Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

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.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

Efecto del catión, del anión y del co-ión sobre la agregación de líquidos iónicos en solución acuosa

The aggregation behavior of thirteen 1-alkyl-3-methylimidazolium based ionic liquids in aqueous solution is presented, considering variations of the alkyl side chain length as well as the anionic moiety. Cation and anion molecular volumes are selected as appropriate molecular descriptors. Additionally, the existing relationship between critical micelle concentration (CMC) and electrolyte concentration in solution is established, aiming to clarify ion effects. CMC values were obtained by measuring electrical conductivity and surface tension. It was confirmed that aggregation of ionic liquids in aqueous solution and in presence of inorganic salts is affected by the factors developed in this study.

Estudo da reação de oxidação preferencial do co sobre o sistema CuO/CeO2-TiO2

Cu catalysts supported on CeO2, TiO2 and CeO2/TiO2 were prepared by precipitation method and used for preferential oxidation of carbon monoxide contained in a hydrogen flow generated by methane steam reforming. The samples were characterized by XRD, BET and TPR techniques. The catalytic properties were studied in the 50-330ºC range by using a quartz micro-reactor vertically positioned on an electrical furnace. The results showed that the small copper particles generated with the lower metal content are the most easily reducible and give the best catalytic performance. In respect of support effect, the strong metal-support interaction and the redox characteristics of the CuOx-CeO2 series resulted in the best catalytic results, especially with the sample with 1% copper content.

Poly(ethylene-co-methyl acrylate)/poly(caprolactone) triol blends for drug delivery systems: characterization and drug release

Poly(ethylene-co-methyl acrylate) (EMA) and poly (caprolactone) triol (PCL-T) blends, a biodegradable aliphatic polyester with low molecular weight and moderate water solubility containing diltiazem hydrochloride (DZ) were studied in terms of the thermal and morphological properties, and drug release mechanism. An increase in the PCL-T content in the EMA/PCL-T/DZ films decreased the degree of DZ crystallinity. Drug release from these films is temperature-dependent, and it is possible to modify the drug release rate by adjusting the EMA/PCL-T composition of the blends. The mechanism of drug release is governed by PCL-T melting and PCL-T leaching from EMA matrix.

Characterization and in vitro release of cyclosporine-A from poly(D,L-lactide-co-glycolide implants obtained by solvent/extraction evaporation

Cyclosporine-A-loaded PLGA implants were developed intended for ocular route. Implants were prepared using solvent extraction/evaporation technique followed by casting of the cake into rods in a heated surface. XRD patterns showed that cyclosporine-A was completely incorporated into PLGA. FTIR and DSC results indicated alterations on drug molecular conformation aiming to reach the most stable thermodynamic conformation at polymer/drug interface. Implants provided controlled/sustained in vitro release of the drug. During the first 7 weeks, the drug release was controlled by the diffusion of the cyclosporine-A; and between 7-23 week period, the drug diffusion and degradation of PLGA controlled the drug release.

Application of ftir in the determination of acrylate content in poly(sodium acrylate-co-acrylamide) superabsorbent hydrogels

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

Conversão química de no e co sobre catalisadores à base de óxidos de cobalto ou de ferro

Cobalt or iron oxides supported or not on zeolite Hbeta were prepared and evaluated in the reduction reaction of NO by CO in presence of O2, SO2 or H2O. XRD results evidenced the Hbeta structure and the formation of Co3O4 and Fe2O3. TPR-H2 analysis showed complete reduction of cobalt oxide at lower temperatures than for iron oxide. The catalysts are quite active and the activity depends on the reaction temperature. The highest conversions rates were observed for pure iron oxide, which can be a relatively low cost catalyst for reduction of NO by CO, with high selectivity towards the N2 formation.

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.

Determinação espectrofotométrica indireta de capsaicinoides em pimentas Capsicum a partir da reação com o complexo de Co(II) com 4-(2-piridilazo) resorcinol

Capsaicinoids (CAPS) are substances responsible for pungency in Capsicum. It is important to quantify these types of compounds owing to their broad application in food, pharmaceuticals, cosmetics and chemical weapons. In this work, we developed an indirect spectrophotometric method based on the colorimetric reaction between CAPS, Co(II) 3.10×10-5 mol L-1 and 4-(2-pyridylazo) resorcinol (PAR) 6.23×10-5 and, in cachaça:water 92:8v/v solutions, for quantification of total CAPS in Capsicum peppers. The product of the reaction is CoPAR2CAPS2 and its absorption in aquo-ethanolic solution at 510 nm is proportional to the total CAPS concentration from 0.60 to 17.94 mg L-1. The values of limit of detection and limit of quantification were 0.0004 and 0.001 mg of CAPS/g of pepper, respectively, with 4% relative standard deviation. The developed method yielded similar results to those obtained from high performance liquid chromatography, with 95% of confidence.

Starch/poly (butylene adipate-co-terephthalate)/montmorillonite films produced by blow extrusion

This study aims to prepare biodegradable films from cassava starch, poly (butylene adipate-co-terephthalate) (PBAT), and montmorillonite (MMT) using blow-extrusion process and analyze the effects of different types and concentrations of MMT on the microstructure, physicochemical, and mechanical properties of the resulting films. The films were produced by blending 30% of PBAT with glycerol (17.5%), starch (49.0-52.5%), and four different types of montmorillonite (Cloisite® Na+, 10A, 15A, and 30B) at two different concentrations (1.75% and 3.5%). All the films prepared in this study showed an increase in the basal spacing of MMT layers. In particular, the films with 10A and 30B showed the highest increase in intercalation basal spacing, suggesting the formation of intercalated composites. The addition of nanoclays decreased the elongation of films. The addition of Cloisite® 10A resulted in films with the lowest WVP values and the highest stability to water adsorption under different RH conditions.

NOVEL SUPERABSORBENT HYDROGEL COMPOSITE BASED ON POLY(ACRYLAMIDE-CO-ACRYLATE)/NONTRONITE: CHARACTERIZATION AND SWELLING PERFORMANCE

A novel superabsorbent hydrogel (SH) composite based on a poly(acrylamide-co-acrylate) matrix filled with nontronite (NONT), a Fe(III)-rich member of the smectite group of clay minerals, is described in this manuscript. A variety of techniques, including FTIR, XRD, TGA, and SEM/EDX, were utilized to characterize this original composite. Experimental data confirmed the SH composite formation and suggested NONT was completely dispersed in the polymeric matrix. Additionally, NONT improved the water uptake capacity of the final material, which exhibited fast absorption, low sensitivity to the presence of salt, high water retention and a pH sensitive properties. These preliminary data showed that the original SH composite prepared here possesses highly attractive properties for applications in areas such as the agriculture field, particularly as a soil conditioner.

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.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.