Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

Hidrogenação eletrocatalítica de substratos orgânicos: estudo da eficiência dos metais nobres níquel, paládio e platina usando eletrodos modificados

Nickel, palladium and platinum micro-crystals were dispersed in films covering a vitreous carbon plate electrode by ion exchange followed by electroreduction of their ions. These modified electrodes were used in the electrocatalytic hydrogenation of several substrates of different classes and their efficiency is reported. A comparison among them was performed based on the structural characteristics of the metals. A modified electrode containing platinum showed to be more efficient than a palladium modified electrode and the one of nickel was the less efficient.

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno

This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO), have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

Aplicação e modificação química da sílica gel obtida de areia

The silica gel was obtained from sand and its surface was modified with POCl3 to produce Si-Cl bonds on the silica surface. Ethylenediamine was covalently bonded onto the chlorinated silica surface. The adsorption of the chlorides of divalent cobalt, nickel and copper was qualitatively studied to show that the bonding of ethylenediamine onto the silica gel surface produces a solid base capable of chelating metal ions from solution. The experiments illustrate the extraction of silica gel, its reactivity, the development of modified surfaces and its application in removing metal ions from water and are deigned for undergraduate inorganic chemistry laboratories.

O modelamento estatístico de misturas: experimento tutorial usando voltametria de redissolução anódica

This work illustrates the modeling procedure for a solvent mixture using the simplex- centroid approach. The selected experiment was the optimization of the peak current observed in the direct determination of nickel by anodic stripping voltammetry (ASV) in a solvent mixture composed of N,N-dimethylformamide, ethanol and water. The text is presented in a tutorial way, showing in detail the several steps which must be followed in such a process. Since not all possible mixtures lead to a measurable instrumental response, pseudocomponents had to be used to rescale the experimental design. This also allows to show how to apply this tool, usually troublesome for non-specialists in mixture modeling procedures.

Estudo eletroquímico de um novo banho galvânico de zinco alcalino livre de cianetos

A systematic electrochemical study of a novel cyanide free galvanic plating solution of alkaline zinc is presented. Cell Hull tests and potentiodynamic linear polarization measurements were carried out to evaluate the influence of operational parameters, such as concentration, current efficiency and degradation of additives. The stability of the bath was assessed by a long term test during 40 h at 200 A m-2. The morphology of the coatings was characterized by scanning electron microscopy. The results showed good performance of the plating solution. The cost is similar to that of the commercial cyanide bath and lower than that of the commercial cyanide free bath.

Recuperação de metais de catalisadores de hidrorrefino usados via fusão com KHSO4

This work describes a process for metal recovery from spent NiMo and CoMo/Al2O3 commercial hydrorefining catalysts. The samples were treated by fusion with potassium hydrogen sulfate (5 h, 600 ºC) with a KHSO4/catalyst mass ratio of 10:1. After fusion the solid was solubilized in water (100 ºC), leaving silicon compounds as residue. Losses of nickel and cobalt may reach 16 wt% of the amount present in the sample, depending on the silicon content. Soluble metals were isolated by selective precipitation techniques (nickel, cobalt, aluminum) or by solvent extraction with methyl-isobutyl ketone (molybdenum) in a hydrochloric acid medium. All metals were recovered in very good yields except for nickel and cobalt in the presence of considerable amounts of silicon. Soluble wastes consist of potassium/sodium sulfates/chlorides. Solid wastes correspond to about 4 wt% of the catalyst and can be discarded in industrial dumps.

Metil coenzima M redutase (MCR) e o fator 430 (F430)

This review presents studies on methyl coenzyme M reductase, the biological system Factor 430 (F430) and the use of nickel(II) complexes as structural and functional models. The ability of F430 and nickel(II) macrocycle complexes to mediate the reductive dehalogenation of cyclohexyl halogens and the CH3-S bond cleavage of methyl CoM (by sodium borohydride and some intermediate species) proposed for the catalytic cycle of the biological system F430 was reviewed. The importance of the structure of the nickel complexes and the condition of the catalytic reduction reaction are also discussed.

Síntese e caracterização de perovskitas LaNi(1-x)Co xO3 como precursores de catalisadores para a conversão do metano a gás de síntese pela reforma com CO2

LaNiO3 perovskite was modified by partial substitution of nickel by cobalt in order to increase the stability and resistance to carbon deposition during the methane CO2 reforming. The results showed that a suitable combination of precipitation and calcination steps resulted in oxides with the desired structure and with important properties for application in heterogeneous catalysis. The partial substitution of Ni by Co resulted in lower rates of conversion of both the reactants, but the catalyst stability was highly increased. The LaNi0.3Co0.7O3 catalyst, calcined at 800 ºC, was the most active under the reaction conditions.

Produção de hidrogênio a partir da reforma a vapor de etanol utilizando catalisadores Cu/Ni/gama-Al2o3

Cu/Ni/gamma-Al2O3 catalysts were prepared by an impregnation method with 2.5 or 5% wt of copper and 5 or 15% wt of nickel and applied in ethanol steam reforming. The catalysts were characterized by atomic absorption spectrophotometry, X-ray diffraction, temperature programmed reduction with hydrogen and nitrogen adsorption. The samples showed low crystallinity, with the presence of CuO and NiO, both as crystallites and in dispersed phase, as well as of NiO-Al2O3. The catalytic tests carried out at 400 ºC, with a 3:1 water/ethanol molar ratio, indicated the 5Cu/5Ni/Al2O3 catalyst as the most active for hydrogen production, with a hydrogen yield of 77% and ethanol conversion of 98%.

Otimização do banho eletrolítico da liga Fe-W-B resistente à corrosão

A study on optimization of bath parameters for electrodeposition of Fe-W-B alloys from plating baths containing ammonia and citrate is reported. A 2³ full factorial design was successfully employed for experimental design analysis of the results. The corrosion resistance and amorphous character were evaluated. The bath conditions obtained for depositing the alloy with good corrosion resistance were: 0.01 M iron sulfate, 0.10 M sodium tungstate and 0.60 M ammonium citrate. The alloy was deposited at 12% current efficiency. The alloy obtained had Ecorr -0.841 V and Rp 1.463 x 10(4) Ohm cm². The deposit obtained under these conditions had an amorphous character and no microcracks were observed on its surface. Besides this, the bath conditions obtained for depositing the alloy with the highest deposition efficiency were: 0.09 M iron sulfate, 0.30 M sodium tungstate and 0.50 M ammonium citrate. The alloy was deposited at 50% current efficiency, with an average composition of 34 wt% W, 66 wt% Fe and traces of boron. The alloy obtained had Ecorr -0.800 V and Rp 1.895 x 10³ Ohm cm². Electrochemical corrosion tests verified that the Fe-W-B alloy deposited under both conditions had better corrosion resistance than Fe-Mo-B.

Recuperação de cádmio de baterias níquel-cádmio via extração seletiva com tributilfosfato (TBP)

This work describes a recovery process of cadmium from spent nickel-cadmium batteries by a new hydrometallurgical route based on the selective extraction in hydrochloric acid medium with tributylphosphate (TBP), alone or dissolved in kerosene. The best results were obtained when TBP concentration was at least 75 vol%. Nickel extraction was negligible under these conditions. It was isolated after processing the rafinate through an anionic ion-exchange column. Final wastes generated are basically sodium chloride solutions, with no turbidity, color or heavy metals present in significant amounts.

Efecto de la naturaleza del precursor sobre las caracteristicas de las nanoparticulas de SnO2 sintetizadas

Tin oxide (SnO2) is widely used in industry as raw material for electronic devices, plating of different types of materials, for dyes and pigments, for electroplating, heterogeneous catalysis, etc. In this work SnO2 was obtained by a controlled precipitation method with special attention to the effects the tin precursor has on the microstructure of the final product. The most appropriate pH for obtaining SnO2 with the rutile structure as the main phase is 6.25 for SnCl2 and 6.40 for SnSO4. After heat treatment at 600 °C, particles of nanometric order (~10 - 30 nm approx) were obtained. The characterization of the solid phase was made by X-ray diffraction (XRD), thermal analysis (DTA/TG), transmission electron microscopy (TEM) and Fourier transformed infrared spectroscopy (FTIR).

Emprego de planejamento fatorial no desenvolvimento de uma metodologia para extração de zinco de resíduos galvânicos

The plating process generates solid waste rich in heavy metals and aiming to reduce environmental impact of such waste, this work suggests a methodology for zinc reduction, through a 2(4) factorial planning, studying the influence of the following variables: acid concentration (15, 20 or 30% v/v), acid type (sulfuric or hydrochloric), acid volume (15, 20 or 25 mL) and extraction time (12, 24 or 36 h). Through this methodology it is possible to establish the optimal conditions (15 mL of a 30% hydrochloric acid concentration during 12 h) to get a 100% efficiency in zinc extraction.