The present study investigated the dynamics of manganese adsorption onto bone char in a continuou... more The present study investigated the dynamics of manganese adsorption onto bone char in a continuous fixed bed column using a mathematical model that incorporates: (i) the backmixing model to describe the fluid flow through the bed and (ii) the shrinking core model to describe the kinetic and mass transfer phenomena within spherical adsorbent particles. The proposed model consists of an ordinary differential equation system. Hydrodynamic, kinetic and diffusive parameters were determined by fitting the mathematical model to the experimental data obtained by Sicupira et al. (2015). For the operating conditions evaluated in this study, the intraparticle diffusion represented the controlling step of the adsorption process (Bi m > 3.8). The increase in the feed rate of the column (3.0-7.5 mL min-1) and the decrease in the height of the bed (8-16 cm) resulted in a decrease in the time required for the saturation of the column bed. The model is flexible for a variety of flow conditions and adequately reproduced the behavior of the manganese adsorption process in the fixed bed column operation (R²> 0.99) with an average percentage error less than15%.
Resumo A indústria siderúrgica gera cerca de 600 quilogramas de resíduos por tonelada de aço brut... more Resumo A indústria siderúrgica gera cerca de 600 quilogramas de resíduos por tonelada de aço bruto produzido. Estes resíduos, conforme estabelecido pela legislação ambiental vigente, devem ter uma destinação final adequada de forma a não acarretar poluição do meio ambiente. Além disso, a preocupação com a sustentabilidade e a escassez de recursos minerais não renováveis tem feito com que as usinas siderúrgicas invistam cada vez mais no desenvolvimento de meios de produção mais econômicos e menos poluidores e na busca de métodos adequados para a reciclagem ou a reutilização dos resíduos gerados, de forma a minimizar a quantidade de resíduos estocados ou destinados a aterros industriais. Neste contexto, destaca-se a escória e a lama de aciaria LD. Assim, este trabalho, avalia as possíveis tecnologias aplicáveis ao gerenciamento ambiental destes resíduos, apontando as tendências e as alternativas tecnológicas para seus tratamentos, de modo a contribuir para o aumento da sustentabilidade deste setor industrial.
The present study assessed the competing behavior between metals and extractants applied to the s... more The present study assessed the competing behavior between metals and extractants applied to the solvent extraction of calcium and/or nickel present in sulfuric solutions using the extractants Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) and/or D2EHPA (di-2-ethylhexyl phosphoric acid). Tests were designed to allow equivalent competing conditions between metals and extractants. Considering metal competition in the aqueous phase, calcium extraction remained unaffected in the presence of nickel, while nickel extraction curves with pH displaced to the right in the presence of calcium when D2EHPA (ΔpH 1/2 = 1.4) or Cyanex 272 + D2EHPA (ΔpH 1/2 = 0.9) were used. Considering extractant competition in the organic phase, metal extractions with Cyanex 272 + D2EHPA closely followed the curves obtained with D2EHPA, thus evidencing that it acts as the main extractant agent, synergism or antagonism effects being attributed to the presence of Cyanex 272. A synergistic increase in the calcium extraction occurred at pH ≥ 4.5, being unaffected in the presence of nickel, whereas rejection for nickel occurred in the whole pH range in the absence of calcium, and at pH < 5.5 in the presence of calcium. For the operating conditions investigated, Ca/Ni separation reached a maximum at pH = 4.5 (calcium extraction > 80%, nickel extraction < 0.25%, β Ca/Ni = 2159).
The present study investigated the dynamics of batch adsorption of manganese onto bone char by us... more The present study investigated the dynamics of batch adsorption of manganese onto bone char by using two distinct mathematical formulations: the diffusion model and the shrinking core model. Both models assumed spherical particles and adequately described the transient behavior of metal adsorption under changing operating conditions. Comparatively, the diffusion model described the manganese adsorption better at distinct particle sizes even when small particles were used (d p ≤ 0.147 mm); the shrinking core model proved to be more reliable when larger adsorbent particles were used (d p > 0.147 mm), and it described experimental data better at changing solid-liquid ratios. Manganese adsorption was favored when: (i) smaller adsorbing particles were used due to the increase in the contact area and easier access to reacting sites of the char; however, such an effect proved to be limited to d p ≤ 0.147 mm, and (ii) higher solid-liquid ratios were used due to the increase in the available reacting sites. External and intraparticle mass transfer dependences on particle size and solid-liquid ratio were also investigated, and results corroborated with prior investigations found in the literature.
The present study investigated the solvent extraction of uranium from sulfate acid solutions usin... more The present study investigated the solvent extraction of uranium from sulfate acid solutions using Alamine 336 as an extractant dissolved in commercial kerosene Exxsol D-100 and 5% v/v of tridecanol as a modifying agent at room temperature (25±2) ºC and an aqueous/organic volumetric ratio of unity. Experiments were carried out at typical concentration levels like those used at the uranium plant of INB (Indústrias Nucleares do Brasil), Brazil. Data fitting using the slope analysis method revealed that uranium is extracted by Alamine 336 as UO2SO4 and UO2(SO4)2 2species, forming (R3NH +)2UO2(SO4)2 2in the organic phase; the extraction of the species UO2(SO4)3 4seems improbable for the operating conditions investigated. The extraction of uranium is significantly reduced when the concentrations of sulfate and chloride ions in the aqueous phase are increased.
Magnetic nanoparticles can improve the efficiency of phase separation time in multi-stage operati... more Magnetic nanoparticles can improve the efficiency of phase separation time in multi-stage operations when a magnetic field is present. As such operations involve contact with aqueous and/or organic solutions, hydrophilic magnetic nanoparticles synthesized through the co-precipitation method were functionalized with oleic acid to attain hydrophobic magnetic nanoparticles. Both nanoparticles were characterized morphologically, chemically and magnetically. The results revealed that the particles (size ≈ 10 nm) consisted of an iron oxide mixture of magnetite and maghemite. The functionalization with oleic acid was effective in converting them into hydrophobic nanoparticles. Both particles were ferro/ferrimagnetic and the presence of oleic acid did not interfere significantly in the saturation magnetization value. The chemical stability of both nanoparticles were also evaluated, as an attempt of simulating broad industrial conditions to which the nanoparticles may be subjected; the hydrophilic nanoparticles were resistant at pH ≥ 4, while the hydrophobic nanoparticles were stable at pH ≥ 3.
The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated ... more The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.210.9%), ...
Separation of the main metals contained in spent Li-ion batteries has been investigated using a t... more Separation of the main metals contained in spent Li-ion batteries has been investigated using a treatment route consisting of the following steps: manual dismantling, acid leaching, precipitation with NH 4 OH and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphinic acid] as the extractant agent. Aluminium, cobalt, lead and lithium were the main metal species identified in the residue. Lead was found solely in the anode of the battery, so this metal can be separated manually from the other metal species, which were found to predominate in the cathode. The following operational variables were investigated in the acid leaching step: temperature, solid/liquid ratio, H 2 SO 4 concentration and H 2 O 2 concentration which was used as the oxidizing agent. Around 55% of aluminium, 80% of cobalt and 95% of lithium were leached from the cathode when leaching solutions with H 2 O 2 were carried out. In the precipitation step, NH 4 OH was added to the leach liquor to raise the pH and aluminium was partially separated from cobalt and lithium at pH 5. After filtration, the aqueous solution was submitted to a purification step by liquid-liquid extraction with Cyanex 272 and around 85% of cobalt was separated.
The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking... more The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.
A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batterie... more A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batteries in order to separate base metals such as nickel, copper, aluminium, cadmium, lithium and cobalt which constitute the main metallic species of spent NiCd, NiMH and Li-ion rechargeable batteries. The route comprises the following main steps: (1) sorting batteries by type, (2) battery dismantling to separate the spent battery dust from plastic, iron scrap and paper, (3) leaching of the dust with sulphuric acid and (4) metal separation by a liquid-liquid extraction using Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant. The metal content of NiCd, NiMH and Li-ion batteries from three distinct manufacturers has been evaluated. A factorial design of experiments was used to investigate the leaching step using operational variables such as temperature, H 2 SO 4 concentration, S/L ratio and H 2 O 2 concentration. Analysis of metal separation by the liquid-liquid extraction with Cyanex 272 identified a pH 1/2 2.5-3.0 for zinc and aluminium, pH 1/2 4.0-4.5 for manganese, cadmium, copper and cobalt, pH 1/2 6.5 for nickel and pH 1/2 8.0 for lithium. These results indicate that batteries must be previously sorted by type and treated separately. In addition, data fitting to an equilibrium model proposed for the reactive test system by the European Federation of Chemical Engineering (EFChE) have indicated that MR 2 (RH) 2 and MR 2 complexes (where M = Zn, Mn, Co, Cd and Cu) co-exist in the organic phase with Cyanex 272 depending on the loading conditions. The route has been found technically viable to separate the main metallic species of all batteries considered in this study.
The use of solvent extraction to recover metals and water from industrial residues is highlighted... more The use of solvent extraction to recover metals and water from industrial residues is highlighted in this work. The method was applied (1) to selectively concentrate Zn from effluents generated by the zinc industry, (2) to separate Zn and Fe from spent pickling effluents produced by the hot-dip galvanizing industry, and (3) to recover Co and Ni from spent batteries. Batch and pilot scale data was used to point out solvent extraction as a feasible method to reuse both metals and water thus resulting in energy savings with reducing environmental impacts, minimizing costs required to transport hazardous materials to waste sites, to replace the discharged wastewater and to produce the raw material that would be previously discharged as wastes.
The present study investigated the dynamics of manganese adsorption onto bone char in a continuou... more The present study investigated the dynamics of manganese adsorption onto bone char in a continuous fixed bed column using a mathematical model that incorporates: (i) the backmixing model to describe the fluid flow through the bed and (ii) the shrinking core model to describe the kinetic and mass transfer phenomena within spherical adsorbent particles. The proposed model consists of an ordinary differential equation system. Hydrodynamic, kinetic and diffusive parameters were determined by fitting the mathematical model to the experimental data obtained by Sicupira et al. (2015). For the operating conditions evaluated in this study, the intraparticle diffusion represented the controlling step of the adsorption process (Bi m > 3.8). The increase in the feed rate of the column (3.0-7.5 mL min-1) and the decrease in the height of the bed (8-16 cm) resulted in a decrease in the time required for the saturation of the column bed. The model is flexible for a variety of flow conditions and adequately reproduced the behavior of the manganese adsorption process in the fixed bed column operation (R²> 0.99) with an average percentage error less than15%.
Resumo A indústria siderúrgica gera cerca de 600 quilogramas de resíduos por tonelada de aço brut... more Resumo A indústria siderúrgica gera cerca de 600 quilogramas de resíduos por tonelada de aço bruto produzido. Estes resíduos, conforme estabelecido pela legislação ambiental vigente, devem ter uma destinação final adequada de forma a não acarretar poluição do meio ambiente. Além disso, a preocupação com a sustentabilidade e a escassez de recursos minerais não renováveis tem feito com que as usinas siderúrgicas invistam cada vez mais no desenvolvimento de meios de produção mais econômicos e menos poluidores e na busca de métodos adequados para a reciclagem ou a reutilização dos resíduos gerados, de forma a minimizar a quantidade de resíduos estocados ou destinados a aterros industriais. Neste contexto, destaca-se a escória e a lama de aciaria LD. Assim, este trabalho, avalia as possíveis tecnologias aplicáveis ao gerenciamento ambiental destes resíduos, apontando as tendências e as alternativas tecnológicas para seus tratamentos, de modo a contribuir para o aumento da sustentabilidade deste setor industrial.
The present study assessed the competing behavior between metals and extractants applied to the s... more The present study assessed the competing behavior between metals and extractants applied to the solvent extraction of calcium and/or nickel present in sulfuric solutions using the extractants Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) and/or D2EHPA (di-2-ethylhexyl phosphoric acid). Tests were designed to allow equivalent competing conditions between metals and extractants. Considering metal competition in the aqueous phase, calcium extraction remained unaffected in the presence of nickel, while nickel extraction curves with pH displaced to the right in the presence of calcium when D2EHPA (ΔpH 1/2 = 1.4) or Cyanex 272 + D2EHPA (ΔpH 1/2 = 0.9) were used. Considering extractant competition in the organic phase, metal extractions with Cyanex 272 + D2EHPA closely followed the curves obtained with D2EHPA, thus evidencing that it acts as the main extractant agent, synergism or antagonism effects being attributed to the presence of Cyanex 272. A synergistic increase in the calcium extraction occurred at pH ≥ 4.5, being unaffected in the presence of nickel, whereas rejection for nickel occurred in the whole pH range in the absence of calcium, and at pH < 5.5 in the presence of calcium. For the operating conditions investigated, Ca/Ni separation reached a maximum at pH = 4.5 (calcium extraction > 80%, nickel extraction < 0.25%, β Ca/Ni = 2159).
The present study investigated the dynamics of batch adsorption of manganese onto bone char by us... more The present study investigated the dynamics of batch adsorption of manganese onto bone char by using two distinct mathematical formulations: the diffusion model and the shrinking core model. Both models assumed spherical particles and adequately described the transient behavior of metal adsorption under changing operating conditions. Comparatively, the diffusion model described the manganese adsorption better at distinct particle sizes even when small particles were used (d p ≤ 0.147 mm); the shrinking core model proved to be more reliable when larger adsorbent particles were used (d p > 0.147 mm), and it described experimental data better at changing solid-liquid ratios. Manganese adsorption was favored when: (i) smaller adsorbing particles were used due to the increase in the contact area and easier access to reacting sites of the char; however, such an effect proved to be limited to d p ≤ 0.147 mm, and (ii) higher solid-liquid ratios were used due to the increase in the available reacting sites. External and intraparticle mass transfer dependences on particle size and solid-liquid ratio were also investigated, and results corroborated with prior investigations found in the literature.
The present study investigated the solvent extraction of uranium from sulfate acid solutions usin... more The present study investigated the solvent extraction of uranium from sulfate acid solutions using Alamine 336 as an extractant dissolved in commercial kerosene Exxsol D-100 and 5% v/v of tridecanol as a modifying agent at room temperature (25±2) ºC and an aqueous/organic volumetric ratio of unity. Experiments were carried out at typical concentration levels like those used at the uranium plant of INB (Indústrias Nucleares do Brasil), Brazil. Data fitting using the slope analysis method revealed that uranium is extracted by Alamine 336 as UO2SO4 and UO2(SO4)2 2species, forming (R3NH +)2UO2(SO4)2 2in the organic phase; the extraction of the species UO2(SO4)3 4seems improbable for the operating conditions investigated. The extraction of uranium is significantly reduced when the concentrations of sulfate and chloride ions in the aqueous phase are increased.
Magnetic nanoparticles can improve the efficiency of phase separation time in multi-stage operati... more Magnetic nanoparticles can improve the efficiency of phase separation time in multi-stage operations when a magnetic field is present. As such operations involve contact with aqueous and/or organic solutions, hydrophilic magnetic nanoparticles synthesized through the co-precipitation method were functionalized with oleic acid to attain hydrophobic magnetic nanoparticles. Both nanoparticles were characterized morphologically, chemically and magnetically. The results revealed that the particles (size ≈ 10 nm) consisted of an iron oxide mixture of magnetite and maghemite. The functionalization with oleic acid was effective in converting them into hydrophobic nanoparticles. Both particles were ferro/ferrimagnetic and the presence of oleic acid did not interfere significantly in the saturation magnetization value. The chemical stability of both nanoparticles were also evaluated, as an attempt of simulating broad industrial conditions to which the nanoparticles may be subjected; the hydrophilic nanoparticles were resistant at pH ≥ 4, while the hydrophobic nanoparticles were stable at pH ≥ 3.
The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated ... more The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.210.9%), ...
Separation of the main metals contained in spent Li-ion batteries has been investigated using a t... more Separation of the main metals contained in spent Li-ion batteries has been investigated using a treatment route consisting of the following steps: manual dismantling, acid leaching, precipitation with NH 4 OH and liquid-liquid extraction using Cyanex 272 [bis(2,4,4-trimethylpentyl) phosphinic acid] as the extractant agent. Aluminium, cobalt, lead and lithium were the main metal species identified in the residue. Lead was found solely in the anode of the battery, so this metal can be separated manually from the other metal species, which were found to predominate in the cathode. The following operational variables were investigated in the acid leaching step: temperature, solid/liquid ratio, H 2 SO 4 concentration and H 2 O 2 concentration which was used as the oxidizing agent. Around 55% of aluminium, 80% of cobalt and 95% of lithium were leached from the cathode when leaching solutions with H 2 O 2 were carried out. In the precipitation step, NH 4 OH was added to the leach liquor to raise the pH and aluminium was partially separated from cobalt and lithium at pH 5. After filtration, the aqueous solution was submitted to a purification step by liquid-liquid extraction with Cyanex 272 and around 85% of cobalt was separated.
The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking... more The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.
A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batterie... more A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batteries in order to separate base metals such as nickel, copper, aluminium, cadmium, lithium and cobalt which constitute the main metallic species of spent NiCd, NiMH and Li-ion rechargeable batteries. The route comprises the following main steps: (1) sorting batteries by type, (2) battery dismantling to separate the spent battery dust from plastic, iron scrap and paper, (3) leaching of the dust with sulphuric acid and (4) metal separation by a liquid-liquid extraction using Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant. The metal content of NiCd, NiMH and Li-ion batteries from three distinct manufacturers has been evaluated. A factorial design of experiments was used to investigate the leaching step using operational variables such as temperature, H 2 SO 4 concentration, S/L ratio and H 2 O 2 concentration. Analysis of metal separation by the liquid-liquid extraction with Cyanex 272 identified a pH 1/2 2.5-3.0 for zinc and aluminium, pH 1/2 4.0-4.5 for manganese, cadmium, copper and cobalt, pH 1/2 6.5 for nickel and pH 1/2 8.0 for lithium. These results indicate that batteries must be previously sorted by type and treated separately. In addition, data fitting to an equilibrium model proposed for the reactive test system by the European Federation of Chemical Engineering (EFChE) have indicated that MR 2 (RH) 2 and MR 2 complexes (where M = Zn, Mn, Co, Cd and Cu) co-exist in the organic phase with Cyanex 272 depending on the loading conditions. The route has been found technically viable to separate the main metallic species of all batteries considered in this study.
The use of solvent extraction to recover metals and water from industrial residues is highlighted... more The use of solvent extraction to recover metals and water from industrial residues is highlighted in this work. The method was applied (1) to selectively concentrate Zn from effluents generated by the zinc industry, (2) to separate Zn and Fe from spent pickling effluents produced by the hot-dip galvanizing industry, and (3) to recover Co and Ni from spent batteries. Batch and pilot scale data was used to point out solvent extraction as a feasible method to reuse both metals and water thus resulting in energy savings with reducing environmental impacts, minimizing costs required to transport hazardous materials to waste sites, to replace the discharged wastewater and to produce the raw material that would be previously discharged as wastes.
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