Síntese e caracterização de alfa-fosfato de zircônio(IV) contendo agregados de cobre metálico

The alpha-zirconium (IV) hydrogenphosphate (alpha-ZrP) has received great attention in the last years due to its properties like ion exchange, intercalation, ionic conductivity and catalytic activity. This work reports a method to produce metallic copper clusters on alpha-ZrP to be used as catalysts in petrochemical processes. It was found that the solids were non-crystalline regardless of the uptake of copper and the reduction. The specific surface area increased as a consequence of the increase of the interlayer distance to accept the copper ions between the layers. During the reduction, big clusters of copper (0,5-11µ) with different sizes and shapes were produced.

Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno

Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

Interações hiperfinas em catalisadores metálicos

Heterogeneous catalysts are of fundamental importance in several modern chemical processes. The characterization of catalysts is an issue of very present interest as it can provide a better understanding of the fundamental aspects of the catalytic phenomena, thus helping in the development of more efficient catalysts. In order to extend and improve the characterization of catalysts, new and less conventional methods are being applied, such as nuclear spectroscopies. In this paper we focus on the application of angular correlation, with can be used to resolve different local environments of probe atoms in solids and can be applied, as shown here, in the characterization of heterogeneous catalysts. A brief theoretical introduction is given and experimental results related to catalytic systems of alumina and niobia-supported Pt-In and Pd-In catalysts are presented.

Efeito do teor metálico em catalisadores Co/Al2O3 aplicados à reação de reforma a vapor de etanol

The development of cobalt catalysts to produce hydrogen from ethanol is the goal of this investigation. Co/Al2O3 catalysts were prepared by impregnation and characterized by atomic absorption, nitrogen adsorption, X-ray diffraction, Raman spectroscopy, temperature programmed reduction and carbon analysis. The catalysts contained Co3O4 oxide and Co3+ and Co2+ species interacting with alumina. The cobalt load affects the crystal size and the crystalline structure and higher Co loads influence the reaction mechanism, changing the selectivity of the catalysts, decreasing the amount of CO produced and avoiding the formation of products catalyzed by the support. The ethanol conversion was 50-70% with 10-<1% of CO in the hydrogen.

A reação de metátese de olefinas: reorganização e ciclização de compostos orgânicos

The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances.

Inovação tecnológica e produção no setor químico

Innovation is the main tool for competitiveness and growth in the chemical sector and the main factors for innovation activities in industry as well as the innovation dynamics are discussed in this paper. Success indicators of innovation in Oxiteno are the following: 54% of the current production derives from RD&E projects, 11% of the gross margin in the internal market is due to new products, the company is a technology licensor, holding 17 patents and keeping a strong participation in the production and service sales in the high technology catalysts area, beyond its core petrochemicals and surfactants area.

Cu and Co exchanged ZSM-5 zeolites: activity towards no reduction and hydrocarbon oxidation

|Cu x|[Si yAl]-MFI and |Co x|[Si yAl]-MFI catalysts were prepared by ion exchange from |Na|[Si yAl]-MFI zeolites (y = 12, 25 and 45). The activity of the catalysts was evaluated in the reduction of NO to N2 in an oxidative atmosphere using propane or methane as reducing agents. The Cu catalysts were only active with propane and they presented higher activity than the Co-based catalysts, the latter being active with both hydrocarbons. H2-TPR and DRS-UV/Vis data allowed correlation between the activity towards NO reduction and the presence of cationic charge-compensating species in the zeolite. It was also verified that the hydrocarbons are preferentially oxidised by O2, a reaction that occurs simultaneously with their oxidation with NO.

Aplicação catalítica de peneiras moleculares básicas micro e mesoporosas

Catalysis by solid acids has received much attention due to its importance in petroleum refining and petrochemical processes. Relatively few studies have focused on catalysis by bases and even les on using basic molecular sieves. This paper deals with the potential application of micro and mesoporous molecular sieves in base catalysis reactions. The paper is divided in two parts, the first one dedicated to the design of the catalysts and the second to some relevant examples of catalytic reactions, which find a huge field of applications essentially in the synthesis of fine chemicals. Here, recent developments in catalysis by basic molecular sieves and the perspectives of applications in correlated catalytic processes are described.

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.

Polimerização de estireno utilizando compostos organolantanídeos ativados por MAO

In an attempt to improve the performance of organolanthanide catalysts we investigated the use of the industrially important cocatalyst methylaluminoxane (MAO) to activate organolanthanide compounds in olefin polymerization. The catalytic systems LnBrCp2(THF)2/MAO (Cp=cyclopentadienyl) and LnBrCp*2THF/MAO (Cp*= pentamethylcyclopentadienyl), Ln=Pr and Yb, were active in styrene polymerization but inactive in ethylene and propylene polymerization. These systems produced atactic polystyrene with conversions of up to 8.2% (PrBrCp*2THF, Al/Ln=200, T=80ºC, t=4 h) in toluene. In the absence of solvent, the conversion is 26.0% (1.5 h) and the molar mass of the atactic polystyrene is almost ten times higher (43 kg/mol).

Atropoisomerismo: o efeito da quiralidade axial em substâncias bioativas

Atropisomerism is a special kind of stereoisomeric relationship that arises from the freezing of a certain conformation of an organic molecule, associated with a high rotational barrier about a single covalent bond. Atropisomerism has been originally described in orto-functionalyzed biphenyl derivatives, but a lot of other organic functionalities can present this structural phenomenon, characterized by the presence of chiral properties in compounds that don't present classical stereogenic centers. Atropisomeric compounds, intermediates and catalysts have well-know importance in organic synthesis, but the influence of the axial chirality in substances able to modulate biological systems is still not very exploited in drug design and development. In this context, the present account describes the importance of this structural property in the medicinal chemistry of different classes of bioactive compounds or therapeutic agents, emphasizing how atropisomerism could affect the molecular recognition of a ligand or a prototype by the target bioreceptor.

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%.

Metátese de olefinas no Brasil: "Brazil is romping it!"

Some aspects of the olefin metathesis reactions are summarized here (types of reactions, mechanism and catalysts). In particular, the research groups that have been working on this chemistry in Brazil are presented. The main goal of this paper is to make this type of reaction more widely known in the Brazilian chemical community.

Redução catalítica seletiva de óxidos de nitrogênio sobre hematita contendo cobre

The activity of copper-doped hematite in the SCR with propane, in the presence of oxygen, was evaluated in this work. It was found that copper sulfate led to the production of solids with different specific surface areas depending on the amount of copper. The sulfur and copper species were mainly located on the surface. The copper-containing catalysts were more active in the reduction of nitrogen oxides and less active in the propane oxidation as compared to pure hematite. This behavior was assigned to an association of both sulfur and copper species to produce new sites active for NO reduction.

Estudo da oxidação total do etanol usando óxidos tipo perovskita LaBO3 (B= Mn, Ni, Fe)

The present work investigated the effect of coprecipitation-oxidant synthesis on the specific surface area of perovskite-type oxides LaBO3 (B= Mn, Ni, Fe) for total oxidation of ethanol. The perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption (BET method), thermogravimetric analysis (TGA-DTA), TPR and X-ray photoelectron spectroscopy (XPS). Through method involving the coprecipitation-oxidant was possible to obtain catalysts with different BET specific surface areas, of 33-51 m²/g. The results of the catalytic test confirmed that all oxides investigated in this work have specific catalytic activity for total oxidation of ethanol, though the temperatures for total conversion change for each transition metal.