Electrochemical production of cuprous oxide and metallic nickel in a two-compartment cell

The purpose of the present investigation was to develop an electrochemical process to obtain simultaneously cuprous oxide powder and metallic nickel in a two-compartment cell. Nafion® 901 bimembrane (Dupont, USA) was employed to separate the compartments to avoid the diffusion of nickel ions from the catholyte to the anolyte. A continuous addition of sodium hydroxide solution to the anodic compartment was necessary to form in situ the cuprous oxide by chemical reaction with the cuprous chlorocomplexes generated at the anode. As an anode system, a titanium basket filled with copper scrap wire was utilized. The anodic operating conditions were: NaCl 250 g dm^?3, pH 10, 80°C, c.d. 6 A dm^?2 and current concentration 0.4 A dm^?3, The cathodic parameters were: Ni²ⁱ 74 g dm^?3, H₃B0₃30 g dm^?3, sodium lauryl sulphate 0.5 g dm^?3, coumarin 0.15 g dm^?3, pH2, 50°C, c.d. 6 A dm^?2 Good quality red-violet cuprous oxide powder, meeting ASTM specifications D912-65 to be used in antifouling paints and metallic nickel (> 99.96% Ni) was obtained.     

Separation of cobalt and nickel from acidic sulfate solutions using mixtures of di(2‐ethylhexyl)phosphoric acid (DP‐8R) and hydroxyoxime (ACORGA M5640)

DP‐8R and ACORGA M5640 extractants diluted in Exxsol D100 were used to co‐extract cobalt and nickel from aqueous acidic sulfate media. The influences of equilibration time, temperature, equilibrium pH and reagent concentrations on the extraction of both metals have been studied. It was observed that both cobalt and nickel extraction are slightly sensitive to temperature but are pH dependent. Metal extraction equilibria are reached within about 5 min contact time. In addition, cobalt extraction depends on the extractant concentration in the organic phase. For a solution containing 0.5 g dm^?3 each of cobalt and nickel and an initial pH of 4.1, conditions were established for the co‐extraction of both metals and selective stripping (with H₂SO₄) of cobalt and nickel. Using the appropriate reagent concentrations the yield (extraction stage) for both metals exceeded 90%, and stripping of cobalt and nickel was almost quantitative. Copyright © 2004 Society of Chemical Industry     

Electrodeposition of nickel-cobalt-zinc alloys from a borate bath

The electrodeposition has been studied of nickel-cobalt-zinc alloys from a borate bath containing nickel sulphate (120–140 g dm^–3), cobalt sulphate (30–46 g dm^–3), zinc sulphate (144–168 g dm^–3), boric acid (30 g dm^–3) and ammonium chloride (2 g dm^–3). The operating conditions were: current density, 2.0–5.0 A dm^–2; temperature, 30–40°C and pH, 2.4 to 5.4. Light grey, semibright, stressed films have been obtained. However, the deposits consist partially of black powder when the concentration of the various components is increased. The brightness is found to increase with decreasing temperature and pH of the solution. The total cathode efficiency increases when the pH and temperature of the solution decrease, whereas at any particular pH and temperature it first decreases, reaches a minimum and then increases with increasing current density.     

Influence of variables in nickel-manganese-zinc alloy plating from a sulphate bath

An Ni-Mn-Zn alloy has been satisfactorily electrodeposited from a sulphate bath containing nickel sulphate (20–23 g dm⁻³), manganese sulphate (76–88 g dm⁻³), zinc sulphate (18–24 g dm⁻³), ammonium sulphate (30 g dm⁻³), thiourea (18g dm⁻³) and ascorbic acid (0.8 g dm⁻³) under various plating conditions, namely, current density 1.0–3.0 A dm⁻²; temperature 30–45° C; pH 2.7–4.2 and duration of electrolysis 15–30 min. Semibright, blackish-grey, thin films were generally deposited with the proportion of nickel and manganese in the deposits increasing with increasing current density, temperature and duration of electrolysis. However, the amount of zinc increased as the pH of the solution was raised. The cathode efficiency for alloy deposition increased linearly as the temperature or the pH of the solution was decreased, whereas at any particular pH and temperature it continuously rose with increasing current density or the time of deposition. The cathode polarization shifted to more negative values on increasing the current density and to less negative values at higher pH values and temperatures which consequently lowered the throwing power under the latter conditions.     

Solvent extraction with LIX 973N for the selective separation of copper and nickel

LIX 973N diluted with Iberfluid was used to co‐extract copper and nickel from ammoniacal/ammonium carbonate aqueous media. The influence of equilibration time, temperature, equilibrium pH and extractant concentration on the extraction of both metals has been studied. It was observed that neither copper nor nickel extraction is sensitive to temperature and equilibrium pH, however nickel extraction equilibrium is reached at a longer contact time (20 min) than that of copper (5 min), in addition nickel extraction depends greatly on the extractant concentration in the organic phase. For a solution containing 3 g dm⁻³ each of copper and nickel and 60 g dm⁻³ ammonium carbonate, conditions were established for the co‐extraction of both metals, ammonia scrubbing and selective stripping (with H₂SO₄) of nickel and copper. Using the appropriate extractant concentration the yield (extraction stage) for both metals is near 100%, whereas the percentage of nickel and copper stripping is also almost quantitative. © 1999 Society of Chemical Industry     

Liquid extraction of metals from sulphate solutions by alkylphosphoric acids. I. Equilibrium distributions of copper,cobalt and nickel with di-(2-ethyl hexyl) phosphoric acid

Liquid-liquid equilibrium data were obtained at 25° for the distribution of copper, cobalt and nickel between aqueous sulphate solutions and kerosene solutions of di-(2-ethyl hexyl) phosphoric acid (EHPA). Two mechanisms of extraction were observed. When the ratio (L) of organic phase equilibrium metal concentration to initial EHPA concentration was less than 0·1, the metals were extracted by the reaction: and a correlation for the equilibrium distribution coefficients was obtained from the thermodynamic equilibrium relationship for this reaction, taking into account metal ion complexing in the aqueous phase. Ammonium hydroxide and sodium hydroxide were used as alkalis for pH adjustment and similar distribution coefficients were obtained with both when L was less than 0·1. For L greater than 0·1, metal-EHPA polymers were also formed in the organic phase, a typical step in their formation being: Equilibrium relationships were obtained from consideration of the equilibrium constants of the typical step and the reaction for monomer formation. The nature of the alkali used for pH adjustment influenced the distribution coefficients when L exceeded 0·1, higher distribution coefficients being obtained with sodium hydroxide than with ammonium hydroxide.     

Electrodeposition of ternary nickel—iron—cobalt alloys from acetate bath

Ternary nickel—iron—cobalt alloys of wide range composition have been deposited from acetate baths under a variety of conditions and the optimum conditions established are: nickel acetate 0.2828 M, ferrous sulphate 0.0359 M, cobalt acetate 0.2828 M, boric acid 0.1617 M, ascorbic acid 0.0056 M, pH 5.0, cd 1.5 A/dm² and temperature 30°. The bath gave bright, smooth and adherent deposits. Iron and cobalt contents decreased with an increase in cd and pH, X-ray studies of the deposits revealed fcc structure within the composition range studied (43.6–54.0% Ni). The results indicate that acetate bath can be successfully employed for plating purposes.     

Mechanism of persulfate decomposition in aqueous solution at 50°C in the presence of vinyl acetate and nitrogen

The rate of the thermal decomposition of potassium persulfate has been studied in an unbuffered aqueous solution at 50°C in nitrogen atmosphere in the presence of vinyl acetate (VA) monomer (M). It has been found that the initial rate of persulfate decomposition may be written as in the concentration range of persulfate (1.85 × 10^?2–1.85 × 10^?3 m/dm³) and VA (0.054–0.27 m/dm³). The pH of the aqueous solution of persulfate was found to decrease continuously at 50°C, but there was no measurable change of pH of the aqueous solution containing persulfate and VA at 50°C in the presence of nitrogen at the early stages of the reaction. VA, methyl acetate, and ethyl acetate have been found to undergo very slow hydrolysis in aqueous solution at 50°C. The partition coefficient (β) of the monomer between the polymer phase and the aqueous phase was found to be 21 ± 2 in the presence and absence of electrolytes (K₂SO₄, 10^?4–10^?3 m/dm³) by the bromometric estimation of the monomer present in the aqueous phase containing known amounts of monomer [1.80–2.20%, w/v] and freshly prepared polymer (0.3–0.5 g/100 mL). Above 10^?2 (m/dm³) persulfate, the polymer obtained was found to be insoluble in common solvents, viz., acetone, benzene, etc. Highly purified sodium dodecyl sulfate (0.5–5.0 × 10^?3 m/dm³) had no measurable effect on the rate of persulfate decomposition.     

Equilibrium characteristics for the extraction of cobalt and nickel into di(2-ethylhexyl) phosphoric acid

The liquid-liquid extraction of cobalt and nickel from aqueous sulphate solutions into di(2-ethylhexyl) phosphoric acid, DZEHPA, has been investigated at 25°C and 60°C. The system studied was made up as follows: the aqueous phase-cobalt and nickel dphates; the organic phase-20% D2EHPA, 75% Esso solvent DX3641 and 5% tri-butyl phosphate. Analogies to vapour-liquid equilibria were made to develop three methods to correlate the binary equilibrium data, namely: 1) a delta Y method, 2) a method based on the correlation of solvent free mole fractions in both phases and 3) a “pseudo activity” coefficient or pseudo gamma method, γ_AB. The methods were evaluated as to their suitability for the prediction of binary isotherms. The delta Y and pseudo gamma methods were found to give the best results.     

Recycling of nickel–metal hydride batteries. II: Electrochemical deposition of cobalt and nickel

A combination of hydrometallurgical and electrochemical processes has been developed for the separation and recovery of nickel and cobalt from cylindrical nickel–metal hydride rechargeable batteries. Leaching tests revealed that a 4 mol dm^?3 hydrochloric acid solution at 95 °C was suitable to dissolve all metals from the battery after 3 h dissolution. The rare earths were separated from the leaching solution by solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid (D2EHPA) in kerosene. The nickel and cobalt present in the aqueous phase were subjected to electrowinning. Galvanostatic tests on simulated aqueous solutions investigated the effect of current density, pH, and temperature with regard to current efficiency and deposit composition and morphology. The results indicated that achieving an Ni? Co composition with desirable properties was possible by varying the applied current density. Preferential cobalt deposition was observed at low current densities. Galvanostatic tests using solutions obtained from treatment of batteries revealed that the aqueous chloride phase, obtained from the extraction, was suitable for recovery of nickel and cobalt through simultaneous electrodeposition. Scanning electron micrography and X‐ray diffraction analysis gave detailed information of the morphology and the crystallographic orientation of the obtained deposits. Copyright © 2004 Society of Chemical Industry     

Adsorption of fulvic acids from aqueous solutions by carbon nanotubes

Carbon nanotubes (CNTs) were used as adsorbent to remove fulvic acids (FA) from aqueous solutions. The adsorption capacity of CNTs for FA can reach 24 mg g^?1 at 5 °C and equilibrium concentration of 18 mg dm^?3. The kinetic and thermodynamic parameters, such as rate of adsorption, standard free energy changes (ΔG⁰), standard enthalpy change (ΔH⁰) and standard entropy change (ΔS⁰), have been obtained. Acidic conditions (pH = 2–5) favor FA removal. An increase in the ionic strength or the addition of divalent cations increase the adsorption of FA dramatically (FA = 60 mg dm^?3). An increase in the maximum adsorbed amount of FA was observed when treating FA in synthetic seawater. Desorption studies reveal that FA can be easily and quickly removed from CNTs by altering the pH values of the solution. Good adsorption capacity and quick desorption indicate that CNTs are a promising adsorbent to remove FA from aqueous solutions. Copyright © 2007 Society of Chemical Industry     

Reactive extraction of succinic acid using supercritical carbon dioxide

Reactive extraction using supercritical carbon dioxide (scCO₂) and tri-n-octylamine (TOA) was evaluated as a separation method of succinic acid from an aqueous solution. The reactive extraction of succinic acid was performed at varying initial acid concentrations in aqueous solution (0.07–0.45 mol?dm^?3), temperature (35–65°C) and pressure (8–16 MPa). The succinic acid separation was conducted in both batch mode and semi-continuous mode. The highest reactive extraction efficiency of approx. 62% was obtained for the process conducted in semi-continuous mode at 35°C and 16 MPa for the initial acid concentrations in aqueous phase of 0.39 mol?dm^?3.     

EXTRACTION OF NICKEL FROM AQUEOUS SULFATE SOLUTION INTO BIS(2,2,4-TRIMETHYLPENTYL)PHOSPHINIC ACID,CYANEX 272TM -EQUILIBRIUM AND KINETIC STUDIES

ABSTRACT

Equilibrium and kinetic studies have been carried out on the extraction of nickel from sulfate solutions using bis(2,2,4 trimethylpentyl) phosphinic acid HDTMPP, “Cyanex 272tm”- It was found that nickel extraction in HDTMPP was favored by the presence of sodium in the organic phase and that equilibrium nickel concentration could be written in terms of the pre-equilibrated extractant concentration

Kinetic studies were carried out using the rising drop method, reaction orders were determined with respect to the aqueous phase nickel concentration, Ni²⁺, the aqueous phase sodium concentration, Na ⁺ the pH, the organic phase dimer concentration ------ and the organic phase sodium salt concentration ---- In addition, it was found that the extraction kinetics could be explained in terms of an aqueous phase interfacial reaction accompanied by diffusion through the interface. Mass transfer coefficient values were determined indicating extraction rates for metal extraction into HDTMPP were the same order of magnitude as those found for HDEHP.     

Simultaneous solvent extraction of cobalt and magnesium in the presence of nickel from sulfate solutions by Ionquest 801

The simultaneous extraction of Co(II) and Mg(II) from nickel sulfate solutions has been carried out using the organophosphonic extractant Ionquest 801 diluted in Exxsol D‐80. Statistical design and analysis of experiments were used in order to determine the main effects and interactions of the solvent extraction parameters, which were the extraction pH at equilibrium, the temperature, the extractant concentration and the organic/aqueous phase ratio. A statistically designed experiment was also carried out to study the stripping of the Ionquest 801 organic phase loaded with cobalt and magnesium by sulfuric acid solution. The number of stages required for both extraction and stripping processes of cobalt and magnesium was evaluated. The results of continuous counter‐current mini‐plant tests demonstrated the simultaneous recovery of cobalt and magnesium from nickel sulfate solution. Copyright © 2005 Society of Chemical Industry     

Purification of nickel sulphate solutions containing iron,copper, cobalt,zinc and manganese

Acidic nickel-bearing solution containing iron, cobalt, manganese, zinc and copper was processed through a solvent extraction and precipitation technique to obtain a pure nickel sulphate solution. Iron was extracted using 0.2M Cyanex-272 (partially neutralised) as the extractant. Stripping of iron from the loaded organic has also been studied. After iron recovery through solvent extraction the raffinate still contained 0·25 g dm^?3 of iron which was quantitatively separated by a lime precipitation technique. During this iron precipitation there was no loss of cobalt and nickel but copper, manganese and zinc were coprecipitated to some extent. From the iron-free nickel sulphate solution the other impurities were extracted using the same extractant (Cyanex-272) in a single stage. The metal ions from the loaded organic were stripped using a 0·5% (v/v) H₂SO₄ solution in a single stage. The entire operation needs only seven stages: two stages for iron extraction, three stages for iron stripping from the loaded organic, and one stage each for extraction and stripping of other impurities. In the entire operation the loss of nickel was less than 0·5%.     

The removal of iron and cobalt from aqueous solutions by ion exchange with Na‐Y zeolite: batch,semi‐batch and continuous operation

The removal of single component and binary mixtures of divalent cobalt and iron from water by ion exchange with synthetic Y zeolite has been studied in batch, semi‐batch and continuous modes of operation; the initial metal solution concentration did not exceed 2 mmol dm^?3. Binary Co/Na and Fe/Na ion exchange equilibrium isotherms (294 K) are presented wherein exchange site heterogeneity is evident in the case of the iron treatment. Under conditions of stoichiometric ion exchange, removal efficiencies for both cobalt and iron decrease with increasing metal concentration (0.2–2 mmol dm^?3) and the values were similar for both metals. Removal of cobalt under transient conditions was found to be temperature dependent. In the fixed bed operation, break‐through behavior was sensitive to changes in both flow rate and inlet concentration. The break‐through profiles for both metals under competitive and non‐competitive conditions are presented; iron removal is lower in the presence of cobalt and vice versa. An in situ regeneration of the fully loaded zeolite by back exchange with sodium is considered and the exchange capacity of the regenerated zeolite is reported. The feasibility of employing cycles of heavy metal uptake/zeolite regeneration is addressed. © 2002 Society of Chemical Industry     

Determination of the efficiency and removal mechanism of cobalt by crab shell particles

The effects of contact time, solution pH and ionic strength on interactions between cobalt (⁵⁹Co) ions in synthetic liquid waste and particles of raw crab shell, Portunus trituberculatus, in batch reactions were studied. Approximately 19.5 mg dm^?3 Co was removed within 6 h after contact with 1.0 g dm^?3 crab shell at an initial concentration of 20 mg dm^?3 Co. Due to the dissolution of calcium carbonate in the crab shell, the solution pH changed spontaneously to 10, leading to precipitation of cobalt ions. The efficiency of cobalt removal depended on solution pH, but was less pH sensitive than for controls without crab shell. The maximum uptake of Co at an initial pH value of 5.0 was 510 mg g^?1 crab shell. The removal efficiency was affected slightly by ionic strength up to 2.0 mol dm^?3 of NaCl. Scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) indicated that the removal mechanism of Co by crab shell resulted primarily from the dissolution of calcium carbonate followed by precipitation of cobalt on the surface of the shell. Compared with commonly used ion‐exchange resins such as natural zeolite, Durasil 70, and Durasil 230, the efficiency of Co removal by a column of mixture of crab shell and activated carbon was at least three‐fold greater, indicating that crab shell is a suitable biosorbent for the removal of cobalt from liquid waste. Copyright © 2004 Society of Chemical Industry     

Corrosion of the zinc negative electrode of zinc–cerium hybrid redox flow batteries in methanesulfonic acid

Corrosion of zinc in aqueous methanesulfonic acid has been evaluated over a wide range of concentrations of acid (0.5–5 mol dm^?3), dissolved zinc (0.5–2 mol dm^?3), and electrolyte temperature (22–50 °C). The corrosion rate of zinc, in terms of weight loss and the volume of hydrogen evolved, varied with time and it was found to be highly dependent on the surface state and electrolyte conditions. With an initial active layer of zinc present, the corrosion rate rapidly increased following a decline when the proton concentration in the solution decreased to ca. 0.56 mol dm^?3. Organic and inorganic inhibitors were added to the electrolyte to suppress the zinc corrosion in 1 mol dm^?3 methanesulfonic acid. The strong adsorption and blocking effects of cationic organic adsorption inhibitors, such as cetyltrimethyl ammonium bromide and butyltriphenyl phosphonium chloride, led to a significant decrease in zinc corrosion over a 10 h immersion period. With the addition of indium and lead ions inhibitors, the zinc surface showed less activity. Zinc corrosion continued to a smaller extent in the presence of these metallic inhibitors during the first few hours, but the metallic layer of the inhibitors did not cover the surface completely resulting in continued hydrogen evolution and making the inhibitors less effective at longer times.     

Separation of Cadmium,Cobalt, and Nickel by Solvent Extraction using the Nickel Salts of the Extractants

A new solvent‐extraction process for the separation of cadmium, cobalt, and nickel in sulphate solutions coming from the hydrometallurgical processing of spent Ni‐Cd batteries is proposed. The main innovation is to use nickel salts of the extractants, thus avoiding external pH control in the extraction operation. The extractants are first loaded with nickel in conditioning steps, using a neutralizer for pH control, and afterwards contacted with the aqueous processing solutions for extraction of interested metals with no further need of neutralization. This process is an alternative to the usual approach, which uses the sodium or ammonium salts of the extractants, avoiding introducing these cations in the process stream. Using this approach, the extraction of cadmium with nickel salt of 1 M DEHPA was performed at resulting pH values of 3.8–4.3 producing an organic phase loaded with 35 g/L Cd. Cobalt extraction with the nickel salt of Cyanex 272 was further achieved at resulting pH of 5.1–5.7 obtaining a organic loaded with 6.5 g/L Co.     

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO<Subscript>2</Subscript> anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm⁻³ were carried out on a Ta/PbO₂ anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm⁻³). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%.