 mg Cu (II) g^?1, 84 mg Ni (II) g^?1, 56 mg Cd (II) g^?1, and 198 mg Cr (VI) g^?1 under optimal conditions. The removal of the metal ions from solutions was assigned to chelation, ionic exchange, and electrostatic attraction. Data from this study proved that the novel organic/inorganic composite presents great potential in the recovery and elimination of noble or heavy metal ions from industrial wastewater. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

One-pot-solid preparation of novel three-dimensional FexS1-x/g-C3N4 heterostructures for efficient photocatalytic mixed-pollutants removal

In order to overcome the problem of low photocatalytic rate of g-C₃N₄, the 3D Fe_xS_1-x/g-C₃N₄ heterojunction was prepared via a simple one-pot solid method. The X-Ray Diffraction (XRD) and scanning electron microscope (SEM) results demonstrated that the Fe_xS_1-x/g-C₃N₄ heterojunction was established and a g-C₃N₄ nanosheet was tightly bound to Fe_xS_1-x. Compared with g-C₃N₄ samples, Fe_xS_1-x coupling resulted in substantial enhancement of visible light absorption, moreover, the bandwidth of heterojunction was also expanded. In addition to effectively degrading RhB and reducing Cr(VI), the redox performance of Fe_xS_1-x/g-C₃N₄ was also increased in the Cr(VI)/RhB mixed system. Based on a variety of experimental results, the enhanced synergistic photocatalytic activity of the 3D Fe_xS_1-x/g-C₃N₄ heterojunction was attributed to enhancement of the separation of e^- and h⁺ in FeS_2, which resulted from the effective conversion of FeS into FeS₂ under UV-light irradiation. The type II heterojunction structure that was produced via one-pot solid fabrication also inhibited the recombination of electron/hole pairs. Fe_xS_1-x doping and heterojunction building improve the photocatalysis capacity of g-C₃N₄ and broaden the visible-light response of pure g-C₃N₄.     

TiO2 catalysed reduction of Cr(VI) in aqueous solutions under ultraviolet illumination

The photoassisted reduction of Cr(VI) to Cr(III) in aqueous suspensions of TiO₂ under ultraviolet (UV) illumination has been studied by determining the amount of Cr(VI) photoreduced at different irradiation times, the mass of catalyst in suspension, the Cr(VI) initial concentration and the pH. Samples of wastes from metal-surface treatment industries have been used to test this photocatalytic procedure for Cr(VI) elimination in a real ease. It has been observed that the presence in these samples of certain species such as Fe(III) and Cr(III) at low concentrations can increase significantly the yield of Cr(VI) photoreduction. It is assumed that these cations act by maintaining the pH during the photoreduction process, preventing the alkalization by hydrolysis of the solution.     

Preparation of Cr(VI)-imprinted polypropylene nonwoven fibers using plasma polymerization-assisted grafting

Polypropylene (PP) fibers were grafted with glycidyl methacrylate (GMA) using plasma polymerization and then aminated, imprinted, and crosslinked to prepare Cr(VI)-imprinted fibers. The plasma polymerization conditions were optimized by single factor experiment and response surface methodology, and various properties and adsorption mechanism of the fibers were analyzed. The results showed that at pH 3, the imprinted fibers had a maximum Cr(VI) adsorption capacity of 173.36 mg/g, and the adsorption equilibrium could be reached within 40 min. In the presence of competing ions (SO₄²⁻, NO₃⁻ and PO₄³⁻) each at a concentration of 5 times of that of Cr(VI), the Cr(VI) adsorption rate of the fibers could be maintained at around 50%, which indicates that the imprinted fibers have high selectivity towards Cr(VI). The results also showed that the imprinted fibers had good reusability and enrichment ability, thus can be a good candidate for treating actual Cr(VI)-contaminated water.     

Synthesis of Calix[4]arene-Based Thiourea Derivatives for Extraction of Toxic Dichromate and Arsenate Ions

In the environment, the presence of toxic oxyanions such as Cr(VI) and As(V), especially in drinking water, creates serious hazards to human health. For efficient and selective detection of these species; novel calix[4]arene-based thiourea derivatives which obtained using p-tert-butylcalix[4]arene as starting material have been prepared from m-aniline or o-aniline or o-aminophenol in moderate yield. The structures of all new synthesized compounds obtained from these reactions were determined by using FTIR, ¹H, and ¹³C NMR spectroscopy. The complexing properties of calix[4]arene-based thiourea derivatives have been studied towards the As(V) and Cr(VI). It was found that calix[4]arene-based thiourea derivative 5,11,17,23-tetra-tert-butyl-25,27-bis(o-amino-phenylthioureido propoxy)-26,28-hydroxycalix[4]arene is an effective extractant for carrying HCr₂O₇^2? anions.     

Lead(II) in a sulfur-rich environment: Synthesis and molecular structure of the first dinuclear bis(mercaptoimidazolyl)methane complex

The first dinuclear bis(mercaptoimidazolyl)methane metal complex, the lead(II) derivative [Pb₂(Bmm^Me)₅](ClO₄)₄, has been prepared and fully characterized using a combination of analytical and spectroscopic techniques. X-ray crystallography confirmed the presence in the solid state of two dicationic [Pb(Bmm^Me)₂]²⁺ fragments bridged by the fifth Bmm^Me ligand, which uses an unprecedented unidentate:bidentate (μ-κ¹-S:κ²-S,S) coordination mode to link the two metal centers.     

Photocatalytic reduction of chromium and oxidation of organics by polyoxometalates

The photocatalytic reduction of Cr(VI) to the less toxic Cr(III) is presented in the presence of the polyoxometalates (POM) PW₁₂O₄₀³⁻ or SiW₁₂O₄₀⁴⁻ as photocatalyst and an organic substrate (salicylic acid or propan-2-ol) as electron donor. Cr(VI), as dichromate, is reduced to Cr(III), according to the 6:1 stoichiometry of PW₁₂O₄₀⁴⁻ versus Cr₂O₇²⁻ indicated from experiments in the dark. Increase of POM or salicylic acid (SA) concentration accelerates, till a saturation value, both the reduction of metal and the oxidation of the organic, suggesting that these two conjugate reactions act synergistically. The photocatalytic action of POM is not so important in the case of highly concentrated solutions of organics that exhibit direct photochemical reduction of Cr(VI), i.e. propan-2-ol (i-prOH), while it becomes important at low concentrations of i-prOH, especially for organics that do not react directly photochemically with Cr(VI), such as SA. Increase of Cr(VI) concentration enhances consumption of SA and Cr(VI) till an optimum value, due to inner filter effect. The method is suitable for a range of chromium concentration from 5–100 ppm achieving complete reduction of Cr(VI) to Cr(III) up to non-detected traces (>98%). The presence of oxygen does not influence the efficiency of SA and Cr(VI) consumption. In contrast to the semiconductor-based heterogeneous photocatalysis, the POM-based homogeneous process seems superior in the frame that: (i) it remains catalytic throughout illumination by providing more active sites and (ii) among the two POM used, the one that is more efficient in the degradation of the organic, that is PW₁₂O₄₀³⁻ compared to SiW₁₂O₄₀⁴⁻, is also more efficient in reducing Cr(VI), due to a kinetic effect, and a compromise is not needed.     

Extraction equilibria of chromium(VI) from sulfuric acid solutions with tri-n-octylphosphine oxide

The extraction equilibria of chromium(VI) from sulfuric acid solutions with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene at 25°C have been studied. The possible complexes of chromium(VI) with TOPO in organic phase and extraction constants were determined by best fitting the distribution coefficient expression of Cr(VI) with experimental data using the Rosenbrock method. The extraction reactions, including the equilibria among seven species in aqueous phase (H₂CrO₄, HCrO₄⁻, HCr₂O₇⁻, Cr₂O₇²⁻, CrSO₇²⁻, HSO₄⁻ and SO₄²⁻) and five possible complexes in organic phase (H₂CrO₄·(TOPO), H₂Cr₂O₇·(TOPO)₃, H₂CrSO₇·(TOPO)₃, H₂SO₄·(TOPO)₂ and (H₂SO₄)₂·(TOPO)₂) were proposed. The influence of initial sulfuric acid concentration on the fraction of extracted complexes and on the distribution coefficients of Cr(VI) is discussed. This result was helpful for the clarification of the extraction reactions of Cr(VI). © 1998 Society of Chemical Industry     

Coals as sorbents for the removal and reduction of hexavalent chromium from aqueous waste streams

The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g⁻¹. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca²⁺, Ba²⁺, Zn²⁺, Cd²) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.     

Simutaneous Removal of Heavy Metal Ions from Wastewater by Foam Separation Techniques

Abstract

The objective of the present work is to extend the application of adsorbing colloid flotation techniques to remove mixtures of metal ions. The systems studied are: 1) Co(II) and Cr(VI); 2) Co(II), Ni(II), and Cr(VI); 3) Cr(VI), Cu(II), and Zn(II); 4) Cr(VI), Cu(II), Zn(II), and Ni(II); 5) Cd(II), Pd(II), and Cu(II). Ferric hydroxide and aluminum hydroxide were used as the coprecipitant, and sodium lauryl sulfate was used as the collector and frother. The ionic strength of the solution was adjusted with NaNO₃ or Na₂SO₄. It was found that all the heavy metals can be removed effectively by a single step foam flotation treatment.     

Chemical and electrochemical considerations on the removal process of hexavalent chromium from aqueous media

Two methods were used to remove Cr(VI) from industrial wastewater. Although both are based in the same general reaction: 3Fe(II)_(aq) + Cr(VI)_(aq) ; 3Fe(III)_(aq) + Cr(III)_(aq) the way in which the required amount of Fe(II) is added to the wastewater is different for each method. In the chemical method, Fe(II)_(aq) is supplied by dissolving FeSO₄ · 7(H₂O)_(s) into the wastewater, while in the electrochemical process Fe(II)_(aq) ions are formed directly in solution by anodic dissolution of an steel electrode. After this reduction process, the resulting Cr(III)_(aq) and Fe(III)_(aq) ions are precipitated as insoluble hydroxide species, in both cases, changing the pH (i.e., adding Ca(OH)_2(s)). Based on the chemical and thermodynamic characteristics of the systems Cr(VI)–Cr(III)–H₂O–e^– and Fe(III)–Fe(II)–H₂O–e^– both processes were optimized. However we show that the electrochemical option, apart from providing a better form of control, generates significantly less sludge as compared with the chemical process. Furthermore, it is also shown that sludge ageing promotes the formation of soluble polynuclear species of Cr(III). Therefore, it is recommended to separate the chromium and iron-bearing phases once they are formed. We propose the optimum hydraulic conditions for the continuous reduction of Cr(VI) present in the aqueous media treated in a plug-flow reactor.     

High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr₂O₃ is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr)₂O₄ phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C₁₂A₇, CA, CA₂ and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr^III)₂O₄ spinel mainly transformed into hauyne (Ca₄Al₆Cr^VIO₁₆) and Ca₅Cr₃O₁₂ which contains both Cr(IV) and Cr(VI). The reaction of C₁₂A₇ and CA with the spinel phase also resulted in the formation of Ca₄Al₆CrO₁₆. Conversely, the reaction of Mg(Al,Cr^III)₂O₄ spinel with CA₂ resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr^III)₂O₄ reacted with either C₁₂A₇ or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr^III)₂O₄ reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca₅Cr₃O₁₂ dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA₂, even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr)₂O₄ is very stable and does not leach in either distilled water or acidic solution.     

Photo‐reduction and adsorption in aqueous Cr(VI) solution by titanium dioxide,carbon nanotubes and their composite

BACKGROUND: This study compared the removal of aqueous Cr(VI) by multi‐walled carbon nanotubes (CNTs) modified by sulfuric acid, titanium dioxide (TiO₂) and composite of CNTs and TiO₂. RESULTS: More than 360 h contact time was needed to completely adsorb 3 mg L^?1 of Cr(VI) by CNTs, indicating that the rate of adsorption by CNTs alone was slow. The reaction time approaching equilibrium depended on the Cr(VI) concentration. XPS analysis of CNTs after adsorbing Cr(VI) showed that the Cr(VI) on the surface of CNTs was partially reduced to Cr(III). A 3 mg L^?1 solution of Cr(VI) was fully photocatalyzed by commercial TiO₂ (Degussa P25) in less than 0.5 h under UV irradiation. Unlike P25, reduction by another commercial TiO₂ (Hombikat UV100) took 4 h and more than 2 h were necessary for reduction by the composite. Thus the efficiency of Cr(VI) photo‐reduction by the composite was lower than by TiO₂, but higher than that by CNTs. XPS analysis of TiO₂ and composite showed the existence of both Cr(VI) and Cr(III) on their surfaces. CONCLUSION: In contrast to TiO₂, the reduction rate of aqueous Cr(VI) using CNTs as adsorbent was slow. P25 had a markedly higher photocatalytic efficiency than the composite or UV100 alone. Using P25 to reduce aqueous Cr(VI) has a higher potential for practical application. The diameters of TiO₂ and CNTs and the ratio of TiO₂/CNTs are key problems in the preparation of TiO₂/CNTs composite. Copyright © 2011 Society of Chemical Industry     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

3D flower like δ-MnO2/MXene Nano-hybrids for the removal of hexavalent Cr from wastewater

Herein, 3D flower-like δ-MnO₂, MXene and δ-MnO₂/MXene in-situ hybrid (IH) composites were prepared (via hydrothermal and solution treatment methods) for the effective removal of Cr (VI) from the contaminated water. The effect of various experimental parameters including contact time, pH levels and initial Cr (VI) ions concentration was determined and compared under static conditions. The kinetics of Cr (VI) adsorption onto δ-MnO₂, MXene, and IH confirmed the existence of a pseudo-second-order model. The obtained results reveal that the removal of Cr (VI) largely depends on the pH of the solution. The adsorption isotherm data fits best for Freundlich model, illustrating a multi-site adsorption mechanism of Cr (VI) ion on these adsorbents. The maximum Cr (VI) adsorption capacities onto δ-MnO₂, MXene and IH are 235.65 mg g⁻¹, 273.1 mg g⁻¹ and 353.87 mg g⁻¹, respectively. The study reveals that hetero-engineered approach of synthesizing transition metal oxides with MXenes provides abundant opportunities to remove contaminants from water with better efficiency due to reduction and electrostatic interaction.     

Adsorptive removal of hexavalent chromium using sawdust: Enhancement of biosorption and bioreduction

Simultaneous biosorption and bioreduction experienced by Cr(VI) species were initially validated by mixing 500 µM of Cr(VI) with 0.20 g of sawdust biosorbent. Accordingly, a complete disappearance of Cr(VI) species with emergence of 25% of Cr(III) ions was recorded; evidencing that both processes transpired simultaneously. An increase in the initial Cr(VI) concentration to 1500 µM could further induce more reduced Cr(VI) concentration. The enhancement of Cr(VI) biosorption and bioreduction was found to occur upon increasing the sawdust dosage to 4 g L^?1 and decreasing the solution pH to 2. However, the presence of a Zn(II) co-pollutant at 2500 µM had deteriorated the removal of Cr(VI) species.     

Application of nanofiltration to separate salts from a hydrogen-sulphide scrubber solution

Experiments were carried out using nanofiltration to separate salts from a hydrogen sulphide scrubber solution taken from an iron-based liquid-redox process. The scrubber solution used in these experiments contained organic chelating agents, iron, and various alkali metal inorganic salts (i.e., sulphates, thiosulphates, carbonates, and bicarbonates). The nanofiltration unit was equipped with monovalent ion-selective membranes. Results indicated that the nanofiltration membranes retained organic materials and iron and allowed ionic species (e.g., SO₄^2-, S₂^3-, CO₃^2-, HCO₃^-) to permeate. Results also indicated that the nanofiltration membranes used in these experiments preferentially removed CO₃^2- and HCO₃^- over SO₄^2- and S₂O₃^2-. The nanofiltration tests did not show any sign of membrane degradation in terms of ion selectivity; however, at high total-dissolved solids concentrations, the permeate flow rate was reduced.     

Transport of Chromium(VI) through a Supported Liquid Membrane Containing Tri-n-octylphosphine Oxide

ABSTRACT

In this study the transport of chromium(VI) from aqueous solutions of pH 2–4 through a supported liquid membrane (SLM) with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene as a mobile carrier was investigated. The transport flux of Cr(VI) increased with an increase in the concentrations of Cr(VI) in the feed phase and of TOPO in the membrane phase, but with a decrease in pH of the feed phase. Considering the equilibria of various Cr(VI) species in the aqueous phase and of the Cr(VI)—TOPO complexes formed in the membrane phase, a permeation model including the aqueous film diffusion of HCrO₄ ^? and Cr₂O₇ ^2? toward the membrane, the interfacial chemical reaction between them and TOPO, and the membrane diffusion of the Cr(VI)—TOPO complexes (H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃) was proposed to describe the transport of Cr(VI) through the SLM. By best fitting the transport flux equations of Cr(VI) with the experimental data using the Rosenbrock method, the apparent mass-transfer coefficients of HCrO₄ ^? and Cr₂O_7^. across the aqueous film, and those of H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃ across the membrane phase, were obtained. This work helps to clarify the transport mechanism of Cr(VI) through an SLM.