Ni catalysts with Mo promoter for methane steam reforming

NiO/Al(2)O(3) catalyst precursors were prepared by simultaneous precipitation, in a Ni:Al molar ratio of 3:1, promoted with Mo oxide (0.05, 0.5, 1.0 and 2.0 wt%). The solids were characterized by adsorption of N(2), XRD, TPR, Raman spectroscopy and XPS, then activated by H(2) reduction and tested for the catalytic activity in methane steam reforming. The characterization results showed the presence of NiO and Ni(2)AlO(4) in the bulk and Ni(2)AlO(4) and/or Ni(2)O(3) and MoO(4)(-2) at the surface of the samples. In the catalytic tests, high stability was observed with a reaction feed of 4:1 steam/methane. However, at a steam/methane ratio of 2: 1, only the catalyst with 0.05% Mo remained stable throughout the 500 min of the test. The addition of Mo to Ni catalysts may have a synergistic effect, probably as a result of electron transfer from the molybdenum to the nickel, increasing the electron density of the catalytic site and hence the catalytic activity. (C) 2009 Elsevier Ltd. All rights reserved.

Adsorption of amyloglucosidase from Aspergillus niger NRRL 3122 using ion exchange resin

Amyloglucosidase enzyme was produced by Aspergillus niger NRRL 3122 from solid-state fermentation, using deffated rice bran as substrate. The effects of process parameters (pH, temperature) in the equilibrium partition coefficient for the system amyloglucosidase - resin DEAE-cellulose were investigated, aiming at obtaining the optimum conditions for a subsequent purification process. The highest partition coefficients were obtained using 0.025M Tris-HCl buffer, pH 8.0 and 25ºC. The conditions that supplied the highest partition coefficient were specified, the isotherm that better described the amyloglucosidase process of adsorption obtained. It was observed that the adsorption could be well described by Langmuir equation and the values of Qm and Kd estimated at 133.0 U mL-1 and 15.4 U mL-1, respectively. From the adjustment of the kinetic curves using the fourth-order Runge-Kutta algorithm, the adsorption (k1) and desorption (k2) constants were obtained through optimization by the least square procedure, and the values calculated were 2.4x10-3 mL U-1 min-1 for k1 and 0.037 min-1 for k2 .

Weekend/weekday differences in concentrations of ozone, nox, and non-methane hydrocarbon in the metropolitan area of São Paulo

Ozone and inhalable particulate matter are the major air pollutants in the Metropolitan Area of São Paulo, Brazil, a region that has more than 19 million inhabitants and approximately 7 million registered vehicles. Proximity of roadways, adjacent land use, and local circulation are just some of the factors that can affect the results of monitoring of pollutant concentrations. The so-called weekend effect (higher ozone concentrations on weekends than on weekdays) might be related to the fact that concentrations of ozone precursors, such as nitrogen oxides (NOx) and Non Methane-Hydrocarbon (NMHC), are relatively lower on weekends. This phenomenon has been reported in some areas of the United States since the 1970s. The differences between the concentrations of ozone in period of weekend and weekday, were obtained from analysis of data hourly average of CETESB for 2004, studied the precursors to the formation of troposphere ozone, the meteorological variables and traffic profile for RMSP. Because of the proximity to sources of emissions from the station Pinheiros showed higher concentrations of NO and NO² and greater variations to the periods weekend and weekday. With fewer vehicles circulating during the weekend, and consequently less emission of pollutants, it has cleaner air and less concentration of NO and NO², there is the ideal setting to the formation of troposphere ozone, despite the lower concentration of NO². The proximity with the source emissions, aided by the increased availability of solar radiation and the presence of ozone precursors, were factors conditions for the occurrence of weekend effect.

Effect of eucalyptus (Eucalyptus citriodora) fresh or residue leaves on methane emission in vitro

Rumen fermentation and methane emission for eucalyptus (Eucalyptus citriodora) fresh leaves (FL) or residue leaves (RL), after essential oil extraction from eucalyptus leaves in comparison with alfalfa (Medicago sativa) hay, were investigated in vitro. Eucalyptus FL and RL were obtained from the Distillery Trees Barras Company, Torrinha City, Sao Paulo, Brazil. The semi-automatic system of gas production was used to measure gas production, methane emission and rumen fermentation after 24 h incubation in vitro. The results showed that the crude protein (CP) contents were 76.4, 78.1 and 181.9 g kg(-1) DM for eucalyptus FL, RL and alfalfa hay, respectively. The neutral-detergent fibre (NDF) and acid-detergent fibre (ADF) were significantly lower in eucalyptus FL and RL than alfalfa hay. The Eucalyptus fresh and residue leaves were rich in total phenols (TP) and total tannins (TT) but had negligible content of condensed tannins (CT). There was significant reduction in cumulative gas production about 54 and 51% with eucalyptus FL and RL, respectively, compared with alfalfa hay. The methane emission (mL/g DM) was reduced (P<0.05) by 53 and 57% with eucalyptus FL and RL, respectively, but the reduction was 21 and 16% when expressed on truly digested organic matter basis. There were a decline (P<0.05) in true dry and organic matter degradation in vitro in eucalyptus FL and RL compared with alfalfa hay substrate. The partitioning factor values were higher (P<0.05) in eucalyptus FL and RL than alfalfa hay. There was no significant difference observed between eucalyptus FL, RL and alfalfa hay in protozoa count. It is concluded that the eucalyptus leaves have potential effect to mitigate CH4 production in vitro, which may be attributed to a decrease in fermentable substrate rather than to a direct effect on methanogenesis.

The influence of adsorption phenomena on the impedance spectroscopy of an electrolytic cell

In this work we investigate the influence of the adsorption of ions on the impedance spectroscopy of an electrolytic cell. We consider that the positive and negative ions present in a dielectric liquid are adsorbed in the electrode surfaces with different adsorption energies. This difference in adsorption energies causes an additional plateaux in the limit of the low-frequency range of the real part of the impedance Z. In the same frequency range, a second minimum in the imaginary part of Z is predicted. The theory is illustrated with measurements of the impedance of an electrolytic solution in the frequency range from 10(-2) Hz to 1 KHz. A comparison between the present model and others from the literature to describe the experimental results is also made.

Comparative study of the adsorption and dissociation of vinylacetic acid and acrylic acid on silicon (001)

In this work, we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of acrylic acid (AAc) and vinylacetic acid (VAA) on the silicon surface. Our total energy calculations support the proposed experimental process, as it indicates that the chemisorption of the molecule is as follows: The gas phase VAA (AAc) adsorbs molecularly to the electrophilic surface Si atom and then dissociates into H(2)C = CH - COO and H, bonded to the electrophilic and nucleophilic surface silicon dimer atoms, respectively. The activation energy for both processes correspond to thermal activations that are smaller than the usual growth temperature. In addition, the electronic structure, calculated vibrational modes, and theoretical scanning tunneling microscopy images are discussed, with a view to contribute to further experimental investigations.

First-principles study of the adsorption of atomic and molecular hydrogen on BC(2)N nanotubes

The adsorption of atomic and molecular hydrogen on armchair and zigzag boron carbonitride nanotubes is investigated within the ab initio density functional theory. The adsorption of atomic H on the BC(2)N nanotubes presents properties which are promising for nanoelectronic applications. Depending on the adsorption site for the H, the Fermi energy moves toward the bottom of the conduction band or toward the top of the valence band, leading the system to exhibit donor or acceptor characteristics, respectively. The H(2) molecules are physisorbed on the BC(2)N surface for both chiralities. The binding energies for the H(2) molecules are slightly dependent on the adsorption site, and they are near to the range to work as a hydrogen storage medium.

Density functional theory and ab initio molecular dynamics study of NO adsorption on Pd(111) and Pt(111) surfaces

The origin of the unique geometry for nitric oxide (NO) adsorption on Pd(111) and Pt(111) surfaces as well as the effect of temperature were studied by density functional theory calculations and ab initio molecular dynamics at finite temperature. We found that at low coverage, the adsorption geometry is determined by electronic interactions, depending sensitively on the adsorption sites and coverages, and the effect of temperature on geometries is significant. At coverage of 0.25 monolayer (ML), adsorbed NO at hollow sites prefer an upright configuration, while NO adsorbed at top sites prefer a tilting configuration. With increase in the coverage up to 0.50 ML, the enhanced steric repulsion lead to the tilting of hollow NO. We found that the tilting was enhanced by the thermal effects. At coverage of 0.75 ML with p(2 x 2)-3NO(fcc+hcp+top) structure, we found that there was no preferential orientation for tilted top NO. The interplay of the orbital hybridization, thermal effects, steric repulsion, and their effects on the adsorption geometries were highlighted at the end.

Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Use of blanks to determine in vitro net gas and methane production when using rumen fermentation modifiers

Blanks (flasks without substrate containing only inoculum and medium) are used in vitro to correct for gas. CH(4) and residual organic matter (OM) fermented in inoculum. However inclusion of rumen fermentation modifiers may affect fermentation of OM in the substrate and inoculum. Thus, data correction using blanks that lack additives may result in inaccurate adjustment for background fermentation. Our objective was to evaluate impacts of using blanks containing additive (i.e., specific blanks) or blanks without additive on estimation of in vitro net gas and CH(4) production. We used the semi-automatic in vitro gas production technique including monensin sodium at 2.08 mg/l of buffered rumen fluid (Experiment 1) or carvacrol, eugenol and 1,8-cineol at 667 mg/l (Experiment 2) in flasks with substrate and in blank flasks. At 16h of incubation, monensin reduced (P <= 0.02) total gas production in flasks containing substrate (162.0 ml versus 146.3 ml) and in blanks (84.4 ml versus 79.2 ml). Total methane production was also decreased (P <= 0.05) by adding monensin to flasks containing substrate (15.7 ml versus 11.9 ml) as well as in blanks (6.4 ml versus 5.0 ml). Inclusion of carvacrol or eugenol reduced (P <= 0.05) total gas and CH(4) production in flasks with substrate and in blanks, but in a more pronounced manner than monensin. For these three additives, correction for blank without additive resulted in lower net gas and CH(4) production than correction for a treatment specific blank. For instance, correcting carvacrol data using a blank without the additive resulted in negative net gas and CH(4) production (-6.5 and -1.5 ml. respectively). These biologically impossible results occurred because total gas and CH(4) production in blanks without carvacrol (46.1 and 2.1 ml, respectively) were higher than in flasks containing substrate plus carvacrol (39.7 and 0.6 ml, respectively). Results demonstrated that inclusion of rumen additives affected fermentation of OM in the substrate and the inoculum. Thus, correction of gas and CH(4) production using blanks without additives resulted in overestimation of these variables. Blanks containing the additive of interest should be included when rumen fermentation modifiers are evaluated in vitro. This paper is part of the special issue entitled: Greenhouse Gases in Animal Agriculture Finding a Balance between Food and Emissions, Guest Edited by T.A. McAllister, Section Guest Editors: K.A. Beauchemin, X. Hao, S. McGinn and Editor for Animal Feed Science and Technology, P.H. Robinson. (C) 2011 Elsevier B.V. All rights reserved.

Effect of some essential oils on in vitro methane emission

The objectives of this study were to characterise four essential oils (EO) chemically and to evaluate their effect on ruminal fermentation and methane emission in vitro. The investigated EO were isolated from Achillea santolina, Artemisia judaica, Schinus terebinthifolius and Mentha microphylla, and supplemented at four levels (0, 25, 50 and 75 l) to 75ml of buffered rumen fluid plus 0.5 g of substrate. The main components of the EO were piperitone (49.1%) and camphor (34.5%) in A. judaica, 16-dimethyl 15-cyclooactdaiene (60.5%) in A. santolina, piperitone oxide (46.7%) and cis-piperitone oxide (28%) in M. microphylla, and -muurolene (45.3%) and -thujene (16.0%) in S. terebinthifolius. The EO from A. santolina (at 25 and 50 l), and all levels of A. judaica increased the gas production significantly, but S. terebinthifolius (at 50 and 75 l), A. santolina (at 75 l) and all levels of M. microphylla decreased the gas production significantly in comparison with the control. The highest levels of A. santolina and A. judaica, and all doses from M. microphylla EO inhibited the methane production along with a significant reduction in true degradation of dry matter and organic matter, protozoa count and NH3-N concentration. It is concluded that the evaluated EO have the potential to affect ruminal fermentation efficiency and the EO from M. microphylla could be a promising methane mitigating agent.

An investigation of phosphate adsorption from aqueous solution onto hydrous niobium oxide prepared by co-precipitation method

The synthetic hydrous niobium oxide has been used for phosphate removal from the aqueous solutions. The kinetic data correspond very well to the pseudo second-order equation The phosphate removal tended. to increase with a decrease of pH. The equilibrium data describe very well the Langmuir isotherm. The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The adsorption capacities are high, and increased with increasing temperature. The evaluated Delta G degrees and Delta H degrees indicate the spontaneous and endothermic nature of the reactions. The adsorptions occur with increase in entropy (Delta S positive) value suggest increase in randomness at the solid-liquid interface during the adsorption. A phosphate desorbability of approximately 60% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. (C) 2008 Elsevier B.V. All rights reserved.

Thermodynamic and kinetic investigations of phosphate adsorption onto hydrous niobium oxide prepared by homogeneous solution method

The adsorption kinetics of phosphate onto Nb(2)O(5)center dot nH(2)O was investigated at initial phosphate concentrations 10 and 50 mg L(-1). The kinetic process was described by a pseudo second-order rate model very well. The adsorption thermodynamics was carried out at 298, 308, 318, 328 and 338 K. The positive values of both Delta H and Delta S suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G values obtained were negative indicating a spontaneous adsorption process. The Langmuir model described the data better than the Freundlich isotherm model. The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The effective desorption could be achieved using water at pH 12. (C) 2010 Elsevier B.V. All rights reserved.

Adsorption kinetic, thermodynamic and desorption studies of phosphate onto hydrous niobium oxide prepared by reverse microemulsion method

A type of Nb(2)O(5)center dot 3H(2)O was synthesized and its phosphate removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The phosphate adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 18.36 mg-Pg(-1). The peak appearing at 1050 cm(-1) in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. A phosphate desorbability of approximately 68% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical attraction. Due to its high adsorption capacity, this type of hydrous niobium oxide has the potential for application to control phosphorus pollution.

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO(2)center dot nH(2)O Was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. The positive values of both Delta H degrees and Delta S degrees suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. Delta G degrees values obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO(2)center dot nH(2)O could be achieved using distilled water at pH 12. (C) 2009 Elsevier B.V. All rights reserved.