Co/Al2O3 catalysts promoted with noble metals for production of hydrogen by methane steam reforming

The effect of noble metal addition on the catalytic properties of Co/Al2O3 was evaluated for the steam reforming of methane. Co/Al2O3 catalysts were prepared with addition of different noble metals (Pt, Pd, Ru and Ir 0.3 wt.%) by a wetness impregnation method and characterized by UV-vis spectroscopy, temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) of the reduced catalysts. The UV-vis spectra of the samples indicate that, most likely, large amounts of the supported cobalt form Co species in which cobalt is in octahedral and tetrahedral symmetries. No peaks assigned to cobalt species from aluminate were found for the promoted and unpromoted cobalt catalysts. TPO analyses showed that the addition of the noble metals on the Co/Al2O3 catalyst leads to a more stable metallic state and less susceptible to the deactivation process during the reforming reaction. The Co/Al2O3 promoted with Pt showed higher stability and selectivity for H(2)production during the methane steam reforming. (C) 2007 Elsevier Ltd. All rights reserved.

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.

Production of hydrogen by ethanol steam reforming on Co/Al2O3 catalysts: Effect of addition of small quantities of noble metals

The catalytic performance of Co/Al2O3 catalysts promoted with small amounts noble metals (Pt, Pd, Ru, Ir) for steam reforming of ethanol (SRE) has been investigated. The catalysts were characterized by the energy dispersive X-ray, X-ray diffraction, BET surface area, X-ray absorption fine structure and temperature reduction programmed techniques. The results showed that the promoting effect of noble metals included a marked decrease of the reduction temperatures of both Co3O4 and cobalt surface species interacting with the support due to the hydrogen spillover effect, leading to a significant increase of the reducibilities of the promoted catalysts. The better catalytic performance for the ethanol steam reforming at 400 degrees C was obtained for the CoRu/Al2O3 catalyst, which presented an effluent gaseous mixture with the highest H, selectivity and the reasonable low CO formation. (C) 2007 Published by Elsevier B.V.

Co catalysts supported on SiO(2) and gamma-Al(2)O(3) applied to ethanol steam reforming: Effect of the solvent used in the catalyst preparation method

Cobalt catalysts were prepared on supports of SiO(2) and gamma-Al(2)O(3) by the impregnation method, using a solution of Co precursor in methanol. The samples were characterized by XRD, TPR, and Raman spectroscopy and tested in ethanol steam reforming. According to the XRD results, impregnation with the methanolic solution led to smaller metal crystallites than with aqueous solution, on the SiO(2) support. On gamma-Al(2)O(3), all the samples exhibited small crystallites, with either solvent, due to a higher Co-support interaction that inhibits the reduction of Co species. The TPR results were consistent with XRD results and the samples supported on gamma-Al(2)O(3) showed a lower degree of reduction. In the steam reforming of ethanol, catalysts supported on SiO(2) and prepared with the methanolic solution showed the best H(2), CO(2) and CO selectivity. Those supported on gamma-Al(2)O(3) showed lower H(2) selectivity. (C) 2011 Elsevier Ltd. All rights reserved.

Cobalt catalysts derived from hydrotalcite-type precursors applied to steam reforming of ethanol

Catalysts derived from Co/Mg/Al hydrotalcite-type precursors modified with La and Ce were characterized by XANES and tested in ethanol steam reforming. The reaction data showed that, with a molar ratio of water: ethanol = 3:1 in the feed, addition of Ce and La favored acetaldehyde production. Increasing the water content (water:ethanol = 5:1) decreased the acetaldehyde formation by favoring the adsorption of water molecules on these samples, enhancing the acetaldehyde conversion. (C) 2011 Elsevier B.V. All rights reserved.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

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.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Solar Collectors for Historic Homes : Linking consumption to perceptions of space

Reduction of household energy consumption is one of the top issues in contemporary discussions on sustainable consumption. This chapter concerns one way through which consumption of purchased energy for house heating can be reduced; by having a solar thermal system added to one's house. However, the fact that one of the components - the solar collector - usually is situated on the roof or the facade of a building, is a recurrent impediment to such installations. In certain contexts, these attributes may melt into the building, while in others, they may be perceived as problematic. The latter may particularly be the case when the appearance of the building is of major imiportance, as with houses deemed worthy of preservation for coming generations. This chapter draws upon a study carried out in Visby Town, a walled Hanseatic town and a World Heritage site on the island of Gotland, Sweden.

Modeling and forecasting long-term natural gas (NG) consumption in Iran, using particle swarm optimization (PSO)

The gradual changes in the world development have brought energy issues back into high profile. An ongoing challenge for countries around the world is to balance the development gains against its effects on the environment. The energy management is the key factor of any sustainable development program. All the aspects of development in agriculture, power generation, social welfare and industry in Iran are crucially related to the energy and its revenue. Forecasting end-use natural gas consumption is an important Factor for efficient system operation and a basis for planning decisions. In this thesis, particle swarm optimization (PSO) used to forecast long run natural gas consumption in Iran. Gas consumption data in Iran for the previous 34 years is used to predict the consumption for the coming years. Four linear and nonlinear models proposed and six factors such as Gross Domestic Product (GDP), Population, National Income (NI), Temperature, Consumer Price Index (CPI) and yearly Natural Gas (NG) demand investigated.

Consumption smoothing in Latin America: an empirical assessment of present value models

The study aims to assess the empirical adherence of the permanent income theory and the consumption smoothing view in Latin America. Two present value models are considered, one describing household behavior and the other open economy macroeconomics. Following the methodology developed in Campbell and Schiller (1987), Bivariate Vector Autoregressions are estimated for the saving ratio and the real growth rate of income concerning the household behavior model and for the current account and the change in national cash ‡ow regarding the open economy model. The countries in the sample are considered separately in the estimation process (individual system estimation) as well as jointly (joint system estimation). Ordinary Least Squares (OLS) and Seemingly Unrelated Regressions (SURE) estimates of the coe¢cients are generated. Wald Tests are then conducted to verify if the VAR coe¢cient estimates are in conformity with those predicted by the theory. While the empirical results are sensitive to the estimation method and discount factors used, there is only weak evidence in favor of the permanent income theory and consumption smoothing view in the group of countries analyzed.

Saving-capm: uma proposta de solução para o equity premium puzzle do consumption-capm

Em 1985, Mehra e Prescott levantaram uma questão que até hoje não foi respondida de forma satisfatória: o prêmio de risco das ações americanas é muito maior do que poderia ser explicado pelo “paradigma neoclássico de finanças econômicas” (financial economics) representado pelo modelo C-CAPM. E, a partir de então, este problema não resolvido ficou conhecido como o “Equity Premium Puzzle” (EPP) ou o “Enigma do Prêmio (de risco) das Ações”. Este enigma estimulou a produção de uma série de artigos, dissertações e teses que tentaram ajustar os modelos intertemporais de utilidade esperada aos dados dos mercados financeiros. Dentro deste contexto, esta tese busca (i) revisar a evolução histórica da teoria dos modelos de maximização da utilidade intertemporal dos agentes, (ii) analisar os pressupostos e conceitos chaves desses modelos, (iii) propor um novo modelo que seja capaz de solucionar o EPP, (iv) aplicar este modelo proposto aos dados históricos anuais entre 1929 e 2004 e (v) validar a lógica deste modelo através das metodologias Mehra-Prescott e Hansen-Jagannathan. Esta tese faz uma crítica de que os estudos até aqui desenvolvidos tentaram explicar a dinâmica de um mercado financeiro altamente sofisticado, através de um modelo de economia não-monetária e de subsistência. Assim, a sua contribuição consiste na alteração desse pressuposto de uma economia de subsistência, considerando que a renda disponível do setor privado não seja integralmente consumida, mas que também possa ser poupada. Assumindo que as pessoas obtêm satisfação (utilidade) tanto pelo consumo atual como pela poupança atual (que será o consumo futuro), será deduzido que a utilidade marginal de consumir é igual à de poupar, em todo e qualquer período. Com base nisso, a utilidade marginal a consumir é substituída pela utilidade marginal de poupar dentro do modelo básico do C-CAPM. Para reforçar a idéia de que o modelo desta tese usa dados de poupança em vez de consumo, ao longo do trabalho ele será chamado de Sanving-CAPM, ou S-CAPM. Este novo modelo mostrou-se capaz de solucionar o EPP quando submetidas às abordagens Mehra-Prescott e Hansen-Jagannathan.

The influence of materialism on consumption indebtedness in the context of low income consumers from the city of São Paulo

This research is in the domains of materialism, consumer vulnerability and consumption indebtedness, concepts frequently approached in the literature on consumer behavior, macro-marketing and economic psychology. The influence of materialism on consumer indebtedness is investigated within a context that is characterized by poverty and by factors that cause vulnerability, such as high interest rates, limited access to credit and to quality affordable goods. The objectives of this research are: to produce a materialism scale that is well adapted to its environment, characterizing materialism adequately for the population studied; to compare results obtained with results of other studies; and to measure the relationship between materialism, socio-demographic variables, attitude to debt and consumption indebtedness. The primary data used in the analyses were collected from field research carried out in August, 2005 that relied on a probabilistic household sample of 450 low income individuals who live in poor regions of the city of Sao Paulo. The materialism scale, adapted and translated into Portuguese from Richins (2004), proved to be very successful and encourages new work in the area. It was noted that younger adults tend to be more materialistic than older ones; that illiterate adults tend to be less materialistic than those who did literacy courses when they were already adults; and that gender, income and race are not associated with the materialism construct. Among the other results, a logistic regression model was developed in order to distinguish those individuals who have an installment plan payment booklet from those who do not, based on materialism, socio-demographic variables and purchasing and consumer habits. The proposed model confirms materialism as a behavioral variable useful for forecasting the probability of an individual getting into debt in order to consume, in some cases almost doubling the chance of occurrence of this event. Findings confirm the thesis that it is not only adverse economic factors that lead people to get into debt; and that the study of demand for credit for consumption purposes must, of necessity, include variables of a psychological nature. It is suggested that the low income materialistic consumer experiences feelings of powerlessness and exclusion because of the gap that exists between their possessions and their desires. Lines of conduct to combat this marginalization from the consumer society are drawn targeting marketing professionals, public policy makers and vulnerability researchers. Finally, the possibility of new studies involving the materialism construct, which is central to literature on consumer behavior, albeit little used in empirical studies in Brazil, are discussed.

Testing the optimality of aggregate consumption decisions: is there rule-of-thumb behavior?

Consumption is an important macroeconomic aggregate, being about 70% of GNP. Finding sub-optimal behavior in consumption decisions casts a serious doubt on whether optimizing behavior is applicable on an economy-wide scale, which, in turn, challenge whether it is applicable at all. This paper has several contributions to the literature on consumption optimality. First, we provide a new result on the basic rule-of-thumb regression, showing that it is observational equivalent to the one obtained in a well known optimizing real-business-cycle model. Second, for rule-of-thumb tests based on the Asset-Pricing Equation, we show that the omission of the higher-order term in the log-linear approximation yields inconsistent estimates when lagged observables are used as instruments. However, these are exactly the instruments that have been traditionally used in this literature. Third, we show that nonlinear estimation of a system of N Asset-Pricing Equations can be done efficiently even if the number of asset returns (N) is high vis-a-vis the number of time-series observations (T). We argue that efficiency can be restored by aggregating returns into a single measure that fully captures intertemporal substitution. Indeed, we show that there is no reason why return aggregation cannot be performed in the nonlinear setting of the Pricing Equation, since the latter is a linear function of individual returns. This forms the basis of a new test of rule-of-thumb behavior, which can be viewed as testing for the importance of rule-of-thumb consumers when the optimizing agent holds an equally-weighted portfolio or a weighted portfolio of traded assets. Using our setup, we find no signs of either rule-of-thumb behavior for U.S. consumers or of habit-formation in consumption decisions in econometric tests. Indeed, we show that the simple representative agent model with a CRRA utility is able to explain the time series data on consumption and aggregate returns. There, the intertemporal discount factor is significant and ranges from 0.956 to 0.969 while the relative risk-aversion coefficient is precisely estimated ranging from 0.829 to 1.126. There is no evidence of rejection in over-identifying-restriction tests.