Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

Síntese e caracterização de perovskitas LaNi(1-x)Co xO3 como precursores de catalisadores para a conversão do metano a gás de síntese pela reforma com CO2

LaNiO3 perovskite was modified by partial substitution of nickel by cobalt in order to increase the stability and resistance to carbon deposition during the methane CO2 reforming. The results showed that a suitable combination of precipitation and calcination steps resulted in oxides with the desired structure and with important properties for application in heterogeneous catalysis. The partial substitution of Ni by Co resulted in lower rates of conversion of both the reactants, but the catalyst stability was highly increased. The LaNi0.3Co0.7O3 catalyst, calcined at 800 ºC, was the most active under the reaction conditions.

Biomassa e energia

Biomass was the dominating source of energy for human activities until the middle 19th century, when coal, oil, gas and other energy sources became increasingly important but it still represents ca. 10% of the worldwide energy supply. The major part of biomass for energy is still "traditional biomass" used as wood and coal extracted from native forests and thus non-sustainable, used with low efficiency for cooking and home heating, causing pollution problems. This use is largely done in rural areas and it is usually not supported by trading activities. There is now a strong trend to the modernization of biomass use, especially making alcohol from sugar cane thus replacing gasoline, or biodiesel to replace Diesel oil, beyond the production of electricity and vegetable coal using wood from planted forests. As recently as in 2004, sustainable "modern biomass" represented 2% of worldwide energy consumption. This article discusses the perspectives of the "first" and "second" technology generations for liquid fuel production, as well as biomass gaseification to make electricity or syngas that is in turn used in the Fischer-Tropsch process.

Atual estágio de desenvolvimento da tecnologia GTL e perspectivas para o Brasil

Although the production of liquid fuels from coal, natural gas (CTL and GTL processes) and other carbon sources has been discovered 90 years ago, the interest was renewed in the last years motivated by stranded gas reserves and by petroleum market instability. This review intends to show the scenario of these technologies nowadays, discussing the applied technologies, the steps in an industrial plant, the ways to produce syngas and liquid fuels, the catalysts used, the type of reactors and the operating plants with their respective capacities, besides the technical, economical and environmental viability, challenges and perspectives for Brazil.

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.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Production of Biofuels by Fischer Tropsch Synthesis

Production of biofuel via biomass gasification followed by Fischer Tropsch synthesis is of considerable interest because of the high quality of fuels produced which do not contain sulphur and are free of carbon dioxide. The purpose of this Master’s thesis is to study feasibility production of biofuels integrated with Fischer Tropsch process using Aspen Plus simulation. The simulation results were used to size process equipment and carry out an economic evaluation. The results show that lowering the reactor temperature from 1000 oC - 850 oC and raising the water gas shift temperature from 500 oC - 600 oC can improve overall gas efficiency, which in turn leads to better production of ultra clean syngas for the Fischer Tropsch synthetic reactor. Similarly, the Fischer Tropsch offgas is converted into a gas turbine for power production, and finally biodiesel is produced as fuels for transportation.

Carboxydothermus hydrogenoformans comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène simultanément a la minéralisation de calcium et phosphate

La gazéification est aujourd'hui l'une des stratégies les plus prometteuses pour valoriser les déchets en énergie. Cette technologie thermo-chimique permet une réduction de 95 % de la masse des intrants et génère des cendres inertes ainsi que du gaz de synthèse (syngaz). Le syngaz est un combustible gazeux composé principalement de monoxyde de carbone (CO), d'hydrogène (H2) et de dioxyde de carbone (CO2). Le syngaz peut être utilisé pour produire de la chaleur et de l'électricité. Il est également la pierre angulaire d'un grand nombre de produits à haute valeur ajoutée, allant de l'éthanol à l'ammoniac et l'hydrogène pur. Les applications en aval de la production de syngaz sont dictées par son pouvoir calorifique, lui-même dépendant de la teneur du gaz en H2. L’augmentation du contenu du syngaz en H2 est rendu possible par la conversion catalytique à la vapeur d’eau, largement répandu dans le cadre du reformage du méthane pour la production d'hydrogène. Au cours de cette réaction, le CO est converti en H2 et CO2 selon : CO + H2O → CO2 + H2. Ce processus est possible grâce à des catalyseurs métalliques mis en contact avec le CO et de la vapeur. La conversion catalytique à la vapeur d’eau a jusqu'ici été réservé pour de grandes installations industrielles car elle nécessite un capital et des charges d’exploitations très importantes. Par conséquent, les installations de plus petite échelle et traitant des intrants de faible qualité (biomasse, déchets, boues ...), n'ont pas accès à cette technologie. Ainsi, la seule utilisation de leur syngaz à faible pouvoir calorifique, est limitée à la génération de chaleur ou, tout au plus, d'électricité. Afin de permettre à ces installations une gamme d’application plus vaste de leurs syngaz, une alternative économique à base de catalyseur biologique est proposée par l’utilisation de bactéries hyperthermophiles hydrogénogènes. L'objectif de cette thèse est d'utiliser Carboxydothermus hydrogenoformans, une bactérie thermophile carboxydotrophe hydrogénogène comme catalyseur biologique pour la conversion du monoxyde de carbone en hydrogène. Pour cela, l’impact d'un phénomène de biominéralisation sur la production d’H2 a été étudié. Ensuite, la faisabilité et les limites de l’utilisation de la souche dans un bioréacteur ont été évaluées. Tout d'abord, la caractérisation de la phase inorganique prédominante lorsque C. hydrogenoformans est inoculé dans le milieu DSMZ, a révélé une biominéralisation de phosphate de calcium (CaP) cristallin en deux phases. L’analyse par diffraction des rayons X et spectrométrie infrarouge à transformée de Fourier de ce matériau biphasique indique une signature caractéristique de la Mg-whitlockite, alors que les images obtenues par microscopie électronique à transmission ont montré l'existence de nanotiges cristallines s’apparentant à de l’hydroxyapatite. Dans les deux cas, le mode de biominéralisation semble être biologiquement induit plutôt que contrôlé. L'impact du précipité de CaP endogène sur le transfert de masse du CO et la production d’H2 a ensuite été étudié. Les résultats ont été comparés aux valeurs obtenues dans un milieu où aucune précipitation n'est observée. Dans le milieu DSMZ, le KLa apparent (0.22 ± 0.005 min-1) et le rendement de production d’H2 (89.11 ± 6.69 %) étaient plus élevés que ceux obtenus avec le milieu modifié (0.19 ± 0.015 min-1 et 82.60 ± 3.62% respectivement). La présence du précipité n'a eu aucune incidence sur l'activité microbienne. En somme, le précipité de CaP offre une nouvelle stratégie pour améliorer les performances de transfert de masse du CO en utilisant les propriétés hydrophobes de gaz. En second lieu, la conversion du CO en H2 par la souche Carboxydothermus hydrogenoformans fut étudiée et optimisée dans un réacteur gazosiphon de 35 L. Parmi toutes les conditions opérationnelles, le paramètre majeur fut le ratio du débit de recirculation du gaz sur le débit d'alimentation en CO (QR:Qin). Ce ratio impacte à la fois l'activité biologique et le taux de transfert de masse gaz-liquide. En effet, au dessus d’un ratio de 40, les performances de conversion du CO en H2 sont limitées par l’activité biologique alors qu’en dessous, elles sont limitées par le transfert de masse. Cela se concrétise par une efficacité de conversion maximale de 90.4 ± 0.3 % et une activité spécifique de 2.7 ± 0.4 molCO·g–1VSS·d–1. Malgré des résultats prometteurs, les performances du bioréacteur ont été limitées par une faible densité cellulaire, typique de la croissance planctonique de C. hydrogenoformans. Cette limite est le facteur le plus contraignant pour des taux de charge de CO plus élevés. Ces performances ont été comparées à celles obtenues dans un réacteur à fibres creuses (BRFC) inoculé par la souche. En dépit d’une densité cellulaire et d’une activité volumétrique plus élevées, les performances du BRFC à tout le moins cinétiquement limitées quand elles n’étaient pas impactées par le transfert de masse, l'encrassement et le vieillissement de la membrane. Afin de parer à la dégénérescence de C. hydrogenoformans en cas de pénurie de CO, la croissance de la bactérie sur pyruvate en tant que seule source de carbone a été également caractérisée. Fait intéressant, en présence simultanée de pyruvate et de CO, C. hydrogenoformans n’a amorcé la consommation de pyruvate qu’une fois le CO épuisé. Cela a été attribué à un mécanisme d'inhibition du métabolisme du pyruvate par le CO, faisant ainsi du pyruvate le candidat idéal pour un système in situ de secours.

Group 11 (Cu, Ag, Au) promotion of 15%Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts

Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts promoted with different quantities of Group 11 metals (Cu, Ag, Au) were characterized and tested. The presence of relatively small quantities of such metals enhanced Co reducibility and, in the cases of Ag and Au, improved the surface Co metal active site densities. EXAFS experiments with the most loaded catalyst samples show that only Co-Co and Me-Me (Me = Cu, Ag and Au) coordination could be observed. This suggests that the greater fraction of the metals form different phases. However, the reduction promoting effect of the Group 11 metal is severely hampered once the catalyst receives a mild passivation treatment following primary reduction. An explanation in terms of promoter segregation during primary reduction is proposed. At lower promoter levels (0.83%Ag and 1.51%Au) and higher Ag levels (2.76%), significant gains in Co active site densities were achieved resulting in improved CO conversion levels relative to the unpromoted catalyst. Moreover, slight decreases in light product (e.g., CH(4)) selectivity and slight increases in C(5)+ selectivity were achieved. At high Au loading (5.05%), however, too much Au was loaded which, although significantly increasing the fraction of Co reduced, blocked Co surface sites and resulted in decreased Co conversion rates. While Cu facilitated Co reduction, the increased fraction of reduced Co did not translate to improved active site densities. It appears that a fraction of Cu tended to cover the rim of Co clusters, resulting in decreases in CO conversion rates and detrimental increases in light product selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis of NiO-MgO-ZrO(2) catalysts and their performance in reforming of model biogas

Catalysts containing NiO/MgO/ZrO(2) mixtures were synthesized by the polymerization method in a single step. They were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR) and physisorption of N(2) (BET) and then tested in the reforming of a model biogas (1.5CH4:1CO(2)) in the presence of air (1.5CH(4) + 1CO(2) + 0.25O(2)) at 750 degrees C for 6h. It was observed that the catalyst Ni20MZ performed better in catalytic processes than the well known catalysts, Ni/ZrO(2) and Ni/MgO, synthesized under the same conditions. The formation of solid solutions, MgO-ZrO(2) and NiO-MgO, increased the rate of conversion of reactants (CH(4) and CO(2)) into synthesis gas (H(2) + CO). The formation of oxygen vacancies (in samples containing ZrO(2) and MgO) seems to promote removal of the coke deposited on the nickel surface. The values of the H(2)/CO ratio were generally found to be slightly lower than stoichiometric, owing to the reverse water gas shift reaction occurring in parallel. (C) 2011 Elsevier B.V. All rights reserved.

Síntese e caracterização de cerâmicas nanométricas para produção de gás de síntese

In this work, ceramic powders belonging to the system Nd2-xSrxNiO4 (x = 0, 0.4, 0.8, 1.2 and 1.6) were synthesized for their use as catalysts to syngas production partial. It was used a synthesis route, relatively new, which makes use of gelatin as organic precursor. The powders were analyzed at several temperatures in order to obtain the perovskite phase and characterized by several techniques such as thermal analysis, X-rays diffraction, Rietveld refinement method, specific surface area, scanning electron microscopy, energy dispersive spectroscopy of X-rays and temperature programmed reduction. The results obtained using these techniques confirmed the feasibility of the synthesis method employed to obtain nanosized particles. The powders were tested in differential catalytic conditions for dry reforming of methane (DRM) and partial oxidation of methane (POM), then, some systems were chosen for catalytic integrals test for (POM) indicating that the system Nd2-xSrxNiO4 for x = 0, 0.4 and 1.2 calcined at 900 °C exhibit catalytic activity on the investigated experimental conditions in this work without showing signs of deactivation

Síntese de catalisadores do tipo LaNixFe1-xO3 como precursores catalíticos para reação oxidação parcial do metano

Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 °C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 °C, whereas the LaFeO3 sample depicted a peak above 1000°C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion

Carregadores de oxigênio a base de níquel suportado em materiais mesooros para aplicação na recirculação química com reforma (RQR)

Oxygen carriers are metal oxides which have the ability to oxidize and reduce easily by various cycles. Due to this property these materials are widely usedin Chemical-Looping Reforming processes to produce H2 and syngas. In this work supports based on MCM-41 and La-SiO2 were synthesized by hydrothermal method. After the synthesis step they were calcined at 550°C for 2 hours and characterized by TG, XRD, surface area using the BET method and FTIR spectroscopy. The deposition of active phase, in this case Nickel, took place in the proportions of 5, 10 and 20% by weight of metallic nickel, for use as oxygen carriers.The XRD showed that increasing in the content of Ni supported on MCM-41 resulted in a decrease in spatial structure and lattice parameter of the material. The adsorption and desorption curves of the MCM-41 samples exhibited variations with the increase of Ni deposited. Surface area, average pore diameter and wall density of silica showed significant changes , due to the increase of the active phase on the mesoporous material. By other hand, in the samples with La-SiO2 composition was not observed peaks characteristic of hexagonal structure, in the XRD diffractogram. The adsorption/desorption isotherms of nitrogen observed are type IV, characteristic of mesoporous materials. The catalytic test indicates that the supports have no influence in the process, but the nickel concentration is very important, because the results for minor concentration of nickel are not good. The ratio H2/O2 was close to 2, for all 15 cycles involving the test storage capacity of O2, indicating that the materials are effective for oxygen transport

Estudo do desempenho de catalisadores tipo Ni/CexM1-xO2 (M = Zr ou Mn) na reação de oxidação parcial do metano

One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 °C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation.

Improved activity and stability of Ce-promoted Ni/γ-A1 2O3 catalysts for carbon dioxide reforming of methane

The CO2 reforming of CH4 was carried out over Ni catalysts supported on γ-Al2O3 and CeO 2-promoted γ-Al2O3. The catalysts were characterized by means of surface area measurements, TPR, CO2 and H2 chemisorption, XRD, SEM, and TEM. The CeO2 addition promoted an increase of catalytic activity and stability. The improvement in the resistance to carbon deposition is attributed to the highest CO2 adsorption presented by the CeO2 addition. The catalytic behavior presented by the samples, with a different CH4/CO2 ratio used, points to the CH4 decomposition reaction as the main source of carbon deposition.