Removal of Cr(VI) from Aqueous Solution: Electrocoagulation vs Chemical Coagulation

Abstract

Hydrolyzed products of Al(III) have affinity below pH_zpc for oppositely charged mono and bi‐nuclear species of hexavalent chromium. This study investigates the comparative performance of electrocoagulation (EC) and chemical coagulation (CC) for the removal of Cr(VI) from aqueous solution. The highest removal of Cr(VI) achieved with EC was about 42% with 4.36 mA/cm² current density. Cathodic adsorption of chromium boosted up Cr(VI) removal during EC. Simultaneous electro‐ and chemical‐dissolution lead to high current efficiency of about 178%. Both the pH and the coagulant dosage have a significant impact on Cr(VI) removal in the pH ranges from 4.9 to 7.0. CC with alum and aluminum sulfate (AS) removed about 11% and 12% of Cr(VI). Co‐adsorption of divalent SO₄ ^2? ions with Cr(VI) is responsible for the lower removal observed with chemical coagulants. About 0.061 and 0.099 mole of SO₄ ^2? was adsorbed per mole Al in the precipitate in the pH range 4.9 to 7.0 with AS and alum. A higher coagulant dosage increases the removal of Cr(VI) but adversely affects the removal efficiency (Cr(VI) removed per unit of Al dosing). Cell current density (CD) has shown little effect on Cr(VI) removal and the pH elevation at the same charge density. Higher initial Cr(VI) concentration improves the removal efficiency as the species of Cr(VI) is acidic in solution and decreases the pH elevation rate.     

Preparation and characterization of NiO/MgO/Al2O3 supported CoPcS catalyst and its application to mercaptan oxidation

MgO/Al₂O₃ and NiO/MgO/Al₂O₃ solid bases were prepared by mixing method. The samples were characterized by X-ray diffraction (XRD), CO₂ temperature-programmed desorption (CO₂-TPD) and surface area measurements. After supported sulfonated cobalt phthalocyanine (CoPcS) the catalytic performance of these catalysts was evaluated in the mercaptan oxidation reaction. The effect of Mg/Al mole ratios on activity, crystal structure, basicity and stability in air was discussed. And the mechanism of the effect of NiO was identified. Results show that the base amount of MgO/Al₂O₃ increases with increasing Mg/Al mole ratio and catalyst with high Mg/Al mole ratio has a higher initial activity. NiO/MgO/Al₂O₃–CoPcS shows a higher initial activity and a much longer lifetime than MgO/Al₂O₃–CoPcS. When nickel oxide is doped into the MgO/Al₂O₃ support more crystal defects are generated, which increases the amount and types of basic sites.     

Interaction of cation-exchange membrane with polycation I. Poly(N-methyl-4-vinylpyridinium chloride)

We elucidated the effect of the molecular weight of poly(N-methyl-4-vinylpyridinium chloride) (PMVP) on its adsorbed or ion-exchanged amount on the cation-exchange membrane and the preferntial permselectivity of the membrane for sodium ion to calcium ion. The amount of the adsorbed or ion-exchanged PMVP increases with time and then attains to a definite value at a definite concentration. Also, the ultimate value increases with increasing the concentration of PMVP. When the molecular weight of PMVP is 3090, the ratio of the pyridinium groups of PMVP ion-exchanged with the sulfonic acid groups on the membrane surface to the total pyridinium groups of the cohered PMVP is in the range of 70–80%. The relative transport number of calcium ions to sodium ions(P_Na^Ca) decreases with increasing the amount of adsorbed or ion-exchanged PMVP and the numbe rof non-ion-exchanged pyridinium groups of PMVP and the number of non-ion-exchanged pyridinium groups of PMVP on the membrane surface. The smaller the molecular weight of PMVP, the more the adsorbed or ion-exchanged amount and the more preferable the permselectivity for sodium ion.     

The Acidity of Zeolites: Concepts,Measurements and Relation to Catalysis: A Review on Experimental and Theoretical Methods for the Study of Zeolite Acidity

In this article, we considered all aspects of acidity (nature of acid sites, strength, density, etc.) in solid catalysts and in zeolites in particular. After reminding the definition of acidity in liquid and solid acids, we emphasized acidity characterization by the most used physical techniques, such as Hammett's indicator titration, microcalorimetry of adsorbed probe molecules (ammonia, pyridine or other amines for acidity characterization and CO₂ or SO₂ for basicity characterization), ammonia or any amine thermodesorption, IR spectroscopy of hydroxyl groups and of several probe molecules adsorbed (ammonia, pyridine, piperidine, amines, CO, H₂, etc.), MAS-NMR of ²⁷Al, ²⁹Si, ¹H elements and of ¹H, ¹³C, ³¹P, etc. of adsorbed probe molecules, and model catalytic reactions.

Modeling the way the acid features of zeolites influence the catalytic activity of these catalysts toward acid-catalyzed reactions (relation between ammonia desorption activation energy values and catalytic activities, reaction mechanism, and kinetics) completes the general analysis of acidity and zeolite chemistry.     

Removal of heavy metal ions with water-insoluble amphoteric sodium tertiary amine sulfonate starches

The removal of heavy metal ions (Pb⁺², Cu⁺² and Zn⁺²) from solutions with high crosslinked amphoteric starch containing the sulfonate anionic group and the tertiary ammonium cationic group was investigated. The adsorption capacity of sodium tertiary amine sulfunate starch is 0.050 meq/g. The adsorption process has been found to be concentration and pH dependent and exothermic, and follows the Langmuir isothermal adsorption. The heat of adsorption (H) of Pb⁺², Cu⁺² and zn⁺² ions is equal to –10.85. –16.20 and –20.00 Kcal/mole, respectively. The amount of adsorbed metal ions on the adsorbent decreases when NaCl or Na₂SO₄ is added to the solution.     

Quantitative characterization of the solid acidity of montmorillonite using combined FTIR and TPD based on the NH3 adsorption system

The complete parameters of montmorillonite solid acidity, namely amount, strength, and types of acidity, were determined and the properties of the acid sites after heating were proposed by combining the temperature-programmed desorption (TPD) and Fourier transform infrared spectroscopy (FTIR) based on the NH₃ adsorption system. The total amount of montmorillonite acid sites was 1.15 mmol/g, which was higher than the value obtained by the Hammett indicator method because of the detection of solid acid sites in the montmorillonite interlayer space. These acid sites were composed of 1.00 mmol/g Brønsted and 0.15 mmol/g Lewis acid sites. The acidity of montmorillonite was primarily derived from the interlayer polarized water, Si–OH, H₃O⁺ adsorbed by negatively charged tetrahedral AlO₄, and unsaturated Al^3 + ions, all of which were attributed to the Brønsted acid sites with the exception of the unsaturated Al^3 + ions (Lewis acid sites). Heating led to an increase in the acid strength and the acid amount and altered the type of the partial acid sites. The interlayer polarized water provided more protons after heating at 120 °C and exhibited higher acid strength than that of raw montmorillonite. After heating at 400 °C, the interlayer polarized water acted as very strong acid sites. The H₃O⁺ adsorbed by tetrahedral AlO₄ was attributed to weak-strength acid sites and transformed into Si–O(H)–Al after dehydration, while displaying strong-strength acidity. The unsaturated Al^3 + ions showed medium-strength Lewis acidity, although a portion of these ions adsorbed water molecules and exhibited weak Brønsted acidity. After dehydroxylation at 600 °C, an abundance of unsaturated Al^3 + ions appeared and the amount of Lewis acid sites increased.     

Preparation and characterization of porous cationic poly[styrene‐co‐(N,N′‐dimethylaminoethyl methacrylate)] nanoparticles and their adsorption of heavy metal ions in water

Using styrene (St) and N,N′‐dimethylaminoethyl methacrylate (DMAEMA) as raw materials, monodispersed P(St‐co‐DMAEMA) nanoparticles (NPs) were first prepared via semi‐continuous emulsion polymerization, and using a stepwise acid–alkali post‐treatment, porous P(St‐co‐DMAEMA) NPs were then obtained and used to adsorb heavy metal ions in aqueous phase. Results showed that the post‐treatment conditions including temperature, initial pH and time of acid–alkali treatment had significant effects on the morphology of the porous P(St‐co‐DMAEMA) NPs, with higher temperature, more extreme pH condition and longer treatment time resulting in larger pores and volume swelling ratio. Under the optimized acid–alkali post‐treatment conditions (60 °C, acid treatment at pH = 4.0 for 1 h and then alkali treatment at pH = 10.0 for 1 h), the obtained porous NPs had nearly 15 times the surface area and 1.5 times the amount of surface amino groups than the corresponding solid NPs. An analysis of the mechanism of metal ion adsorption on the porous NPs indicated that the adsorbed amount of metal ions was the result of synergistic effect of physical and chemical adsorption, which was closely related to the porous NP surface area, amount of surface of amino groups and the volume of the ions. © 2018 Society of Chemical Industry     

Sorption of Al (III) from aqueous solution by fresh macrophyte alligator weed: Equilibrium and kinetics

The removal of Al (III) ions from aqueous solution by locally abundantly low-cost fresh macrophyte, alligator weed, was examined in batch system. Effect of initial solution pH on Al (III) adsorption was investigated and the Al (III) species present in aqueous solution were identified. The main functional groups of the alligator weed were characterized by Fourier transform infrared spectrometer (FT-IR). The equilibrium data fitted to Freundlich and Langmuir isotherms satisfactorily. The pseudo-second-order equation fitted the kinetic data very well. The intraparticle diffusion played an important role in the Al (III) sorption process. Al (III) ions were favorably adsorbed by alligator weed and the values of K_f and 1/n (Freundlich constant) at 25 °C and pH 3.5 were found as 1.9963 (mg/g)/(mg/L)^1/n and 0.7875, respectively, which are comparable to those of granular activated carbon (2.20 (mg/g)/(mg/L)^1/n and 0.8695, respectively).     

Fluorination synthesis of MgF2 nanoparticles synthesized for manufacturing IR windows by hot-pressing

In this study, magnesium fluoride (MgF₂) nanoparticles were synthesized through the fluoridation method, by dissolving magnesium chloride and hydrofluoric acid (HF) in deionized water. The influences of some parameters, including pH, concentration ratio of reactants, F:Mg mole ratio, washing method and calcination temperature were investigated on the particle size, morphology, chemical purity and phase purity of MgF₂ nanoparticles. In order to study the impact of pH on the properties of MgF₂ nanoparticles, different samples at pH values of 1, 5 and 9 were synthesized. The obtained results revealed that as pH value increased from 1 to 9, the morphology of MgF₂ nanoparticles changed from rod to spherical shape. The effect of mole ratio of fluorine ions to magnesium ions on the MgF₂ nanoparticles at three ratios of 2, 6 and 12 also demonstrated that by increment of F:Mg mole ratio, the particle size was decreased from 150 nm to 30 nm. In addition, it was figured out that by the increment of F:Mg mole ratio, the MgO phase was eliminated. Afterwards, by decreasing the HF:MgCl₂ molar ratios from 0.1 to 0.03 the particle size reduced from 300 nm to 30 nm. After determining the optimal synthesis conditions, magnesium fluoride nanoparticles were calcined at 470, 530 and 600 °C. Regarding the results, the powder that was calcined at 600 °C with a particle size of about 30–40 nm was selected as the optimal sample. Ultimately, the resulting powder was sintered using hot-press (HP) at a temperature of 700 °C for 45min in the vacuum pressure of 10^?3 bar. After polishing the sintered piece, its inferred (IR) transparency was over 90% in the wavelength ranges of 3–5 μm.     

Nature of the sites of dissociative adsorption of dihydrogen and light paraffins in ZnHZSM-5 zeolite prepared by incipient wetness impregnation

A DRIFT study of ZnHZSM-5 zeolites with Si/Al ratios of 15 or 41 and a Zn loading of 0.8 wt% revealed a high thermal stability of bridging OH groups that was practically the same as in the pure hydrogen forms. It was concluded that the incipient wetness impregnation of NH₄ZSM-5 zeolite with zinc nitrate and the subsequent high-temperature treatment results only in a minor amount of ion exchange. A considerable part of the modifying zinc forms nanometric ZnO clusters inside the channels of the zeolite. The use of the low-temperature adsorption of dihydrogen as a probe indicated the appearance, after high-temperature vacuum pretreatment, of three different Lewis acid sites connected with coordinatively-unsaturated Zn²⁺ ions. The strongest Lewis sites, with an H–H stretching frequency of adsorbed molecular hydrogen of 3940 cm⁻¹, dissociatively adsorbed hydrogen, methane and propane at both room and elevated temperatures. These sites are represented either by Zn²⁺ ions on the walls of the main channels of the zeolite (α sites according to Mole et al.) or by Lewis-base pairs on the surface of nanometric clusters of zinc oxide. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phosphorus sorption by three cultivated savanna alfisols as influenced by pH

An earlier study of phosphate sorption by some savanna soils from Nigeria suggested that increased P sorption when pH was raised might be due to precipitation of exchangeable Al as amorphous polymeric Al species with increased sorption sites. But these savanna soils have Ca as the dominant cation in their exchange sites, and low exchangeable Al. The objective of this study was to determine the role played by Ca in pH-induced P sorption of three savanna soils under continuous cultivation. Phosphorus sorption increased when pH was raised from 4.5 to 7.0. Similarly, Ca retention increased with increasing pH. Regression of P sorption on Ca retention indicated a significant linear relationship in the three soils. Three possible mechanisms were proposed to explain the increasing P sorption with increasing pH: precipitation of Ca-phosphates, Ca-induced P sorption or co-adsorption of Ca and H₂PO ₄ ^– or HPO ₄ ^2– as ion pairs or complexes. Available evidence suggests that all three mechanisms can operate together to enhance P retention as pH increases. The paper proposes that increased P sorption by savanna soils when pH is raised is likely to be related to the chemistry and retention of Ca rather than to hydrolytic reactions of Al.     

Enhancement of uranyl ion uptake by prestructuring of acrylamide–maleic acid hydrogels

Acrylamide–maleic acid (AAm–MA) hydrogels were prepared by gamma‐irradiation of their aqueous solutions. UO₂⁺² ion uptake on P(AAm–MA) hydrogels was investigated using two types of gel systems prepared by a simple irradiation method and a prestructured reaction. It has been observed that gels prestructured with UO₂⁺² ions adsorbed approximately 15–20% more UO₂⁺² ions than gels prepared in pure water (the usual method). It was also found that the uranyl ion adsorption capacity of hydrogels increased with an increasing amount of maleic acid in the gel system and an increasing concentration of uranyl ion in the solution. A possible interaction mechanism between the groups in the copolymeric gels and UO₂⁺² ion has been proposed based on the stoichiometry and the spectroscopic evidence. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 284–289, 2000     

31P and119Sn high resolution solid state CP/MAS NMR study of Al2O3-SnO2 systems

A series of Al₂O₃-SnO₂ catalysts with the mole ratio of Al₂O₃ to SnO₂ equal to 1:1, 1 0.5, 1 0.1, 1 0.05 and 1 0.01 were characterized by³¹P NMR of adsorbed trimethyl phosphine (TMP) and¹¹⁹Sn MAS NMR spectroscopy. It was found from³¹P NMR that no Brønsted acid sites exist in these samples. Pure SnO₂ shows two different types of Lewis acid sites; in the mixed oxide samples a Lewis peak characteristic of pure Al₂O₃ is always seen, together with either one or two other Lewis peaks, depending on the Sn concentration.¹¹⁹Sn CP/MAS NMR spectra of the highest Sn-content sample show one narrow line at –603 ppm superimposed on a very broad line, indicating a strong interaction between Al and Sn oxides.     

Preparation of aminoalkyl celluloses and their adsorption and desorption of heavy metal ions

Aminoalkyl celluloses (AmACs) were prepared from 6-chlorodeoxycellulose and aliphatic diamines H₂N(CH₂)_mNH₂ (m = 2, 4, 6, 8). Their adsorption and desorption of divalent heavy metal ions such as Cu²⁺, Mn²⁺, Co²⁺, Ni²⁺ and their mixtures were also investigated in detail. Adsorption of metal ions on AmACs was remarkably affected by the pH of the solution, the metal ion and its initial concentration, and also the number of methylene units in the diamines. No adsorption of metal ions occurred on AmACs in strongly acidic solutions. However, metal ions were adsorbed rapidly on AmACs from weakly acidic solutions and the amount of adsorption increased with increasing pH. The effectiveness of AmACs as adsorbents decreased with increasing length of the methylene moiety, and AmACs from ethylenediamine (m = 2) was most effective. The adsorption of metal ions on AmACs was in the order Cu²⁺ > Ni²⁺ > Co²⁺ > Mn²⁺. Accordingly, their behavior followed the Irving-Williams series and Cu²⁺ ions were preferentially adsorbed from solutions containing metal ion mixtures. The adsorbed ions were easily desorbed from the AmACs by stirring in 0.1 M HCl.     

Adsorption of hexavalent chromium from aqueous solutions using 4-vinyl pyridine grafted poly(ethylene terephthalate) fibers

Summary Sorption of hexavalent chromium ions from aqueous solution by 4- vinyl pyridine (4-VP) grafted poly(ethylene terephthalate) (PET) fibers was studied. The Influences of adsorption time, pH of solution and Cr(VI) concentration on the adsorbed amount were investigated. 30 minutes of treatment time was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value in the process. The maximum adsorption capacity of the material (k_s) was found to be 263.16 mg g^-1. It was found that the reactive fibers are stable and regenerable by acid or base without losing their activity.     

Selectivity and competitive mechanism of cation exchange resin for Fe,Mg, and Al ions in phosphoric acid

The presence of iron, magnesium, and aluminum elements as the primary impurities in wet-process phosphoric acid (WPA) adversely affects the industrial phosphoric acid and subsequent phosphorus chemical products. This study aims to investigate the selectivity and competition mechanism of Sinco-430 cation exchange resin for Fe, Mg, and Al ions in phosphoric acid solution. By studying the effects of different process conditions on the removal efficiency, the suitable conditions for the static removal of metal ions from Fe-Mg, Al-Mg, and Fe-Al binary systems were determined: solid–liquid mass ratio (S/L) of 0.3, phosphoric acid concentration of 27.61 wt.%, system temperature of 50°C, and rotational speeds of 200, 400, and 200 rpm, respectively. By calculating the selectivity coefficients of the resin for metal ions under different experimental conditions and mutual replacement experiments, the semi-empirical formulas for the selectivity coefficients were derived and order of selectivity was determined as follows: Mg²⁺ > Fe²⁺ > Al³⁺. Visual MINTEQ 3.1 software and density functional theory (DFT) calculations demonstrated that at low pH, the main forms of Fe, Mg, and Al present in phosphoric acid were FeH₂PO₄⁺, Mg²⁺, and AlH₂PO₄²⁺, respectively. This finding explained the differences in selectivity of the resin for Fe, Mg, and Al. The dynamic removal of metal ions from phosphoric acid was investigated. The order of metal ion selectivity of the resin by the dynamic method is the same as that of the static method, and the dynamic exchange behaviour was most consistent with the Yan model.     

The effect of external stimuli on the invertase adsorption capacity of poly(N-vinyl-2-pyrrolidone-co-itaconic acid) hydrogels

Polyelectrolyte Poly(N-vinyl-2-pyrrolidone-co-itaconic acid) hydrogels (P(VP/IA)) with varying compositions were prepared from ternary VP/IA/water mixtures. The effect of external stimuli such as pH of the solution, temperature, substrate concentration of solution, and storage stability on the invertase adsorption capacity of P(VP/IA) hydrogels was investigated. The adsorption capacity of the hydrogels was found to increase from 4.4 to 18.4 mg invertase/g dry gel with increasing amount of IA in the gel system, while P(VP) gel adsorbed only 3.1 mg invertase/g dry gel. Kinetic parameters were calculated as Michaelis-Menten constant K_m = 20.6 mmol L^–1 and maximum velocity V_max = 6.44×10^–5 mol dm^–3 min^–1 for free enzyme and in the range of K_m = 26.4–41.1 mmol L^–1 and V_max = 6.35·10^–5–6.66·10^–5 mol dm^–3 min^–1, depending on the amount of IA in the hydrogel. Enzyme activities were found to increase from 59.0% to 72.0% with increasing amount of IA in the gel system and retained their activities for one month storage. The enzyme activities, after storage for one month at 4°C, were found to be 21.0% and 59.0–74.0% of the initial activity values for free and adsorbed enzyme, respectively. The optimal pH values for free and adsorbed enzymes were determined as 4.56 and 5.00, respectively. The optimum temperature for free and adsorbed enzymes was 55°C. Adsorption studies have shown that not only the gel composition but also the stimuli, temperature and pH of the solution play an important role on the invertase adsorption capacity of poly(VP/IA) hydrogels.     

Understanding the solidification and leaching behavior of synthesized Cr-containing stainless steel slags with varying Al2O3/SiO2 mass ratios

This study investigated the effect of Al₂O₃/SiO₂ mass ratios on the equilibrium crystallization behavior of synthesized CaO–SiO₂–MgO–Al₂O₃–Cr₂O₃ stainless steel slags to understand the selective concentration behavior of Cr into a primary Mg(Cr,Al)₂O₄ spinel phase during slag solidification and to determine the leaching stability of Cr-containing slags. The spinel solid solution was precipitated within the temperature range of 1600-1400 °C, where the Cr/(Cr+Al) mole ratio in the Mg(Cr,Al)₂O₄ spinel phase gradually decreased for slags with higher Al₂O₃/SiO₂ mass ratios. When the Al₂O₃/SiO₂ mass ratio increased from 0.125 to 0.5, the Cr content in the amorphous glass phase gradually decreased, with a subsequent increase in the Cr content in the crystalline phase. For slags with a unit Al₂O₃/SiO₂ mass ratio and MgO mole percent comprising less than the combined sum of the Cr₂O₃ and Al₂O₃ mole percents, the Cr content in the amorphous glass phase increased, which was correlated with the enhanced substitution of Cr³⁺ with Al³⁺ in the spinel. The trend of the amount of Cr-related ions in the leachate was consistent with the trend of Cr in the amorphous glass phase: the amount decreased for slags with Al₂O₃/SiO₂ mass ratios from 0.125 to 5 and then increased for slags with an Al₂O₃/SiO₂ mass ratio of 1. The results suggest that the addition of appropriate amounts of Al₂O₃ to stainless steel slags could be conducive to stabilizing Cr into the primary spinel phase to minimize Cr leaching into the environment.     

Adsorption of metal cations from aqueous solutions onto the pH responsive poly(vinylidene fluoride grafted poly(acrylic acid) (PVDF-PAA) membrane

This study investigated the influence of pH of adsorption medium and co-adsorptive metal cations for the adsorption of potassium (K⁺) and magnesium (Mg²⁺) ions onto poly (vinylidene fluoride) grafted poly(acrylic acid) (PAA-PVDF) membrane. At pH 4.8, the adsorption of potassium and magnesium was minimal, because of nearly non-dissociated carboxylic acid groups of PAA-chains, but adsorption increased with increasing ion concentration. The interaction of the studied cations between PVDF-PAA membranes increased considerably at pH 7.0 the dissociation of carboxylic acid groups of PAA. The addition of ionic substances (calcium (Ca²⁺) and sodium (Na⁺) to the adsorption medium reduced the adsorption of potassium and magnesium onto the membrane, because of co-adsorption. Divalent calcium reduced more effectively than univalent sodium the adsorption of potassium and magnesium onto the membrane. In conclusion, co-adsorbing ions reduced the adsorbed amount of potassium and magnesium ions due to binding competition. The percentual adsorbed values suggest that adsorption affinity of studied ions onto the PVDF-PAA membrane followed the order Na⁺ < K⁺ < Mg²⁺ < Ca²⁺. The effect of metal cations on drug adsorption from biological fluids needs research in the future, because e.g. PVDF-PAA membrane has been used in drug separation processes.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.