Non-Dispersive Extraction of Chromium(VI) by Cyphos IL102/Solvesso 100 Using the Pseudo-Emulsion-Based Strip Dispersion Membrane Operation.

The removal of chromium(VI) from an acidic (HCl) medium through non-dispersive extraction with strip dispersion (NDXSD) was investigated using a microporous PVDF membrane support in a permeation cell. The ionic liquid Cyphos IL102 (phosphonium salt) in Solvesso 100 was used as an organic phase. In NDXSD, the stripping phase (NaOH) is dispersed in the organic phase on the cell side with an impeller stirrer adequate to form a strip dispersion. This pseudo-emulsion phase (organic + strip solutions) provides a constant supply of the Cyphos IL102/Solvesso 100 to the membrane phase. Various hydrodynamic and chemical parameters, such as variation in the feed and pseudo-emulsion stirring speeds, HCl and Cr(VI) concentrations in the feed phase, and carrier concentration, were investigated. Results indicated that the best chromium(VI) transport was obtained under the following conditions: feed and pseudo-emulsion stirring speeds of 1000 min-1 and 600 min-1, respectively; an HCl concentration in the feed phase of 0.1 M; a chromium concentration of 0.01 g/L in the same phase; and carrier concentration in the organic phase in the 2-5-10% v/v range. From the experimental data, several mass transfer coefficients were estimated: a bulk diffusion coefficient of 3.1·10-7 cm2/s and a diffusion coefficient of 6.1·10-8 cm2/s in the membrane phase and mass transfer coefficients in the feed (5.7·10-3 cm/s) and membrane phases (2.9·10-6 cm/s). The performance of the present system against other ionic liquids and the presence of base metals in the feed phase were investigated.

Utilizing Deep Eutectic Solvents in the Recycle, Recovery, Purification and Miscellaneous Uses of Rare Earth Elements.

The boosted interest in using rare earth elements (REEs) in modern technologies has also increased the necessity of their recovery from various sources, including raw materials and wastes. Though hydrometallurgy plays a key role in these recovery processes, some drawbacks (apparent or not) of these processes (including the use of aggressive mineral acids, harmful extractants, and diluents, etc.) have led to the development of an environmental friendship subclass named solvometallurgy, in which non-aqueous solvents substituted to the aqueous media of the hydrometallurgical processing. Together with ionic liquids (ILs), the non-aqueous solvents chosen for these usages are the chemicals known as deep eutectic solvents (DEEs). The utilization of DEEs included the leaching of REEs from the different sources containing them and also in the separation-purification steps necessary for yielding these elements, normally oxides or salts, in the most purified form. This work reviewed the most recent literature (2023 year) about using deep eutectic solvents to recover REEs from various sources and coupling these two (DESs and REEs) to derive compounds to be used in other fields.

Solvent Extraction with Cyanex 923 to Remove Arsenic(V) from Solutions.

The removal of harmful arsenic(V) from aqueous solutions using Cyanex 923 (solvation extractant) was investigated using various experimental variables: equilibration time, the acidity of the aqueous phase, temperature, extractant and arsenic concentrations, and O/A ratio. Cyanex 923 extracted As(V) (and sulfuric acid) from acidic solutions; however, it could not be used to remove the metal from slightly acid or neutral solutions. The extraction of arsenic is exothermic and responded to the formation of H3AsO4·nL species in the organic phase (L represents the extractant, and the stoichiometric factor, n = 1 or 2, depends on the acidity of the aqueous phase). Extraction isotherms are derived from the experimental results. Both arsenic and sulfuric acid loaded onto the organic phase can be stripped with water, and stripping isotherms are also derived from the experimental results. The selectivity of the system against the presence of other metals (Cu(II), Ni(II), Bi(III), and Sb(III)) is investigated, and the ability of Cyanex 923 to extract As(V) and sulfuric acid compared to the use of other P=O-based solvation reagents, such dibutyl butylphosphonate (DBBP) and tri-butyl phosphate (TBP), is also investigated.

Treatment of Stainless Steel Rinse Waters Using Non-Dispersive Extraction and Strip Dispersion Membrane Technology.

The extraction of Fe(III), Cr(III), and Ni(II) from stainless steel rinse water using non-dispersive extraction and strip dispersion membrane technology was carried out in a microporous hydrophobic hollow-fibre module contactor. The fibres were of polypropylene, whereas the organic extractant DP8R (bis(2-ethylhexyl) phosphoric acid) diluted in ExxsolD100 was used as the carrier phase. The rinse water containing the three elements was passed through the tube side, and the pseudo-emulsion formed by the organic phase of DP8R in Exxol D100 and an acidic strip solution were passed through the shell side in a counter-current operation; thus, a unique hollow fibre module was used for extraction and stripping. In non-dispersive extraction and strip dispersion technology, the stripping solution was dispersed into the organic membrane solution in a vessel with an adequate mixing device (impeller) designed to form strip dispersion. This pseudo-emulsion was circulated from the vessel to the membrane module to provide a constant supply of the organic phase to the membrane pores. Different hydrodynamic and chemical variables, such as variation in feed and pseudo-emulsion flow rates, strip phase composition, feed phase pH, and extractant concentration in the organic phase, were investigated. Mass transfer coefficients were estimated from the experimental data. It was possible to separate and concentrate the metals present in the rinse water using the non-dispersive extraction and strip dispersion technique.

Iron Control in Liquid Effluents: Pseudo-Emulsion Based Hollow Fiber Membrane with Strip Dispersion Technology with Pseudo-Protic Ionic Liquid (RNH3+HSO4-) as Mobile Carrier.

The transport of iron(III) from aqueous solutions through pseudo-emulsion-based hollow fiber with strip dispersion (PEHFSD) was investigated using a microporous hydrophobic hollow fiber membrane module. The pseudo-protic ionic liquid RNH3HSO4- dissolved in Solvesso 100 was used as the carrier phase. This pseudo-protic ionic liquid was generated by the reaction of the primary amine Primene JMT (RNH2) with sulphuric acid. The aqueous feed phase (3000 cm3) containing iron(III) was passed through the tube side of the fiber, and the pseudo-emulsion phase of the carrier phase (400 cm3) and sulphuric acid (400 cm3) were circulated through the shell side in counter-current operational mode, using a single hollow fiber module for non-dispersive extraction and stripping. In the operation, the stripping solution (sulphuric acid) was dispersed into the organic membrane phase in a tank with a mixing arrangement (a four-blade impeller stirrer) designed to provide strip dispersion. This dispersed phase was continuously circulated from the tank to the membrane module in order to provide a constant supply of the organic solution to the fiber pores. Different hydrodynamic and chemical parameters, such as feed (75-400 cm3/min) and pseudo-emulsion phases (50-100 cm3/min) flows, sulphuric acid concentration in the feed and stripping phases (0.01-0.5 M and 0.5-3 M, respectively), metal concentration (0.01-1 g/L) in the feed phase, and PPILL concentration (0.027-0.81 M) in the carrier phase, were investigated. From the experimental data, different diffusional parameters were estimated, concluding that the resistance due to the feed phase was not the rate-controlling step of the overall iron(III) transport process. It was possible to concentrate iron(III) in the strip phase using this smart PEHFSD technology.

On the Use of Pseudo-Protic Ionic Liquids to Extract Gold(III) from HCl Solutions.

Solvent extraction of gold(III) from HCl media using pseudo-protic ionic liquids (PPILs) dissolved in toluene as the extractant phase is investigated. Three PPILs are generated from the reaction of commercially available amines and 1 M HCl solution and named as pri-NH2H+Cl- (derived from the primary amine Primene 81R), sec-NHH+Cl- (derived from the secondary amine Amberlite LA2) and ter-NH+Cl- (derived from the tertiary amine Hostarex A327). In the above structures, -NH2H+Cl-, -NHH+Cl- and -NH+Cl- represented the active groups (anion exchangers) of the respective PPIL. In the case of gold(III) extraction, the experimental variables investigated included the equilibration time (2.5-30 min), temperature (20-60 °C), HCl concentrations (1-10 M) in the aqueous phase, gold(III) concentration (0.005-0.05 g/L) in this same phase, and PPILs concentrations in the organic phase. From the experimental data, and using the Specific Interaction Theory, the interaction coefficients (ε) for the pair AuCl4-, H+ are estimated for the systems involving the three PPILs. Gold(III) is recovered from the metal-loaded organic phases using sodium thiocyanate solutions, and from these, gold is finally recovered by the precipitation of zero-valent gold (ZVG) nanoparticles.

Dynamic Adsorption of H2S onto a Goethite-Based Material.

The use of adsorption technology to remove H2S from synthetic gas (H2S and N2) using a goethite-based adsorbent was investigated. The influence of the H2S feed concentration (150-600 mg), the adsorbent dosage (1-4 g), and the gas flow rate (210-540 cm3/min) on the breakthrough curves and H2S adsorption on the adsorbent at the breakthrough point was investigated. Dynamic column experiments were performed to provide data for the theoretical models and to verify the performance of the system in the adsorption process. The theoretical models used in the present work were found to predict the adsorption breakthrough performance reasonably well.

The Pseudo-Protic Ionic Liquids TOAH+Cl- and TODAH+Cl- as Carriers for Facilitated Transport of In(III) from HCl Solutions.

A study of indium(III) transport across an immobilized liquid membrane using the pseudo-protic ionic liquids TOAH+Cl- and TODAH+Cl- as carriers has been carried out using batch experiments. Metal transport is investigated as a function of different variables: hydrodynamic conditions in the feed (375-1500 min-1) and receiving (500-750 min-1) phases, HCl (0.5-7 M) and indium (0.01-0.2 g/L) concentrations in the feed phase and carrier (1.25-40% v/v) concentration in the membrane phase. Indium is conveniently recovered in the receiving phase, using a 0.1 M HCl solution. Models are reported describing the transport mechanism, which consists of a diffusion process through the feed aqueous diffusion layer, fast interfacial chemical reaction, and diffusion of the respective indium-pseudo-protic ionic liquid through the membrane. The equations describing the rate of transport are derived by correlating the membrane permeability coefficient to diffusional and equilibrium parameters as well as the chemical composition of the respective indium-pseudo-protic ionic liquid system, i.e., the carrier concentration in the membrane phase. The models allow us to estimate diffusional parameters associated with each of the systems; in addition, the minimum thickness of the feed boundary layer is calculated as 3.3 × 10-3 cm and 4.3 × 10-3 cm for the In-TOAH+Cl- and In-TODAH+Cl- systems, respectively.

Liquid-Liquid Extraction of Indium(III) from the HCl Medium by Ionic Liquid A327H+Cl- and Its Use in a Supported Liquid Membrane System.

Ionic liquid A327H+Cl- was generated by reaction of tertiary amine A327 and HCl, and the liquid-liquid extraction of indium(III) from the HCl medium by this ionic liquid dissolved in Solvesso 100 was investigated. The extraction reaction is exothermic. The numerical analysis of indium distribution data suggests the formation of A327H+InCl4- in the organic phase. The results derived from indium(III) extraction have been implemented in a supported liquid membrane system. The influence of the stirring speed (600-1200 min-1), carrier concentration (2.5-20% v/v) in the membrane phase, and indium concentration (0.01-0.2 g/L) in the feed phase on metal transport have been investigated.

Dispersion-free extraction of In(III) from HCl solutions using a supported liquid membrane containing the HA324H+Cl- ionic liquid as the carrier.

By reaction of HCl and the tertiary amine HA324, an ionic liquid denoted HA324H+Cl- was generated and used in the transport of indium(III) from HCl solutions. Metal transport experiments were carried out with a supported liquid membrane, and several variables affecting the permeation of indium(III) across the membrane were tested: stirring speed, metal and acid concentrations in the feed solutions and the carrier concentration in the supported organic solution. The metal transport results were also compared with those obtained using different carriers in the solid support. A model that described indium(III) transport across the membrane was proposed, and the corresponding diffusional parameters were estimated.

Dysprosium Removal from Water Using Active Carbons Obtained from Spent Coffee Ground.

This paper describes the physicochemical study of the adsorption of dysprosium (Dy3+) in aqueous solution onto two types of activated carbons synthesized from spent coffee ground. Potassium hydroxide (KOH)-activated carbon is a microporous material with a specific Brunauer-Emmett-Teller (BET) surface area of 2330 m2·g-1 and pores with a diameter of 3.2 nm. Carbon activated with water vapor and N2 is a solid mesoporous, with pores of 5.7 nm in diameter and a specific surface of 982 m2·g-1. A significant dependence of the adsorption capacity on the solution pH was found, but it does not significantly depend on the dysprosium concentration nor on the temperature. A maximum adsorption capacity of 31.26 mg·g-1 and 33.52 mg·g-1 for the chemically and physically activated carbons, respectively, were found. In both cases, the results obtained from adsorption isotherms and kinetic study were better a fit to the Langmuir model and pseudo-second-order kinetics. In addition, thermodynamic results indicate that dysprosium adsorption onto both activated carbons is an exothermic, spontaneous, and favorable process.

Facilitated Chromium(VI) Transport across an Ionic Liquid Membrane Impregnated with Cyphos IL102.

Chromium(VI) is a well-known hazardous element, thus, its removal from aqueous sources is of a general concern. Among the technologies used for the removal of this type of toxic elements, liquid membranes are gaining in importance and the same has occurred with the use of ionic liquids, considered for many, due to their properties, as green solvents. Thus, the present work joined the three previous points, presenting an experimental study about the removal of chromium(VI) by the use of a liquid membrane operation which used the commercially available Cyphos IL102 ionic liquid as a carrier. The experimental variables included: the stirring speed applied to the feed and receiving solution (a key-parameter to gain maximum transport), acid, chromium(VI), sodium hydroxide and Cyphos IL102 concentrations in their various phases. Additionally, the performance of the present system was evaluated both against the presence of other metals in solution and other carriers. The experimental results confirmed that Cyphos IL102 is a good carrier for chromium(VI) transport and, thus, its removal from aqueous streams, and it also performed well in the presence of accompanying metals and against the performance of other commercially available carriers.

Synthesis of Calcium Aluminates from Non-Saline Aluminum Dross.

The present work examines the synthesis of tricalcium aluminate (for use as a synthetic slag) from the non-saline dross produced in the manufacture of metallic aluminum in holding furnaces. Three types of input drosses were used with Al2O3 contents ranging from 58 to 82 wt %. Calcium aluminates were formed via the mechanical activation (reactive milling) of different mixtures of dross and calcium carbonate, sintering at 1300 °C. The variables affecting the process, especially the milling time and the Al2O3/CaO molar ratio, were studied. The final products were examined via X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The reactive milling time used was 5 h in a ball mill, for a ball/dross mass ratio of 6.5. For a molar relationship of 1:3 (Al2O3/CaO), sintered products with calcium aluminate contents of over 90% were obtained, in which tricalcium aluminate (C3A) was the majority compound (87%), followed by C12A7 (5%).

Tin and silver recovery from wave soldering dross.

This work proposes a method for the recovery of tin and silver from wave soldering dross produced during the manufacture of printed circuit boards. Samples of wave soldering dross were first subjected to carbothermic reduction to obtain an ingot containing the above metals plus other elements. This ingot was then subjected to electrorefining at different densities of electrical current, electrolyte flow rate, and cathode-anode separation distance, to determine the optimum conditions for recovering pure tin. Under such conditions, 82 wt% of the tin in the ingot was recovered at a purity of 99.94%. After subjecting ingots to continuous electrorefining under optimum conditions for 845 h, the slime collected at the anode was removed for the recovery of silver. This slime was subjected to thin-layer leaching with concentrated nitric acid. The leachate produced was subjected to copper-cementation; the silver adhering to the copper rod was collected by washing. This process recovered 92% of the silver in the wave soldering dross ingot at a purity of >99.6%. Some 99% of the copper entering the leachate from the copper rod during cementation was recovered by liquid-liquid extraction with 40% LIX84 (dissolved in EXXOL D100). This method could provide a rapid, inexpensive means of recovering pure tin and silver from wave soldering dross.

Gasification of the char derived from distillation of granulated scrap tyres.

This work reports the effect of pressure on the steam/oxygen gasification at 1000°C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank. In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34MJkg(-1). The combustion properties of the char (E(A)≈50 kJ mol(-1)), its temperature of self-heating (≈264°C), ignition temperature (≈459°C) and burn-out temperature (≈676°C) were found to be similar to those of a semi-anthracite. It is observed that the yield, H(2) and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm(3)kg(char)(-1) of syngas was produced, containing 28%v/v of H(2) and CO and with a HHV around 3.7 MJ Nm(-3). At 1.5 MPa, the syngas yield achieved 4.9N m(3)kg(char)(-1) with 30%v/v of H(2)-CO and HHV of 4.1 MJ Nm(-3). Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa. It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.

Microencapsulation of phosphogypsum into a sulfur polymer matrix: physico-chemical and radiological characterization.

The aim of this work is to prepare a new type of phosphogypsum-sulfur polymer cements (PG-SPC) to be utilised in the manufacture of building materials. Physico-chemical and radiological characterization was performed in phosphogypsum and phosphogypsum-sulfur polymer concretes and modeling of exhalation rates has been also carried out. An optimized mixture of the materials was obtained, the solidified material with optimal mixture (sulfur/phosphogypsum=1:0.9, phosphogypsum dosage=10-40 wt.%) results in highest strength (54-62 MPa) and low total porosity (2.8-6.8%). The activity concentration index (I) in the PG-SPC is lower than the reference value in the most international regulations and; therefore, these cements can be used without radiological restrictions in the manufacture of building materials. Under normal conditions of ventilation, the contribution to the expected radon indoor concentration in a standard room is below the international recommendations, so the building materials studied in this work can be applied to houses built up under normal ventilation conditions. Additionally, and taking into account that the PG is enriched in several natural radionuclides as (226)Ra, the leaching experiments have demonstrated that environmental impact of the using of SPCs cements with PG is negligible.

Distillation of granulated scrap tires in a pilot plant.

This paper reports the pyrolytic treatment of granulated scrap tires (GST) in a pilot distillation unit at moderate temperature (550°C) and atmospheric pressure, to produce oil, char and gas products. Tire-derived oil is a complex mixture of organic C(5)-C(24) compounds, including a very large proportion of aromatic compounds. This oil has a high gross calorific value (∼ 43 MJ kg(-1)) and N and S contents of 0.4% and 0.6%, respectively, falling within the specifications of certain heating fuels. The distillation gas is composed of hydrocarbons; methane and n-butane are the most abundant, investing the distillation gas with a very high gross calorific value (∼ 68 MJ Nm(-3)). This gas is transformed into electric power by a co-generation turbine. The distillation char is mostly made of carbon but with significant inorganic impurities (∼ 12 wt%). The quality of the solid residue of the process is comparable to that of some commercial chars. The quantity of residual solids, and the qualities of the gas, liquid and solid fractions, are similar to those obtained by conventional pyrolytic treatments of waste tires. However, the simplicity of the proposed technology and its low investment costs make it a very attractive alternative.

Recycling of hazardous waste from tertiary aluminium industry in a value-added material.

The recent European Directive on waste, 2008/98/EC seeks to reduce the exploitation of natural resources through the use of secondary resource management. Thus the main objective of this study was to explore how a waste could cease to be considered as waste and could be utilized for a specific purpose. In this way, a hazardous waste from the tertiary aluminium industry was studied for its use as a raw material in the synthesis of an added-value product, boehmite. This waste is classified as a hazardous residue, principally because in the presence of water or humidity, it releases toxic gases such as hydrogen, ammonia, methane and hydrogen sulfide. The low temperature hydrothermal method developed permits the recovery of 90% of the aluminium content in the residue in the form of a high purity (96%) AlOOH (boehmite). The method of synthesis consists of an initial HCl digestion followed by a gel precipitation. In the first stage a 10% HCl solution is used to yield a 12.63 g L(-1) Al( 3+) solution. In the second stage boehmite is precipitated in the form of a gel by increasing the pH of the acid Al(3+) solution by adding 1 mol L(-1) NaOH solution. Several pH values were tested and boehmite was obtained as the only crystalline phase at pH 8. Boehmite was completely characterized by X-ray diffraction, Fourier transform infrared and scanning electron microscopy. A study of its thermal behaviour was also carried out by thermogravimetric/differential thermal analysis.

Pseudo-emulsion membrane strip dispersion (PEMSD) pertraction of chromium(VI) using CYPHOS IL101 ionic liquid as carrier.

The transport of chromium(VI) from hydrochloric acid medium by pseudoemulsion membrane strip dispersion (PEMSD), using CYPHOS IL101 (phosphonium salt) as ionophore, is investigated under various experimental variables in the feed phase [hydrodynamic conditions, concentration of Cr(VI) (0.01-1 g/L), concentration of HCl (0.01-1M)], in the organic phase [carrier concentration (1-10% v/v)], and in the strip phase (stripping agent). Other variables investigated were the volume organic/strip phase ratios in the pseudoemulsion phase and also the type of membrane support. Under given experimental conditions, i.e., [Cr(VI)](0) = 0.01 g/L and [HCl](0) = 0.01 M in the feed phase and organic solution of 10% v/v CYPHOS IL101 in cumene, extractions exceeding 95% are obtained, and it is possible to strip using 1 M NaoH solution (also with recoveries in the 60% range). The performance of the system is also compared against other membrane operational configurations.

A hazardous waste from secondary aluminium metallurgy as a new raw material for calcium aluminate glasses.

A solid waste coming from the secondary aluminium industry was successfully vitrified in the ternary CaO-Al(2)O(3)-SiO(2) system at 1500 degrees C. This waste is a complex material which is considered hazardous because of its behaviour in the presence of water or moisture. In these conditions, the dust can generate gases such as H(2), NH(3), CH(4), H(2)S, along with heat and potential aluminothermy. Only silica sand and calcium carbonate were added as external raw materials to complete the glasses formula. Different nominal compositions of glasses, with Al(2)O(3) ranging between 20% and 54%, were studied to determine the glass forming area. The glasses obtained allow the immobilisation of up to 75% of waste in a multicomponent oxide system in which all the components of the waste are incorporated. The microhardness Hv values varied between 6.05 and 6.62GPa and the linear thermal expansion coefficient, alpha, varied between (62 and 139)x10(-7)K(-1). Several glasses showed a high hydrolytic resistance in deionised water at 98 degrees C.