Efeitos dos parâmetros operacionais na fotodegradação do azo corante direct red 23 na interface dióxido de titânio/água

The decolorization and degradation of direct red 23 azo dye have been investigated in aqueous suspension of titanium dioxide under artificial irradiation. The effects of some operational parameters such as azo dye concentration, catalyst loading, and solution pH were investigated at 30.0 ºC and optimized values were obtained. The first-order kinetic model was used to discuss the results. The UV-Vis spectra changes showed that the azo dye sample, collected after 6 h irradiation, was 98% decolorized while the residual total carbon was 97.9% degraded, indicating simultaneous photodecolorization and degradation.

Low metal loading catalysts used for the selective hydrogenation of styrene

A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects.

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%). The most active prepared catalyst, PdNi(1%), was more selective than the Lindlar catalyst.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Caracterização textural e estrutural de V2O5/TiO2 obtidos via sol-gel: comparação entre secagem convencional e supercrítica

This work describes a modified sol-gel method for the preparation of V2O5/TiO2 catalysts. The samples have been characterized by N2 adsorption at 77K, x-ray diffractometry (XRD) and Fourier Transform Infrared (FT-IR). The surface area increases with the vanadia loading from 24 m² g-1, for pure TiO2, to 87 m² g-1 for 9wt.% of V2O5. The rutile form is predominant for pure TiO2 but became enriched with anatase phase when vanadia loading is increased. No crystalline V2O5 phase was observed in the catalysts diffractograms. Two species of surface vanadium observed by FT-IR spectroscopy a monomeric vanadyl and polymeric vanadates, the vanadyl/vanadate ratio remains practically constant.

H3PW12O40 (HPA), an efficient and reusable catalyst for biodiesel production related reactions: esterification of oleic acid and etherification of glycerol

In esterification of oleic acid with methanol at 25 °C HPA displayed the highest activity. Moreover the HPA could be reused after being transformed into its cesium salt. In the reaction of etherification of glycerol HPA and Amberlyst 35W showed similar initial activity levels. The results of acid properties demonstrate that HPA is a strong protonic acid and that both surface and bulk protons contribute to the acidity. Because of its strong affinity for polar compounds, HPA is also seemingly dissolved in both oleic acid and methanol. The reaction in this case proceeds with the catalyst in the homogenous phase.

In situ synthesis of nanoclay filled polyethylene using polymer supported metallocene catalyst system

In situ ethylene polymerizations were performed using bis(cyclopentadiene)titanium dichloride supported on polyethersulfone as catalyst. The bis(cyclopentadiene)titanium dichloride supported on polyethersulfone catalyst activity estimated by ethylene polymerization was 360 kgPE/molTi/h. During polymerization the fillers used were montmorillionite nanoclays having surface modifications with 35-45 wt% dimethyl dialkyl(14-18)amine (FA) and 25-30 wt% trimethyl stearyl ammonium (FB). These fillers were pretreated with methylaluminoxine (MAO; cocatalyst) for better dispersion onto the polymer matrix. The formation of polyethylene within the whole matrix was confirmed by FTIR studies. It was found that the nature of nanofiller did not have any remarkable effect on the melting characteristics of the polymer. TGA study indicates that nanoclay FB filled polyethylene has higher thermal stability than nanoclay FA filled polyethylene. The melting temperature of the obtained polyethylenes was 142 ºC, which corresponds to that synthesized by the polyether sulfone supported catalyst.

Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

Enzyme loading dependence of cellulose hydrolysis of sugarcane bagasse

The enzymatic hydrolysis of steam-pretreated sugarcane bagasse, either delignified or non-delignified, was studied as a function of enzyme loading. Hydrolysis experiments were carried out using five enzyme loadings (2.5 to 20 FPU/g cellulose) and the concentration of solids was 2% for both materials. Alkaline delignification improved cellulose hydrolysis by increasing surface area. For both materials, glucose concentrations increased with enzyme loading. On the other hand, enzyme loadings higher than 15 FPU/g did not result in any increase in the initial rate, since the excess of enzyme adsorbed onto the substrate restricted the diffusion process through the structure.

Characterization and catalytic performance of potassium loaded on rice husk silica and zeolite nay for transesterification of jatropha seed oil

Rice husk silica (RHS) and NaY were used as supports for potassium (K) prepared from acetate buffer (B) and acetate (A) solutions. K loading did not destroy the NaY structure, but it caused a decrease in the surface area; the K species resided in micropores and on the external surface. In contrast, K loading resulted in the collapse and a decrease in the surface area of RHS. It was found that 12K/NaY-B was the most active catalyst for the transesterification of Jatropha seed oil. The minimum K content in K/NaY-B that provided complete conversion of the Jatropha seed oil was 11 wt%, and the biodiesel yield was 77.9%.

Nanopartículas de poli-hidroxibutirato-co-valerato como suporte para a imobilização da lipase de Candida antarctica fração B

This work evaluates the immobilization of Candida antarctica lipase (Fraction B) using poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) nanoparticles as support. The effects of immobilization time (30-150 min) and pH (5-10) on lipase loading were evaluated. The stability of the immobilized enzyme towards temperature (40, 60, and 80 ºC), reuse and storage (at 4 ºC) were also determined. Furthermore, to assess its potential application in a system of interest, the immobilized lipase was used as a catalyst in the esterification of geraniol with oleic acid. The results indicated a time of 120 minutes and pH of 7 as optimal for immobilization. A 21 hour exposure of the PHBV-lipase derivative to 60 ºC showed a 33% reduction of the initial activity while storage at 4 ºC led to a residual activity (5% of the original activity). The derivative was used without significant loss of activity for 4 successive cycles. The use of the immobilized lipase as a catalyst in the production of geranyl oleate led to about 88% conversion of the initial reactants to products.

Desenvolvimento de reator tipo "dip catalyst" para filmes poliméricos contendo nanopartículas de metais de transição

This article describes the development of a new catalytic reactor designed to operate with nanoparticle-embedded polymer thin films. Stabilization of metal nanoparticles in films that serve as catalysts in organic reactions is relatively new; therefore, the development of reactors to facilitate their use is necessary. We describe in detail the preparation of the GDCR reactor-type "dip catalyst" and its evaluation in the Suzuki - Miyaura cross-coupling reaction of phenylboronic acid and 4-bromoanisole catalyzed by palladium nanoparticle-embedded cellulose acetate thin film (CA/PD(0)). Compared with earlier prototypes, GDCR reactor showed excellent results when operating with CA/PD(0) thin films.

SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Materials based on tungstophosphoric acid (TPA) immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET) decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH4)3PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO) in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68%) and selectivity (100%) for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.