PROCESSING OF SPENT ULTRA-DEEP HYDRODESULFURIZATION CATALYSTS. This work discusses the recycling of spent NiMo/Al2O3 catalysts from ultra-deep hydrodesulfurization (HDS) units. They contain a refractory coke and fouling elements from the processed feedstocks. Samples were preoxidized (600 ºC) for 12 h using a very slow heating rate to eliminate coke and volatiles. Experiments were performed in the presence of HF + H2O2 mixtures under stirring at 25-60oC for 1-4 h. The amount of insoluble matter was the lowest (< 1 wt.% of the initial mass) after leaching for 2 h at 60oC using an excess of 50 vol.% HF and 20 vol.% H2O2. Leached molybdenum and vanadium were extracted together with Alamine 304 (tri-dodecylamine) in n-heptane at pH below 2. Aluminum and iron were precipitated from the raffinate as Na3AℓF6 (+ Na3FeF6) by adjusting pH at ~4 using 6 mol L-1 NaOH. Nickel was either recovered by solvent extraction using D2EHPA (bis-(2-ethylhexyl)phosphoric acid) in n-heptane at pH 6 or precipitated at pH 8 using 6 mol L-1 NaOH. The first method proved better as less contaminants were present. After slow evaporation of the final aqueous solution, a mixture of Na2SiF6 and NaF was recovered. Fluoride losses were very low (~0.10 wt.%).

Historical aspects related to eight reagents that were present in analytical chemistry laboratories in the first decades of the twentieth century are described. They have peculiarities that are based on their curious names or the purposes for which they were intended. Their presence in the laboratory environment reflected their industrial applications and the chemical analysis procedures used at that time. From the mid XXth century, with the migration of qualitative analysis to the chemistry teaching, these reagents have been replaced by others that today serve the same purposes as those previously used. However, many of them still retain their industrial importance. This historical overview emphasizes the importance of the evolution of chemicals and chemical assays for security and efficiency reasons. Learning from past experiences develops a critical spirit and laboratory behavior more committed to occupational hygiene and safety, without losing sight the learning power that qualitative analytical chemistry offers.

The recovery of precious and base metals of a metal concentrate from ground waste printed circuit boards (PCBs) is described in detail. Samples were treated with NaOHaq. to remove the soldering mask. Experiments were performed in acidic medium (HF, H2SO4, CH3COOH or H3PO4) using H2O2 as oxidant. Base metals were leached in high yields (>99 wt.%) at ~40 ºC after ~1 h (HF), ~2 h (H2SO4), ~4 h (H3PO4) and ~5 h (CH3COOH). Lead precipitated in the presence of H2SO4 and HF. Precious metals were not oxidized. Ceramic/fiberglass components were dissolved in the presence of HF. Silver, palladium and gold were recovered from the insoluble solid, in this order, by a sequential oxidative treatment in aqueous medium. Recovery of leached elements was possible by a combination of solvent extraction and precipitation. The choice of the extractant and the precipitant were essential to recover them with high yields. The leachates from H3PO4 + H2O2 experiments could not be processed above pH 2.5. Leaching of waste PCBs in the presence of a weak organic acid is possible but a multistage separation scheme for elements recovery is unavoidable as PCBs is a complex material in terms of composition.

This work describes the occurrence and the economic importance of manganese in Brazil, covering a period of almost 130 years. After the gold cycle, manganese ores became the most important mineral commodity of Brazil’s export agenda until 1945. Brazil has one of the largest world reserves and has been among the world’s largest producers of manganese ore for over a century. The influence of international scenario on the manganese market affected its trade balance throughout the twentieth century. The Brazilian manganese ore production was strongly stimulated by external events (such as the I and II World Wars) and the development of the US and the European steel industries in the early XXth century. However, internal consumption increased as the Brazilian steel industry developed. The chief use of manganese in Brazil and in the world is in the steel production. Nonmetallurgical uses include battery cathodes, fertilizers, animal feed, water treatment, analytical chemistry (permanganometry), pigments, cosmetics and glasses. The perspectives for manganese in Brazil in the future are encouraging, but it is necessary to search for new deposits and develop processing of tailings and low grade ores.

A new silicon-aluminum-zirconium ternary oxide (SiO2/Al2O3/ZrO2) was prepared by the sol-gel method followed by one-step washing with absolute ethanol or two-step washing with absolute ethanol followed by ultra-pure water. Both ternary oxides presented high surface area (over 340 m2 g-1). The binding energy values for Zr3d and Al2p levels showed the insertion of Zr and Al atoms in silica matrix, confirming the dispersion surface of these elements as shown by scanning electron microscope (SEM) and energy dispersive X-ray fluorescence spectroscopy (EDXRF) data. A weight loss around 40 wt.% was found for both samples submitted to thermogravimetric analysis (TGA). Crystallographic data showed the presence of monoclinic and tetragonal ZrO2 phases in different proportions according to the calcination temperature. Regarding the acid-base properties, temperature-programmed desorption of CO2 (CO2-TPD) profiles suggested that washing with water reduced the overall basicity of the samples and removed the strongest basic sites. However, according to temperature-programmed desorption of NH3 (NH3-TPD) profiles, washing significantly increased the amount of weak acid sites, in agreement with pyridine adsorption data. Brønsted acid sites (BAS) are ever dominant but washing with ethanol followed by water reduced the number of Lewis acid sites (LAS).

This work examines the leaching of printed circuit boards (PCBs) from cell phones in aqueous solutions containing HF + H2O2 or HF + NaClO under mild experimental conditions. The PCBs were not ground but were previously treated with 6 mol L-1 NaOH at 50 ºC for 1 h to remove their soldering mask. The HF + H2O2 mixtures leached copper and base metals (except lead) at 35-40 ºC, leaving a solid residue containing lead and noble metals. Leaching was fastest (1 h) when HF and H2O2 concentrations were at least 5 mol L-1 and 3 mol L-1, respectively. The processing of the solid residue is also described in detail. It was leached with water at ~90 ºC followed by HNO3aq. at 25 ºC. Lead, palladium and silver were recovered in this order, leaving gold as final solid. After 1 h at 35-40 ºC, 5 mol L-1 HF + 0.3 mol L-1 NaClO mixtures leached the base metals, copper, gold and palladium. Gold was recovered by liquid-liquid extraction with methyl isobutyl ketone. Silver precipitated as chloride. This salt was isolated by leaching with NH3aq. Loss of fluoride ions (as HF) was below 0.5 wt.% after leaching and handling the solid residue.

This paper describes a route for recovering manganese and zinc from spent zinc-MnO2 dry cells via acid leaching using sulfuric or hydrochloric acids as leachants. Hydrogen peroxide was added as reductant. Experiments were run at 25-40 °C for 1-3 h. Under the best optimal conditions, over 97.5 wt.% of zinc and manganese were leached by both acids. Zn(II) was best extracted at high free acidity (≥ 1 mol L-1) with tributylphosphate (TBP) or trialkylphosphine oxides (Cyanex 923) diluted in n-heptane. Cyanex 923 was a better extractant than TBP, and the extraction was better performed in hydrochloric leachates. Mn(II) was more co-extracted from hydrochloric leachates and when Cyanex 923 was the extractant, but was easily scrubbed with dilute leachant (~1-2 mol L-1). Zn(II) striping was possible using 5 mol L-1 HCl or H2SO4. Manganese was precipitated as oxalate (MnC2O4.2H2O), free of leached contaminants. High-purity sodium salts of the anions of the leachants were recovered after slow evaporation of the final solution.

This paper describes a route for recovering cobalt and lithium from spent Li-ion batteries via acidic leaching. Sulfuric, hydrochloric, hydrofluoric and formic acids were used as leachants. Hydrogen peroxide was added as reductant, except for formic acid since it is itself a reductant. Experiments were run at 25-40 ºC for 1-3 h. Under the best optimal conditions, the leaching efficiency order was HCl ≈ HF > H2SO4 > HCOOH. Over 90 wt.% of cobalt and lithium were leached by the inorganic acids. The insoluble matter corresponds mainly to the carbon from the cathode. Co(II) was extracted with D2EHPA 16 vol.% diluted in n-hexane at pH ~5 (A/O ratio 1/1 vol/vol, one stage, 25 ºC). Co(II) striping was possible using a dilute leachant (1-2 mol L-1 HCl or H2SO4, 4-5 mol L-1 HF or HCOOH). Lithium was isolated from the raffinate by precipitation as carbonate or phosphate.

This paper describes a route for recovering manganese and zinc from spent zinc-MnO2 dry cells via acid leaching. Sulfuric, hydrofluoric and formic acids were used as leachants. Hydrogen peroxide was added as reductant, except for formic acid since it is itself a reductant. Experiments were run at 25-40 ºC for 1-3 h. Under the best optimal conditions, over 95 wt.% of zinc and manganese were leached irrespective of the leachant. Leaching of contaminants was strongly dependent on the leachant due to the insolubility of salts or complexing reactions. Zn(II) was best extracted with D2EHPA diluted in n-heptane at pH > 1, particularly from the leachates of weak acids. Mn(II) was much more co-extracted from sulfuric leachates, but was easily scrubbed with dilute leachant (~2 mol L -1). Zn(II) striping was possible using 5 mol L -1 H2SO4. Manganese was isolated as MnO2 carrying the leached contaminants. High-purity sodium salts of the anions of the leachants were recovered after slow evaporation of the final solution.

<p>This work describes the fundamentals and evolution of two current solid-liquid separation methods found in the chemical laboratory: the filter paper and the centrifuge. Both methods were developed in the 19th century and are recognized as valuable techniques for industrial and laboratory purposes. However, significant improvements were introduced only from the end of the 19th century. The classical manual centrifuge was replaced by electric models: safety, maximum speed and number of samples that can be centrifuged at a time were greatly increased. The manufacture of filter paper was initially done by hand, but later benefited from papermaking industrial technologies. Many pretreatments of the wooden fibers were developed, particularly after 1880, thus resulting in many filter paper types for qualitative and quantitative applications. These two separation techniques are also found in various procedures in our everyday life.</p>

Este trabalho analisa os três volumes da obra Problemas Práticos de Physica Elementar, de Heitor Lyra da Silva, editada entre 1916 e 1929, destinada a alunos dos então cursos regulares (primário e secundário) e profissional. Rompendo com os padrões de ensino da época, sua didática pretendia ser a mais simples e objetiva possível. O instrumental proposto foi concebido para que fosse acessível a todas as regiões do país. A metodologia de ensino é de aprendizado direto, por repetição e análise crítica dos resultados experimentais. A estrutura e a finalidade da obra se inseriam no contexto do chamado Movimento Renovador, consolidado na década de 1920, que visava uma educação individualizada que respeitasse as diferenças no desenvolvimento de cada estudante. No entanto, as ideias inovadoras da educação sob princípios liberais não conseguiram se impor às correntes conservadoras que dominavam o cenário educacional brasileiro, sendo a nova proposta didática relegada ao esquecimento.

This work analyses the book Practical Problems of Elemental Physics, written by Heitor Lyra da Silva and published between 1916 and 1929. It was written to students of the elementary and high schools, and technical courses. Unlike the current teaching methods, didactics intended to be as simple and objective as possible. The proposed instruments are of a basic conception and can be easily assembled by teachers and students anywhere in the country. The teaching method is direct learning, based on repetition of the experiments and a critical analysis of experimental data. The structure and the objective of the book show characteristics of the so called Renovation Movement, consolidated in the 1920s, whose objective was to establish an individual education, respecting the differences of the development of each student. However, the new educational ideas under liberal principles have failed to overcome the conservative currents that dominated the Brazilian educational scenario. This new didactic proposal was later abandoned.

Este trabalho passa em revista o conceito de densidade e descreve o densímetro, instrumento destinado a medir a densidade de líquidos puros ou soluções sem o auxílio de uma balança. A concepção do densímetro se baseia no princípio de Arquimedes (flutuabilidade). O emprego desse instrumento ganhou impulso a partir do século XVII. Duas versões foram propostas: os de volume constante e os de peso constante. O formato básico praticamente não mudou em mais de 250 anos. A evolução mais perceptível se deu no elemento de equilíbrio (lastro), que passou do mercúrio líquido ás bolas de chumbo unidas por resina hoje em dia. O densímetro é um instrumento prático e barato para se realizar experiências simples que despertam nos jovens a inserção da química e da física no cotidiano, e mostram a importância da densidade no controle de qualidade de produtos (como o etanol combustível e bebidas).

This work presents the definition of density and describes the densitometer, apparatus which measures density of pure liquids or solution without the use of a balance. The conception of the densitometer is based on the Archimedes's Principle (flotation). The use of this instrument was greatly accelerated in the XVII century. Two models were proposed: constant weight and constant volume. Its basic format has not changed much over the last 250 years. The most interesting evolution was the change of the ballast: from liquid mercury to solid lead balls fixed by a resin. The densitometer is a cheap and practical apparatus to make some simple experiences that show the importance of the density in chemistry and physics and in our everyday life, as well as in the quality control of some goods (like ethanol and beverages) via density measurement.

A hydrometallurgical process applicable to printed circuit boards of small electrical and electronic devices was developed. This involved three leaching steps (60 ºC, 2 h): 6 mol L-1 NaOH, 6 mol L-1 HCl and aqua regia. NaOH removed the resin and flame retardant that covered the circuit boards. HCl dissolved the most electropositive metals and a small amount of copper (~0.3 wt%). Aqua regia dissolved the noble metals. Silver precipitated as AgCl. Gold and platinum were quantitatively extracted with pure methyl-isobutylketone and Alamine 336 (10 % vol. in kerosene), respectively. Slow evaporation of the raffinate crystallized CuCl2.4H2O (89% yield).

This study investigated the treatment of a liquid radioactive waste containing uranium (235U + 238U) using nanofiltration membranes. The membranes were immersed in the waste for 24-5000 h, and their transport properties were evaluated before and after the immersion. Surface of the membranes changed after immersion in the waste. The SW5000 h specimen lost its coating layer of polyvinyl alcohol, and its rejection of sulfate ions and uranium decreased by about 35% and 30%, respectively. After immersion in the waste, the polyamide selective layer of the membranes became less thermally stable than that before immersion.

This work examines traditional and new routes for removal of H2S and other sulfur compounds from spent sufidic caustic (SSC). SH- (hydrogenosulfide) and S2- (sulfide) ions were quantitatively oxidized at 25 ºC using H2O2, NaOCl or a spent sulfochromic mixture. SH-/S2- ions were also removed via reaction with freshly prepared iron or manganese hydroxides, or after passing the SSC through strong basic anion exchange resins (OH- form). The treated caustic solution, as well as iron/manganese hydroxides, removed H2S from diesel samples at 25 ºC. SSC treatment via strong basic anion-exchange resins produced the treated caustic solution with the highest free alkalinity.