984 resultados para temperature-programmed techniques


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Edible oil is an important contaminant in water and wastewater. Oil droplets smaller than 40 μm may remain in effluent as an emulsion and combine with other contaminants in water. Coagulation/flocculation processes are used to remove oil droplets from water and wastewater. By adding a polymer at proper dose, small oil droplets can be flocculated and separated from water. The purpose of this study was to characterize and analyze the morphology of flocs and floc formation in edible oil-water emulsions by using microscopic image analysis techniques. The fractal dimension, concentration of polymer, effect of pH and temperature are investigated and analyzed to develop a fractal model of the flocs. Three types of edible oil (corn, olive, and sunflower oil) at concentrations of 600 ppm (by volume) were used to determine the optimum polymer dosage and effect of pH and temperature. To find the optimum polymer dose, polymer was added to the oil-water emulsions at concentration of 0.5, 1.0, 1.5, 2.0, 3.0 and 3.5 ppm (by volume). The clearest supernatants obtained from flocculation of corn, olive, and sunflower oil were achieved at polymer dosage of 3.0 ppm producing turbidities of 4.52, 12.90, and 13.10 NTU, respectively. This concentration of polymer was subsequently used to study the effect of pH and temperature on flocculation. The effect of pH was studied at pH 5, 7, 9, and 11 at 30°C. Microscopic image analysis was used to investigate the morphology of flocs in terms of fractal dimension, radius of oil droplets trapped in floc, floc size, and histograms of oil droplet distribution. Fractal dimension indicates the density of oil droplets captured in flocs. By comparison of fractal dimensions, pH was found to be one of the most important factors controlling droplet flocculation. Neutral pH or pH 7 showed the highest degree of flocculation, while acidic (pH 5) and basic pH (pH 9 and pH 11) showed low efficiency of flocculation. The fractal dimensions achieved from flocculation of corn, olive, and sunflower oil at pH 7 and temperature 30°C were 1.2763, 1.3592, and 1.4413, respectively. The effect of temperature was explored at temperatures 20°, 30°, and 40°C and pH 7. The results of flocculation of oil at pH 7 and different temperatures revealed that temperature significantly affected flocculation. The fractal dimension of flocs formed in corn, olive and sunflower oil emulsion at pH 7 and temperature 20°, 30°, and 40°C were 1.82, 1.28, 1.29, 1.62, 1.36, 1.42, 1.36, 1.44, and 1.28, respectively. After comparison of fractal dimension, radius of oil droplets captured, and floc length in each oil type, the optimal flocculation temperature was determined to be 30°C. ^

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Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the "hydrogen economy" faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH 3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. ^ Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. ^ Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn2 1 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.^

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The rainbow smelt (Osmerus mordax) is an anadromous teleost that produces type II antifreeze protein (AFP) and accumulates modest urea and high glycerol levels in plasma and tissues as adaptive cryoprotectant mechanisms in sub-zero temperatures. It is known that glyceroneogenesis occurs in liver via a branch in glycolysis and gluconeogenesis and is activated by low temperature; however, the precise mechanisms of glycerol synthesis and trafficking in smelt remain to be elucidated. The objective of this thesis was to provide further insight using functional genomic techniques [e.g. suppression subtractive hybridization (SSH) cDNA library construction, microarray analyses] and molecular analyses [e.g. cloning, quantitative reverse transcription - polymerase chain reaction (QPCR)]. Novel molecular mechanisms related to glyceroneogenesis were deciphered by comparing the transcript expression profiles of glycerol (cold temperature) and non-glycerol (warm temperature) accumulating hepatocytes (Chapter 2) and livers from intact smelt (Chapter 3). Briefly, glycerol synthesis can be initiated from both amino acids and carbohydrate; however carbohydrate appears to be the preferred source when it is readily available. In glycerol accumulating hepatocytes, levels of the hepatic glucose transporter (GLUT2) plummeted and transcript levels of a suite of genes (PEPCK, MDH2, AAT2, GDH and AQP9) associated with the mobilization of amino acids to fuel glycerol synthesis were all transiently higher. In contrast, in glycerol accumulating livers from intact smelt, glycerol synthesis was primarily fuelled by glycogen degradation with higher PGM and PFK (glycolysis) transcript levels. Whether initiated from amino acids or carbohydrate, there were common metabolic underpinnings. Increased PDK2 (an inhibitor of PDH) transcript levels would direct pyruvate derived from amino acids and / or DHAP derived from G6P to glycerol as opposed to oxidation via the citric acid cycle. Robust LIPL (triglyceride catabolism) transcript levels would provide free fatty acids that could be oxidized to fuel ATP synthesis. Increased cGPDH (glyceroneogenesis) transcript levels were not required for increased glycerol production, suggesting that regulation is more likely by post-translational modification. Finally, levels of a transcript potentially encoding glycerol-3-phosphatase, an enzyme not yet characterized in any vertebrate species, were transiently higher. These comparisons also led to the novel discoveries that increased G6Pase (glucose synthesis) and increased GS (glutamine synthesis) transcript levels were part of the low temperature response in smelt. Glucose may provide increased colligative protection against freezing; whereas glutamine could serve to store nitrogen released from amino acid catabolism in a non-toxic form and / or be used to synthesize urea via purine synthesis-uricolysis. Novel key aspects of cryoprotectant osmolyte (glycerol and urea) trafficking were elucidated by cloning and characterizing three aquaglyceroporin (GLP)-encoding genes from smelt at the gene and cDNA levels in Chapter 4. GLPs are integral membrane proteins that facilitate passive movement of water, glycerol and urea across cellular membranes. The highlight was the discovery that AQP10ba transcript levels always increase in posterior kidney only at low temperature. This AQP10b gene paralogue may have evolved to aid in the reabsorption of urea from the proximal tubule. This research has contributed significantly to a general understanding of the cold adaptation response in smelt, and more specifically to the development of a working scenario for the mechanisms involved in glycerol synthesis and trafficking in this species.

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Planktonic foraminiferal census counts are used to construct high-resolution sea surface temperature (SST) and subsurface (thermocline) temperature records at a core site in the Tobago Basin, Lesser Antilles. The record is used to document climatic variability at this tropical site in comparison to middle- and high-latitude sites and to test current concepts of cross-equatorial heat transports as a major player in interhemispheric climate variability. Temperatures are estimated using transfer function and modern analog techniques. Glacial - maximum cooling of 2.5°-3°C is indicated; maximum cooling by 4°C is inferred for isotope stage 3. The SST record displays millennial-scale variability with temperature jumps of up to 3°C and closely tracks the structure of ice-core Dansgaard/Oeschger cycles. SST variations in part of the record run opposite to the SST evolution at high northern latitude sites, pointing to thermohaline circulation and marine heat transport as an important factor driving SST in the tropical and high-latitude Atlantic, both on orbital and suborbital timescales.

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We generated a high-resolution SSTMg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides from the core MD99-2346 collected in the Gulf of Lion, and compared it to that obtained using modern analogue techniques applied to fossil foraminiferal assemblages (SSTMAT). The two temperature records display similar patterns during the last 28,000 years but the SSTMg/Ca estimates are several degrees warmer (~+4 °C) than SSTMAT. The temperature shift between SSTMg/Ca and SSTMAT remained relatively constant over time. This seems to exclude a bias on the Mg/Ca record associated with salinity or secondary Mg-rich calcite encrustation on the foraminiferal tests during early diagenesis. Therefore, anomalously high Mg/Ca suggests either: (1) the empirical equation for G. bulloides of Elderfield and Ganssen (2000) is incorrect; or (2) there is a specific Mediterranean genotypes of G. bulloides for which a specific Mg/Ca-temperature calibration is needed.

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Quantitative and qualitative analyses of planktonic foraminiferal assemblages from 134 core-top sediment samples collected along the western Iberian margin were used to assess the latitudinal and longitudinal changes in surface water conditions and to calibrate a Sea Surface Temperature (SST) transfer function for this seasonal coastal upwelling region. Q-mode factor analysis performed on relative abundances yielded three factors that explain 96% of the total variance: factor 1 (50%) is exclusively defined by Globigerina bulloides, the most abundant and widespread species, and reflects the modern seasonal (May to September) coastal upwelling areas; factor 2 (32%) is dominated by Neogloboquadrina pachyderma (dextral) and Globorotalia inflata and seems to be associated with the Portugal Current, the descending branch of the North Atlantic Drift; factor 3 (14%) is defined by the tropical-sub-tropical species Globigerinoides ruber (white), Globigerinoides trilobus trilobus, and G. inflata and mirrors the influence of the winter-time eastern branch of the Azores Current. In conjunction with satellite-derived SST for summer and winter seasons integrated over an 18 year period the regional foraminiferal data set is used to calibrate a SST transfer function using Imbrie & Kipp, MAT and SIMMAX(ndw) techniques. Similar predicted errors (RMSEP), correlation coefficients, and residuals' deviation from SST estimated for both techniques were observed for both seasons. All techniques appear to underestimate SST off the southern Iberia margin, an area mainly occupied by warm waters where upwelling occurs only occasionally, and overestimate SST on the northern part of the west coast of the Iberia margin, where cold waters are present nearly all year round. The comparison of these regional calibrations with former Atlantic and North Atlantic calibrations for two cores, one of which is influenced by upwelling, reveals that the regional one attests more robust paleo-SSTs than for the other approaches.

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In order to optimize frontal detection in sea surface temperature fields at 4 km resolution, a combined statistical and expert-based approach is applied to test different spatial smoothing of the data prior to the detection process. Fronts are usually detected at 1 km resolution using the histogram-based, single image edge detection (SIED) algorithm developed by Cayula and Cornillon in 1992, with a standard preliminary smoothing using a median filter and a 3 × 3 pixel kernel. Here, detections are performed in three study regions (off Morocco, the Mozambique Channel, and north-western Australia) and across the Indian Ocean basin using the combination of multiple windows (CMW) method developed by Nieto, Demarcq and McClatchie in 2012 which improves on the original Cayula and Cornillon algorithm. Detections at 4 km and 1 km of resolution are compared. Fronts are divided in two intensity classes (“weak” and “strong”) according to their thermal gradient. A preliminary smoothing is applied prior to the detection using different convolutions: three type of filters (median, average and Gaussian) combined with four kernel sizes (3 × 3, 5 × 5, 7 × 7, and 9 × 9 pixels) and three detection window sizes (16 × 16, 24 × 24 and 32 × 32 pixels) to test the effect of these smoothing combinations on reducing the background noise of the data and therefore on improving the frontal detection. The performance of the combinations on 4 km data are evaluated using two criteria: detection efficiency and front length. We find that the optimal combination of preliminary smoothing parameters in enhancing detection efficiency and preserving front length includes a median filter, a 16 × 16 pixel window size, and a 5 × 5 pixel kernel for strong fronts and a 7 × 7 pixel kernel for weak fronts. Results show an improvement in detection performance (from largest to smallest window size) of 71% for strong fronts and 120% for weak fronts. Despite the small window used (16 × 16 pixels), the length of the fronts has been preserved relative to that found with 1 km data. This optimal preliminary smoothing and the CMW detection algorithm on 4 km sea surface temperature data are then used to describe the spatial distribution of the monthly frequencies of occurrence for both strong and weak fronts across the Indian Ocean basin. In general strong fronts are observed in coastal areas whereas weak fronts, with some seasonal exceptions, are mainly located in the open ocean. This study shows that adequate noise reduction done by a preliminary smoothing of the data considerably improves the frontal detection efficiency as well as the global quality of the results. Consequently, the use of 4 km data enables frontal detections similar to 1 km data (using a standard median 3 × 3 convolution) in terms of detectability, length and location. This method, using 4 km data is easily applicable to large regions or at the global scale with far less constraints of data manipulation and processing time relative to 1 km data.

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A fundamental step in understanding the effects of irradiation on metallic uranium and uranium dioxide ceramic fuels, or any material, must start with the nature of radiation damage on the atomic level. The atomic damage displacement results in a multitude of defects that influence the fuel performance. Nuclear reactions are coupled, in that changing one variable will alter others through feedback. In the field of fuel performance modeling, these difficulties are addressed through the use of empirical models rather than models based on first principles. Empirical models can be used as a predictive code through the careful manipulation of input variables for the limited circumstances that are closely tied to the data used to create the model. While empirical models are efficient and give acceptable results, these results are only applicable within the range of the existing data. This narrow window prevents modeling changes in operating conditions that would invalidate the model as the new operating conditions would not be within the calibration data set. This work is part of a larger effort to correct for this modeling deficiency. Uranium dioxide and metallic uranium fuels are analyzed through a kinetic Monte Carlo code (kMC) as part of an overall effort to generate a stochastic and predictive fuel code. The kMC investigations include sensitivity analysis of point defect concentrations, thermal gradients implemented through a temperature variation mesh-grid, and migration energy values. In this work, fission damage is primarily represented through defects on the oxygen anion sublattice. Results were also compared between the various models. Past studies of kMC point defect migration have not adequately addressed non-standard migration events such as clustering and dissociation of vacancies. As such, the General Utility Lattice Program (GULP) code was utilized to generate new migration energies so that additional non-migration events could be included into kMC code in the future for more comprehensive studies. Defect energies were calculated to generate barrier heights for single vacancy migration, clustering and dissociation of two vacancies, and vacancy migration while under the influence of both an additional oxygen and uranium vacancy.

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Optical mapping of voltage signals has revolutionised the field and study of cardiac electrophysiology by providing the means to visualise changes in electrical activity at a high temporal and spatial resolution from the cellular to the whole heart level under both normal and disease conditions. The aim of this thesis was to develop a novel method of panoramic optical mapping using a single camera and to study myocardial electrophysiology in isolated Langendorff-perfused rabbit hearts. First, proper procedures for selection, filtering and analysis of the optical data recorded from the panoramic optical mapping system were established. This work was followed by extensive characterisation of the electrical activity across the epicardial surface of the preparation investigating time and heart dependent effects. In an initial study, features of epicardial electrophysiology were examined as the temperature of the heart was reduced below physiological values. This manoeuvre was chosen to mimic the temperatures experienced during various levels of hypothermia in vivo, a condition known to promote arrhythmias. The facility for panoramic optical mapping allowed the extent of changes in conduction timing and pattern of ventricular activation and repolarisation to be assessed. In the main experimental section, changes in epicardial electrical activity were assessed under various pacing conditions in both normal hearts and in a rabbit model of chronic MI. In these experiments, there was significant changes in the pattern of electrical activation corresponding with the changes in pacing regime. These experiments demonstrated a negative correlation between activation time and APD, which was not maintained during ventricular pacing. This suggests that activation pattern is not the sole determinant of action potential duration in intact hearts. Lastly, a realistic 3D computational model of the rabbit left ventricle was developed to simulate the passive and active mechanical properties of the heart. The aim of this model was to infer further information from the experimental optical mapping studies. In future, it would be feasible to gain insight into the electrical and mechanical performance of the heart by simulating experimental pacing conditions in the model.

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Low-temperature magneto-photoluminescence is a very powerful technique to characterize high purity GaAs and InP grown by various epitaxial techniques. These III-V compound semiconductor materials are used in a wide variety of electronic, optoelectronic and microwave devices. The large binding energy differences of acceptors in GaAs and InP make possible the identification of those impurities by low-temperature photoluminescence without the use of any magnetic field. However, the sensitivity and resolution provided by this technique rema1ns inadequate to resolve the minute binding energy differences of donors in GaAs and InP. To achieve higher sensitivity and resolution needed for the identification of donors, a magneto-photoluminescence system 1s installed along with a tunable dye laser, which provides resonant excitation. Donors 1n high purity GaAs are identified from the magnetic splittings of "two-electron" satellites of donor bound exciton transitions 1n a high magnetic field and at liquid helium temperature. This technique 1s successfully used to identify donors 1n n-type GaAs as well as 1n p-type GaAs in which donors cannot be identified by any other technique. The technique is also employed to identify donors in high purity InP. The amphoteric incorporation of Si and Ge impurities as donors and acceptors in (100), (311)A and (3ll)B GaAs grown by molecular beam epitaxy is studied spectroscopically. The hydrogen passivation of C acceptors in high purity GaAs grown by molecular beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD) 1s investigated using photoluminescence. Si acceptors ~n MBE GaAs are also found to be passivated by hydrogenation. The instabilities in the passivation of acceptor impurities are observed for the exposure of those samples to light. Very high purity MOCVD InP samples with extremely high mobility are characterized by both electrical and optical techniques. It is determined that C is not typically incorporated as a residual acceptor ~n high purity MOCVD InP. Finally, GaAs on Si, single quantum well, and multiple quantum well heterostructures, which are fabricated from III-V semiconductors, are also measured by low-temperature photoluminescence.

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The black-lip pearl oyster Pinctada margaritifera is a protandrous hermaphrodite species. Its economic value has led to the development of controlled hatchery reproduction techniques, although many aspects remain to be optimized. In order to understand reproductive mechanisms and their controlling factors, two independent experiments were designed to test hypotheses of gametogenesis and sex ratio control by environmental and hormonal factors. In one, pearl oysters were exposed under controlled conditions at different combinations of temperature (24 and 28°C) and food level (10,000 and 40,000 cells mL−1); whereas in the other, pearl oysters were conditioned under natural conditions into the lagoon and subjected to successive 17β-estradiol injections (100 μg per injection). Gametogenesis and sex ratio were assessed by histology for each treatment. In parallel, mRNA expressions of nine marker genes of the sexual pathway (pmarg-foxl2, pmarg-c43476, pmarg-c45042, pmarg-c19309, pmarg-c54338, pmarg-vit6, pmarg-zglp1, pmarg-dmrt, and pmarg-fem1-like) were investigated. Maximum maturation was observed in the treatment combining the highest temperature (28°C) and the highest microalgae concentration (40,000 cells mL−1), where the female sex tended to be maintained. Injection of 17β-estradiol induced a significant increase of undetermined stage proportion 2 weeks after the final injection. These results suggest that gametogenesis and gender in adult pearl oysters can be controlled by environmental factors and estrogens. While there were no significant effects on relative gene expression, the 3-gene-pair expression ratio model of the sexual pathway of P. margaritifera, suggest a probable dominance of genetic sex determinism without excluding a mixed sex determination mode (genetic + environmental)

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The In Situ Analysis System (ISAS) was developed to produce gridded fields of temperature and salinity that preserve as much as possible the time and space sampling capabilities of the Argo network of profiling floats. Since the first global re-analysis performed in 2009, the system has evolved and a careful delayed mode processing of the 2002-2012 dataset has been carried out using version 6 of ISAS and updating the statistics to produce the ISAS13 analysis. This last version is now implemented as the operational analysis tool at the Coriolis data centre. The robustness of the results with respect to the system evolution is explored through global quantities of climatological interest: the Ocean Heat Content and the Steric Height. Estimates of errors consistent with the methodology are computed. This study shows that building reliable statistics on the fields is fundamental to improve the monthly estimates and to determine the absolute error bars. The new mean fields and variances deduced from the ISAS13 re-analysis and dataset show significant changes relative to the previous ISAS estimates, in particular in the southern ocean, justifying the iterative procedure. During the decade covered by Argo, the intermediate waters appear warmer and saltier in the North Atlantic and fresher in the Southern Ocean than in WOA05 long term mean. At inter-annual scale, the impact of ENSO on the Ocean Heat Content and Steric Height is observed during the 2006-2007 and 2009-2010 events captured by the network.

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An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.

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Dissertação de mestrado, Engenharia Electrónica e Telecomunicações, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2011

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Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2