Removal of Cu(II) from Aqueous Solutions by the Foam Separation Techniques of Precipitate and Adsorbing Colloid Flotation

Abstract

Experimental investigations on the removal of Cu(II) from aqueous solution were carried out through two foam separation techniques: precipitate flotation and adsorbing colloid flotation with Fe(III). The optimum pH for good removal was found to be about 9 for the former and about 7 for the latter. The effects of surfactant (sodium lauryl sulfate), foreign ions (Na⁺, Ca²⁺, NO^? ₃, and SO^2- ₄), and Al(III) addition on the efficiency of Cu(II) removal are discussed.     

Electrical Aspects of Adsorbing Colloid Flotation. X. Pretreatments,Multiple Removals,Interferences, and Specific Adsorption

Abstract

The compatibility of the adsorbing colloid flotation of Cu(II) with Fe(OH)₃ and sodium lauryl sulfate with a variety of precipitation pretreatment techniques was studied. Procedures were developed which permitted precipitation pretreatment and effective foam flotation polishing. The interferences of glycerol, ClO₄ ^?, NO₃ ^?, C1^?, CN^?, CNS^?, F^?, SO4₄ ^2?, HPO₄ ^2?, HAsO₄ ^2?, C₂O₄ ^2?, (PO₃)₆ ^6?, and EDTA with the precipitate flotation of ferric hydroxide by sodium lauryl sulfate were studied. The simultaneous adsorbing colloid flotation of Cu(II), Pb(II), and Zn(II) with Fe(OH)₃ and sodium lauryl sulfate was found to be effective in the pH range 6 to 7 at ionic strengths below 0.1 mole/l. A model was analyzed for calculating surface potentials for floe surfaces having the charge distributed at discrete sites in the presence of electrolytes. Plots of surface potential versus adsorbable ion concentration were calculated for various values of the model parameters.     

Foam Separation of Mercury(II) and Cadmium(II) from Aqueous Systems

Abstract

Mercury(II) and cadmium(II) were separated from aqueous systems by a number of batch-type precipitate flotation and adsorbing colloid flotation techniques. HgS, CdS, and Cd(OH)₂ were removed by precipitate flotation; Fe(OH)₃, Al(OH)₃, FeS, and CuS were used as adsorbing colloids. Sodium lauryl sulfate and hexadecyltrimethylammonium bromide (HTA) were used as collectors. Dependence of separation efficiency on pH and ionic strength was investigated. Floc foam flotation of both metals with CuS and HTA was found to be quite effective, resulting in residual Hg(II) levels as low as 5 ppb and residual Cd(II) levels as low as 20 ppb. Floc foam flotation of Cd(II) with FeS and HTA yielded residual Cd(II) levels as low as 10 ppb.     

Removal of Organophosphorus Pesticides from Aqueous Solution by Using Adsorptive Bubble Separation Techniques

Abstract

Two organophosphorus pesticides, ddvp (phosphoric acid 2,2-dichlorovinyl dimethyl ester) and phorate (phosphorodithioic acid o,o-diethyl s-[(ethylthio)methyl] ester) were removed from aqueous solution by three adsorptive bubble separation techniques: air stripping, solvent sublation, and adsorbing colloid flotation. The effects of pH, flow rate, surfactant, ethanol, ionic strength, and coprecipitant concentration on the efficiency of pesticide removal were studied. Over 97% of phorate was removed in 30 min by solvent sublation, and 90% of phorate was removed in 10 min by adsorbing colloid flotation with Fe(OH)₃, floc. The separations of ddvp by these techniques were not effective.     

Removal of Direct Red from Aqueous Solution by Foam Separation Techniques of Ion and Adsorbing Colloid Flotation

Abstract

Experimental investigations on the removal of Direct Red from an aqueous solution were carried out through two foam separation techniques: ion flotation and adsorbing colloid flotation with Fe(III). The residual concentration of Direct Red can be lowered to below 0.5 ppm in 3 minutes by ion flotation and below 0.1 ppm in 2 minutes by adsorbing colloid flotation. The optimum pH for the removal of Direct Red was found to be 4 for ion flotation and 3–5 for adsorbing colloid flotation. The effects of surfactant, foreign ions, and Al(III) addition on the removal of Direct Red are discussed.     

The Adsorbing Colloid Flotation of Lead(II) and Zinc(II) by Hydroxides

Abstract

The effects of pH, ionic strength, and specific ions on the adsorbing colloid flotation of lead(II) and zinc(II) with AI(OH)₃ and Fe(OH)₃ with sodium lauryl sulfate (NLS) as collector are reported. Floc foam flotation of lead with Fe(OH)₃ and gelatin, with MnO₂ and NLS, and with CaCO₃ and NLS or hexadecyltrimethylammonium bromide was studied. Lead is efficiently removed with Fe(OH)₃ and NLS; zinc with Al(OH)₃ and NLS. A theoretical study was made of the effect of the charges of ions present as inert electrolyte; separations decrease in efficiency with increasing charge at constant ionic strength.     

Removal of Molybdate and Arsenate from Aqueous Solutions by Flotation

Abstract

Ion flotation and adsorbing colloid flotation have been studied in this paper for the effective removal of molybdenum(VI) and arsenic(V) from dilute aqueous solutions. These different flotation methods were also compared. Ion flotation using a cationic surfactant (dodecylamine) as collector, as well as adsorbing colloid flotation using ferric hydroxide as coprecipitant (or sorbent) and an anionic surfactant (sodium dodecyl sulfate) as collector were examined. Laboratory-scale experiments were conducted in order to assess the effects of the following parameters on the efficiency of the process: pH value, dosages of chemical reagents, initial concentrations of arsenic and molybdenum, and the presence of foreign anions, such as Cl^- and SO² ₄ ^-. In practical applications, ion flotation or adsorbing colloid flotation may be selected according to the concentration of arsenic, molybdenum, and also the initial [Mo]/[As] molar ratios in solution.     

Effect of Al(III) as an Activator for Adsorbing Colloid Flotation

Abstract

The effect of Al(III) on adsorbing colloid flotation using Fe(OH)₃ as the coprecipitant and sodium lauryl sulfate as the collector was studied, and the results of foam separation were compared with the zeta potential of the floc before and after Al(III) being added to the solution. It was found that when Al(III) is used as an activator, the zeta potential of the floc is more positive, which presumbly gives the floc a stronger affinity for anionic surfactant adsorption, resulting in better separation efficiency. The working range of pH for an effective separation is extended and good separation efficiency can be achieved at pH values closer to neutral with the aid of Al(III). Furthermore, the separation efficiency is significantly improved for solutions containing interfering ions, such as sulfate, by using Al(III) as an activator.     

CO2‐Switchable Oil/Water Emulsion for Pipeline Transport of Heavy Oil

By mixing an aqueous solution of tertiary amine, N,N‐dimethylethanolamine (DMEA), with naphthenic acid (RCOOH) derived from heavy oil, a CO₂ switchable zwitterionic surfactant (RCOO^?DMEAH⁺) aqueous system was constructed. The CO₂ switchability of this zwitterionic surfactant was confirmed by visual inspection, pH measurements, and conductivity tests, i.e., the RCOO^?DMEAH⁺ decomposed into RCOOH, DMEAH⁺ and HCO₃^? after bubbling CO₂ through but switched back to its original state by subsequent bubbling N₂ through at 80 °C to remove the CO₂. The interfacial tension tests of heavy oil in DMEA aqueous solutions indicated that the solution containing 0.5 wt% of DMEA and 0.2 wt% of NaCl resulted in the lowest interfacial tension. The O/W emulsion formed when aqueous solutions of DMEA were used to emulsify heavy oil exhibited the best performance when the oil/water volume ratio, DMEA concentration, and NaCl concentration were 65:35, 0.5 and 0.2 wt%, respectively. The feasibility of pipeline transport of the O/W heavy oil emulsion was evaluated. The results illustrated that the demulsification of the O/W emulsion after transport could be easily realized by bubbling CO₂ through. Although demulsification efficiency still needs to be improved, the recycling of the aqueous phase after demulsification by removal of CO₂ looks promising.     

Electrical Aspects of Adsorbing Colloid Flotation. XXI. Flotation with Dodecylphosphate/n-Hexanol Mixtures

Abstract

The adsorbing colloid flotation of Pb(II), Cd(II), and Cu(II) with ferric hydroxide floc and the mixed surfactant system sodium dodecylphosphate (SDP)/n-hexanol was investigated. Good removals of Pb and Cu were obtained; removal of Cd was less satisfactory. The effects of interfering anions (sulfate, oxalate, silicate, phosphate) were studied; higher concentrations of these ions could be tolerated with SDP/n-hexanol than with sodium dodecylsulfate. Measurements of the cmc of SDP were made; low solubility prevented determinations in the pH range ^4–8.5.     

Precipitate Flotation Studies with Monolauryl Phosphate and Monolauryldithiocarbamate

Abstract

Monolauryl phosphate has been employed for the removal of copper(II), manganese(II), and zinc(II) by foam flotation at various pH's and ionic strengths. Good removals of all three metal ions were obtained in the basic pH range and in the presence of up to 0.2 M sulfate. Coprecipitation of Zn(II) with ferric hydroxide was essential to attain good removal of Zn(II). The removal of Cu(II) was also good from solutions containing oxalate, silicate, phosphate, and metaphosphate; however, the presence of EDTA hinders the removal of Cu(II). The potential of lauryldithiocarbamate as a chelating surfactant for the removal of Cu(II) was explored at various pH's and in the presence of various anions. We conclude that lauryldithiocarbamate is a weak chelating agent, unable to compete efficiently for Cu(II) with anions such as CO₃ ^2?, HPO₄ ^2?, SiO₃ ^2?, and EDTA. The relatively rapid decomposition of lauryldithiocarbamate in solution coupled with its weakness as a chelating surfactant make it unsuitable for the removal of Cu(II) by foam flotation.     

Removal of Chromium and Organic Pollutants from Industrial Chrome Tanning Effluents by Electrocoagulation

The treatment of industrial chrome tanning effluents by electrocoagulation (EC) in a laboratory‐scale reactor was investigated. Mild‐steel (MS) electrodes have been found to outperform aluminum (Al) electrodes in reducing the Cr(III) concentration to <2 mg L^–1. The conversion of Fe(II) to Fe(III) is slow in the lower pH range (<6), and OH^– ions generated during EC are amply available for Cr(III) removal by precipitation in the case of the MS electrode. Formation of Al(OH)₃(s) in competition with Cr(OH)₃(s) while consuming the OH^– ion is a cause for lower Cr(III) removal with Al. EC with the MS electrode and chemical coagulation (CC) with addition of alkali proved to be equally efficient for removing Cr(III).     

Surfactant Recovery in Adsorbing Colloid Flotation

Abstract

The displacement of surfactants from floc–water interfaces by salts is examined by statistical mechanical methods. The effect of added salts on the adsorption isotherm is exhibited, and it is found that surfactant condensed films can readily be displaced. This may markedly improve the economics of adsorbing colloid flotation by facilitating surfactant recovery. Preliminary experimental results supporting the theory are presented; Na₂CO₃ is used to displace sodium lauryl sulfate from Fe(OH)₃. The viscous drag forces on floc particles attached to rising bubbles are calculated for bubbles having diameters in the range 0 to 1 mm. At the upper end of this range these forces appear to be large enough to reduce the efficiency of foam flotation.     

Denitrification in aqueous FeEDTA solutions

The biological reduction of nitric oxide (NO) in aqueous solutions of FeEDTA is an important key reaction within the BioDeNOx process, a combined physico‐chemical and biological technique for the removal of NO_x from industrial flue gasses. To explore the reduction of nitrogen oxide analogues, this study investigated the full denitrification pathway in aqueous FeEDTA solutions, ie the reduction of NO₃^?, NO₂^?, NO via N₂O to N₂ in this unusual medium. This was done in batch experiments at 30 °C with 25 mmol dm^?3 FeEDTA solutions (pH 7.2 ± 0.2). Also Ca²⁺ (2 and 10 mmol dm^?3) and Mg²⁺ (2 mmol dm^?3) were added in excess to prevent free, uncomplexed EDTA. Nitrate reduction in aqueous solutions of Fe(III)EDTA is accompanied by the biological reduction of Fe(III) to Fe(II), for which ethanol, methanol and also acetate are suitable electron donors. Fe(II)EDTA can serve as electron donor for the biological reduction of nitrate to nitrite, with the concomitant oxidation of Fe(II)EDTA to Fe(III)EDTA. Moreover, Fe(II)EDTA can also serve as electron donor for the chemical reduction of nitrite to NO, with the concomitant formation of the nitrosyl‐complex Fe(II)EDTA–NO. The reduction of NO in Fe(II)EDTA was found to be catalysed biologically and occurred about three times faster at 55 °C than NO reduction at 30 °C. This study showed that the nitrogen and iron cycles are strongly coupled and that FeEDTA has an electron‐mediating role during the subsequent reduction of nitrate, nitrite, nitric oxide and nitrous oxide to dinitrogen gas. Copyright © 2004 Society of Chemical Industry     

Polystyrene anchored vanillin Schiff base—Complexation and ion removal studies

A set of six new polystyrene anchored metal complexes have been synthesized by the reaction of the metal salt with the polystyrene anchored Schiff base of vanillin. These complexes were characterized by elemental analyses, Fourier transform infrared spectroscopy, diffuse reflectance studies, thermal studies, and magnetic susceptibility measurements. The elemental analyses suggest a metal : ligand ratio of 1 : 2. The ligand is unidentate and coordinates through the azomethine nitrogen. The Mn(II), Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic while Zn(II) is diamagnetic. The Cu(II) complex is assigned a square planar structure, while Zn(II) is assigned a tetrahedral structure and Mn(II), Fe(III), Co(II), and Ni(II) are all assigned octahedral geometry. The thermal analyses were done on the ligand and its complexes to reveal their stability. Further, the application of the Schiff base as a chelating resin in ion removal studies was investigated. The polystyrene anchored Schiff base gave 96% efficiency in the removal of Ni(II) from a 20‐ppm solution in 15 min, without any interference from ions such as Mn(II), Co(II), Fe(III), Cu(II), Zn(II), U(VI), Na⁺, K⁺, NH₄⁺, Ca²⁺, Cl^?, Br^?, NO₃^?, NO₂^?,and CH₃CO₂^?. The major advantage is that the removal is achieved without altering the pH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1536–1539, 2005     

Removal of Copper(II) from a Concentrated Sulphate Medium by Cloud Point Extraction Using an N,N′-Bis(salicylaldehyde)Ethylenediimine Di-Schiff Base Chelating Ligand

Various chelating ligands have been investigated for the cloud point extraction of several metal ions. However, limited studies on the use of the Schiff base ligands have been reported. In this work, cloud point extraction behavior of copper(II) with N,N′‐bis(salicylaldehyde)Ethylenediimine Schiff base chelating ligand, (H₂SALEN), was investigated in aqueous concentrated sulphate medium. The extraction process used is based on the formation of hydrophobic H₂SALEN–copper(II) complexes that are solubilized in the micellar phase of a non‐ionic surfactant, i.e. ethoxylated (9.5EO) tert‐butylphenol. The copper(II) complexes are then extracted into the surfactant‐rich phase above cloud point temperature. Different parameters affecting the extraction process of Cu(II), such as equilibrium pH, extractant concentration, and non‐ionic surfactant concentration were explored. The extraction of Cu(II) was studied in the pH range of 2–11. The results obtained showed that it was profoundly influenced by the pH of the aqueous medium. The concentration factor, C_f, of about 17 with extraction efficiency of E % ≈100 was achieved. The stoichiometry of the extracted complex of copper(II) was ascertained by the Yoe–Jones method to give a composition of 1:1 (Cu:H₂L). The optimum conditions of the extraction‐removal have been established as the following: (1) 1.86 × 10^?3 mol/L ligand; (2) 3 wt% surfactant; (3) pH of 8 (4) 0.5 mol/L Na₂SO₄ and (5) temperature of 60 °C.     

Cation composition during recrystallization of layered double hydroxides from mixed (Mg, Al) oxides

Changes in cation composition and M²⁺/M³⁺ ratio during hydrotalcite regeneration were studied. Regenerated hydrotalcites were obtained by recrystallization of mixed (Mg, Al) oxides in solutions of divalent (Mg, Zn, Co, Ni, Cu) or trivalent (Al, Fe) cations.Heating Mg–Al–CO₃ hydrotalcites with Mg/Al=2, 3 and 3.7, at 600 °C for 2 h yielded periclase-like mixed (Mg, Al) oxides (HT-P). The hydrotalcite structure was restored by dispersing oxides 48 h in water or aqueous solutions of different cations.The presence of Mg²⁺, Zn²⁺, Ni²⁺, Co²⁺, Cu²⁺ salts or of low soluble hydromagnesite increased the M²⁺/Al ratio, reaching a maximum value of 3.8. An incorporation of Zn²⁺, Ni²⁺, Co²⁺ and Cu²⁺ cations in the newly formed hydrotalcite was detected, while Mg²⁺ remained in solution. In the presence of soluble Al salts or freshly precipitated Al(OH)₃, the M²⁺/Al ratio approximated the minimal possible value of 2.The Mg/Al ratio of a hydrotalcite crystallized from a mixture of two HT-P samples with different Mg/Al ratios is equal to the weighted average value.The results obtained support the conception of the dissolution–crystallization mechanism of hydrotalcite regeneration from mixed (Mg, Al) oxides contrary to the widely accepted concept of topotactic processes.     

Microstructures and strength of microporous MgO-Mg(Al,Fe)2O4 refractory aggregates

Microporous MgO-Mg(Al, Fe)₂O₄ refractory aggregates were prepared using magnesite, Al(OH)₃ and Fe₂O₃ applying an in-situ decomposition synthesis method. At 1400–1600 °C, there was a Mg(Al, Fe)₂O₄ with Fe³⁺, which had two structures. One was a ring structure formed from Al(OH)₃ pseudomorph particle as a template and a low content of Fe³⁺. The other was the dot and strip structures precipitated in magnesite pseudomorph particles with a high content of Fe³⁺. Besides, at 1550–1600 °C, microporous MgO-Mg(Al, Fe)₂O₄ refractory aggregates had an excellent compressive strength (75.8–81.5 MPa) and apparent porosity (26.8%?28.2%).     

Removal of Cu(II), Fe(III), and Cr(III) from Aqueous Solution by Aniline Grafted Silica Gel

Abstract

The aniline moiety was covalently grafted onto silica gel surface. The modified silica gel with aniline groups (SiAn) was used for removal of Cu(II), Fe(III), and Cr(III) ions from aqueous solution and industrial effluents using a batch adsorption procedure. The maximum adsorption of the transition metal ions took place at pH 4.5. The adsorption kinetics for all the adsorbates fitted better the pseudo second‐order kinetic model, obtaining the following adsorption rate constants (k₂): 1.233 · 10^?2, 1.902 · 10^?2, and 8.320 · 10^?3 g · mg^?1 min^?1 for Cr(III), Cu(II), and Fe(III), respectively. The adsorption of these transition metal ions were fitted to Langmuir, Freundlich, Sips, and Redlich‐Peterson isotherm models; however, the best isotherm model fitting which presented a lower difference of the q (amount adsorbed per gram of adsorbent) calculated by the model from the experimentally measured, was achieved by using the Sips model for all adsorbates chosen. The SiAn adsorbent was also employed for the removal of the transition metal ions Cr(III) (95%), Cu(II) (95%), and Fe(III) (94%) from industrial effluents, using the batch adsorption procedure.     

Adsorbing Colloid Flotation of Zn(II) with Fe(OH)(3) and Polyelectrolytes

Abstract

It was found that zinc ion could be removed from aqueous solutions by adsorbing colloid flotation with Fe(OH)³ and sodium lauryl sulfate (SLS) provided that the ionic strength of the solution is low (containing no greater than 0.02 M NaNO³). An excess dose of iron resulted in poor separation. Three types of polyelectrolytes were used as the activators to compensate for the effect of increasing ionic strength of the solutions. Betz 1150 (a weakly cationic acrylamide copolymer) was found to be the most effective activator. The separation was effective from a solution containing NaNO³ as high as 0.7 M when Betz 1150 was used as the activator.