Dinâmica do fósforo em cultivo heterotrófico e produção de compostos celulares por cianobactéria integrado a biorrefinarias agroindustriais

O objetivo desta tese foi avaliar a dinâmica do fósforo em cultivo heterotrófico e produção de compostos celulares por Aphanothece microscopica Nägeli visando avaliar a perspectiva de implementação de uma biorrefinaria microalgal. Desta forma, foi avaliado o comportamento do micro-organismo em estudo no cultivo heterotrófico, utilizando como meio de cultivo o efluente de laticínios. O trabalho foi desenvolvido em 3 etapas. Em um primeiro momento foi avaliada a influência da temperatura (20 e 30°C) e os valores máximos e mínimos de nutrientes, em especial do fósforo dissolvido reativo (PDR), disponíveis no efluente de laticínio, na remoção de nutrientes. Os resultados demonstraram que a concentração inicial de fósforo dissolvido e a temperatura exerceram influência no crescimento celular e na eficiência de remoção de nutrientes. Em termos de otimização de processo os cultivos conduzidos a 20°C e maiores concentrações de PDR (5,5 mg.L-1 ) no efluente de laticínio, foram os mais eficientes na conversão de poluentes em biomassa e remoção de nutrientes. A segunda etapa foi desenvolvida com o objetivo de avaliar a dinâmica de distribuição de fósforo na fase líquida e sólida do reator heterotrófico, quando o efluente de laticínio foi tratado pela Aphanothece microscopica Nägeli, a 20°C e nas máximas concentrações de fósforo dissolvido encontradas no efluente. Foi demonstrado que as formas fosforadas na fase líquida do reator se caracterizam pela predominância da fração dissolvida em comparação à particulada e por apresentar como fração predominante a de fósforo orgânico. No que se refere à fase sólida, ficou demonstrado que a Aphanothece microscopica Nägeli, quando cultivada heterotroficamente apresenta 3,8 vezes mais fósforo que o requerido para o crescimento celular. Ficando demonstrado ainda que a remoção biológica de fósforo por Aphanothece microscopica Nägeli pode resultar em substanciais aportes financeiros para as estações de tratamento de efluentes. Uma terceira etapa foi desenvolvida, a qual teve como objetivo avaliar a estimativa de produção de compostos celulares por Aphanothece microscopica Nägeli, a partir do efluente de laticínio, bem como o efeito da redução de temperatura de cultivo no teor de lipídios , no momento em que é obtida a máxima concentração deste componente celular, nas condições otimizadas.Foi obtido na fase logarítmica de crescimento, concentrações de 41,8 % de proteinas, carboidratos 28,5 %, lipídios 10,4 % e minerais 10,8 %. O maior teor de lipídio registrado a 20°C correspondeu a biomassa analisada na fase logarítmica.Com a redução da temperatura para 5°C por um período de 30 h é possível obter concentrações de lipídios 2,4 vezes superior ao registrado na fase logarítmica a 20 °C. No entanto, não foram indicadas diferenças significativas (p≤0,05) em função da temperatura entre as concentrações de lipídios obtidas para a biomassa a 10°C em 40 h. O perfil de ácidos graxos da biomassa gerada a 20°C, apresentou como ácidos graxos majoritários, os ácidos graxos: palmítico, oléico, γ-linolênico, palmitoleico e esteárico, resultando um aumento na concentração de ácidos graxos saturados as espensa dos insaturados, quando a temperatura é reduzida. Em paralelo,um reator heterotrófico descontinuo foi definido, ficando demonstrado que a extrapolação da operação em batelada para contínua requer um biorreator heterotrófico com volume útil de trabalho de 240,51 m 3 , permitindo tratar 950 m3 diários de efluente, gerando 11,8 kg.d-1 de biomassa útil para produção de compostos celulares por Aphanothece microscopica Nägeli, visando à simultânea remoção de matéria orgânica, nitrogênio total e fósforo total, gerando insumos que podem suportar a implementação de uma biorrefinaria microalgal.

Desenvolvimento de uma Metodologia para a Seletividade cinética aplicada ao processo de hidroconversão do petróleo, ocorrendo em reator gás-líquido

Este trabalho tem como objetivo desenvolver uma metodologia de seletividade cinética, para os pseudocomponentes do petróleo em escoamento gás-liquido em colunas de bolhas usando a Fluidodinâmica Computacional (CFD). Uma geometria cilíndrica de 2,5m de altura e 0,162m de diâmetro foi usada tanto na validação fluidodinâmica com base em dados experimentais da literatura, como na análise cinética do reator operando em dois modos distintos em relação a fase líquida: batelada e contínuo. Todos os casos de estudo operam em regime heterogêneo de escoamento, com velocidade superficial do gás igual a 8 cm/s e diâmetro médio de bolhas de 6 mm. O modelo fluidodinâmico validado apresentou boa concordância com os dados experimentais, sendo empregado como base para a implementação do modelo cinético de rede de Krishna e Saxena (1989). A análise da hidroconversão foi realizada a 371ºC, e os resultados mostraram o comportamento esperado para o processo reativo estudado, definindo-se os tempos (batelada) e posições axiais (contínuo) de coleta ideal para os pseudocomponentes leves. Em síntese, ressaltase o uso da ferramenta CFD no entendimento, desenvolvimento e otimização de processos.

Amphiphilic catalysts for the treatment of oily wastewaters

The main objective of this study was to obtain an effective catalyst for removal of diazo dye - Sudan IV by Catalytic Wet Peroxide Oxidation (CWPO). For this purpose liquid phase treatment was used to increase the basicity of activated carbon surface favoring the adsorption of organic pollutants. Modified activated carbon catalysts were used in different types of experiments: 1) decomposition of H2O2 in aquatic media, 2) decomposition of H2O2 in organic media, 3) adsorption of Sudan IV, 4) Sudan IV removal by CWPO. As the result of all of these experiments the most effective catalyst was obtained and discussed. It was not observed removal of Sudan IV from biphasic system by CWPO. The obtained results in some cases show a slight increase in concentration of Sudan IV, which may be ascribed to experimental errors. Different factors could be the reason of those errors. For example, the high volatility properties of organic media used in experiments should be taken into account during experiments. Under settled reaction temperature the decrease of cyclohexane volume during experiment could give rise in Sudan IV concentration. The initial concentration of model diazo dye also should be reviewed more detailed for CWPO experiments. Despite of these experimental errors the behavior of our catalysts in different media was observed.

Resistência ao choque térmico de carbeto de silício sinterizado via fase líquida

Tese (Doutorado em Tecnologia Nuclear)

Two-State Thermodynamics of Supercooled Water

Water has been called the “most studied and least understood” of all liquids, and upon supercooling its behavior becomes even more anomalous. One particularly fruitful hypothesis posits a liquid-liquid critical point terminating a line of liquid-liquid phase transitions that lies just beyond the reach of experiment. Underlying this hypothesis is the conjecture that there is a competition between two distinct hydrogen-bonding structures of liquid water, one associated with high density and entropy and the other with low density and entropy. The competition between these structures is hypothesized to lead at very low temperatures to a phase transition between a phase rich in the high-density structure and one rich in the low-density structure. Equations of state based on this conjecture have given an excellent account of the thermodynamic properties of supercooled water. In this thesis, I extend that line of research. I treat supercooled aqueous solutions and anomalous behavior of the thermal conductivity of supercooled water. I also address supercooled water at negative pressures, leading to a framework for a coherent understanding of the thermodynamics of water at low temperatures. I supplement analysis of experimental results with data from the TIP4P/2005 model of water, and include an extensive analysis of the thermodynamics of this model.

Caracterização de compósitos Nb-20%cu obtidos por moagem de alta energia e sinterizados por fase líquida

In this work, was studied the formation of a composite of the refractory metal niobium with copper, through the process of high-energy milling and liquid phase sintering. The HEM can be used to synthesize composite powders with high homogeneity and fine size particle distribution. It may also produce the solid solubility in immiscible systems such as Nb-Cu, or extend the solubility of systems with limited solubility. Therefore, in the immiscible system Cu-Nb, the high-energy milling was successfully used to obtain the composite powder particles. Initially, the formation of composite particles during the HEM and the effect of preparation technique on the microstructure of the material was evaluated. Four loads of Nb and Cu powders containing 20%wt Cu were synthesized by MAE in a planetary type ball mill under different periods of grinding. The influence of grinding time on the metal particles is evaluated during the process by the withdrawal of samples at intermediate times of milling. After compaction under different forces, the samples were sintered in a vacuum furnace. The liquid phase sintering of these samples prepared by HEM produced a homogeneous and fine grained. The composite particles forming the sintered samples are the addition of a hard phase (Nb) with a high melting point, and a ductile phase (Cu) with low melting point and high thermal and electrical conductivities. Based on these properties, the Nb-Cu system is a potential material for many applications, such as electrical contacts, welding electrodes, coils for generating high magnetic fields, heat sinks and microwave absorbers, which are coupled to electronic devices. The characterization techniques used in this study, were laser granulometry, used to evaluate the homogeneity and particle size, and the X-ray diffraction, in the phase identification and to analyze the crystalline structure of the powders during milling. The morphology and dispersion of the phases in the composite powder particles, as well the microstructures of the sintered samples, were observed by scanning electron microscopy (SEM). Subsequently, the sintered samples are evaluated for density and densification. And finally, they were characterized by techniques of measuring the electrical conductivity and microhardness, whose properties are analyzed as a function of the parameters for obtaining the composite

New Catalysts for the Renewable Production of Monomers for Bioplastics

Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H₂ reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr⁴⁺ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

Estudo da molhabilidade de ligas de adição à base de prata sobre insertos cerâmicos para aplicação em brocas perfuração de poços de petróleo

Metal-ceramic interfaces are present in tricone drill bits with hard ceramic inserts for oil well drilling operations. The combination of actions of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. Also the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. Wetting phenomena plays an essential role in the production of metal/ceramic interfaces when a liquid phase is present in the process. In this work, 72Silver-28Copper eutectic based brazing alloys were melted onto zirconia, silicon nitride and tungsten carbide/Co substrates under high vacuum. Contact angle evolution was measured and graphically plotted, and the interfaces produced were analysed by SEM-EDX. The AgCu eutectic alloy did not wet any ceramic substrates, showing high contact angles, and so without chemical interaction between the materials. Better results were found for the systemns containing 3%wt of titanium in the AgCu alloy. The presence os titanium as a solute in the alloy produces wettable cand termodinamically stable compounds, increasing the ceramics wetting beahviour

Formulação de bloco intertravado cerâmico com adição de resíduos urbanos e industriais

The production of waste from urban and industrial activities is one of the factors of environmental contamination and has aroused attention of the scientific community, in the sense of its reuse. On the other hand, the city of Salvador/Ba, with approximately 262 channels, responsible for storm water runoff, produces every year, by the intervention of cleaning and clearing channels, a significant volume of sediments (dredged mud), and thus an appropriate methodology for their final destination. This study aims to assess the influence of incorporation of these tailings in arrays of clay for production of interlocked block ceramic, also known as ceramic paver. All the raw materials from the metropolitan region of Salvador (RMS) were characterized by x-ray fluorescence, x-ray diffraction, thermal analysis (TG and TDA), particle size analysis and dilatometry. With the use of statistical experimental planning technique, ternary diagram was defined in the study region and the analyzed formulations. The specimens were prepared with dimensions of 60x20x5mm³, by uniaxial pressing of 30 MPa and after sintering at temperatures of 900°, 1000º and 1100ºC the technological properties were evaluated: linear shrinkage, water absorption, apparent porosity, apparent specifies mass, flexural rupture and module. For the uniaxial compression strength used cylindrical probe body with Ø 50 mm. The standard mass (MP) was prepared with 90% by weight of clay and 10% by weight of Channel sediment (SCP), not being verified significant variations in the properties of the final product. With the incorporation of 10% by weight of manganese residue (PFM) and 10% by weight of the Ceramic waste (RCB) in the mass default, in addition to adjusting the plasticity due to less waste clay content, provided increased linear firing shrinkage, due the significant concentration of K2O, forming liquid phase at low temperature, contributing to decreased porosity and mechanical resistance, being 92,5 MPa maximum compressive strength verified. After extract test leachate and soluble, the piece containing 10% of the PFM, was classified as non-hazardous and inert material according to NBR10004/04 ABNT. The results showed the feasibility on using waste, SCP, RCB and PFM clay mass, at temperatures above 900ºC, paver ceramic production, according to the specifications of the technical standards, so that to exceed the 10% of the PFM, it becomes imperative to conduct studies of environmental impacts

Adição de subprodutos da cinza da casca de café (coffea canephora) em massa cerâmica para porcelanato

To produce porcelain tiles fluxing agents are used in order to obtain a liquid phase during firing. This liquid phase fills the pores decreasing porosity, water absorption and contributes to material densification. In the porcelain tiles industry, feldspar is the main flux material used, with quantities ranging between 35 and 50%. Studies focus on the discovery of materials with flux characteristics that can reduce the consumption of feldspar by porcelain tiles industry. In this context, the coffee husk ashes, a residue obtained when coffee husks are burned to produce heat for the dryers during the processing of the green fruit, have as main chemical constituents potassium, calcium and magnesium, giving them characteristics of fluxing material. Brazil is the largest coffee producer in the world and is responsible for over 30% of the world s production. In this work a physical treatment of coffee husk ash was carried out in order to eliminate the organic matter and, after this, two by-products were obtained: residual wastes R1 and R2. Both residues were added separately as single fluxes and also in association with feldspar in mixtures with raw materials collected in a porcelain industry located in Dias d Ávila-Ba. The addition of these residues aimed to contribute to the reduction of the consumption of feldspar in the production of porcelain tiles. Specimens were produced with dimensions of 60 mm x 20 mm x 6 mm in an uniaxial die with compacting pressure of 45 MPa. The samples were heated to a temperature of 1200 °C, for 8 minutes. Tests were performed to characterize the raw materials by XRF, XRD, particle size analysis, DTA and TGA and, additionally, the results of the physical properties of water absorption, apparent porosity, linear shrinkage, density, dilatometry, flexural strength and SEM of sintered body were analyzed. Additions of less than 8% of the residue R1 contributed to the decrease of porosity, but the mechanical strength of the samples was not satisfactory. Additions of 5% the R2 residue contributed significantly to decrease the water absorption and apparent porosity, and also to increase the mechanical strength. Samples with addition of feldspar associated with the R2 residue, in proportions of 6.7% of R2 and 6.7% of feldspar, led to results of water absorption of 0.12% and mechanical strength of 46 MPa, having parameters normalized to the manufacture of porcelain stoneware tiles

Influência da vermiculita expandida na formulação de pastas leves para evitar a migração de gás em cimentação de poços petrolíferos

The gas migration during the cementing of wells is one of the main problems of oil wells engineering. Its occurrence can cause severe problems since shortly to loss of control of the well after cementation. Recently, 20/04/2010 In an accident of major proportions in the Gulf of Mexico, among other factors, faulty cementing operation provided the gas migration, causing the accident, in which 11 people died and 17 were injured occurred. Besides the serious consequences that can be caused by gas migration, remediation of the problem, which is made by injecting cement in damaged areas, usually involves additional costs and is not always effective. Therefore, preventing gas migration to be preferred. Some methods are used to prevent the migration of the pressurized gas as the annular space, application of pressure pulses, reducing the height of the cement column compressible cement pastes of low permeability, pastes and to control free filtered water, and binders of thixotropic cement expandable and flexible. Thus, the cement pastes used to prevent gas migration must meet the maximum these methods. Thus, this study aimed to formulate a cement paste to prevent gas migration, using the expanded vermiculite, and evaluate the behavior of the folder trials necessary for use in oil wells. Free water content, rheological properties, compressive strength, loss of liquid phase sedimentation of solids, specific weight, thickening time and gas migration: The following tests were performed. The results show that meets the specifications paste formulated for use in oil wells and the use of expanded vermiculite contribute to the absorption of free water, thixotropy and low density. The absorption of free water is proven to result in zero percentage test free water content, thixotropy is observed with the high value of the initial gel strength (Gi) in testing rheological properties and low density is proven in test weight specific

Ir supported over carbon materials for the selective hydrogenation of chloronitrobenzenes

In the present work we have studied the effect of carbon supports with different graphitic character (carbon nanotubes, mesoporous graphite and activated carbon) on the catalytic performance of iridium nanoparticles on the liquid phase chemoselective hydrogenation of para-chloronitrobenzene at room temperature. The effect of the oxygen groups was also evaluated by oxidizing a portion of the carbon nanotubes. The Raman and XRD spectra showed that the mesoporous graphite displayed the strongest graphitic character. The characterization of the catalysts by HR-TEM, XPS and TPR-H2, showed that the catalysts had similar particle size and that the catalysts prepared over the previously oxidized support, Ir/CNTox, was not fully reduced. The activity and selectivity achieved with the catalyst Ir/CNT was the best among the samples and the presence of irdium oxide on Ir/CNTox diminished the yield to p-chloroaniline, being the worse catalyst. The reactivity of different isomers was also studied over Ir/CNT and it followed the order m > o > p.

Dysprosium transport in Nd-Fe-B pellets

The addition of heavy rare earth (RE) elements to Nd2Fe14B based magnets to form (Nd,Dy)2Fe14B is known to increase the coercivity and high temperature performance required for hybrid vehicle electric motors and other extreme temperature applications. Attempts to conserve heavy rare earth elements for high temperature (RE)2Fe14B based magnets have led to the development of a grain boundary diffusion process for bulk magnets. This process relies on transport of a heavy rare earth, such as Dy, into a bulk Nd2Fe14B magnet along pores, a low volume fraction of eutectic liquid along grain boundary grain triple junctions and grain boundaries. This enriches the grain surfaces in Dy through the thickness of the bulk magnet, leading to larger increases coercivity with a smaller Dy concentration than can be achieved with homogeneous alloys. Attempts to carry out the same process during sintering require significant control of Dy transport efficiency. The macroscopic transport of Dy in Nd2.7Fe14B1.4 based powder packs is studied using a 'layered' pellet, where Nd2.7Fe14B1.4powder is an interlayer and Dy source as a center layer. The sintering of this layered pellet provided evidence for very large effective diffusion lengths aided by Dy rich liquid flow through connected porosity. Approaches to controlling Dy transportation include decreasing the liquid phase transport capability of the powder pack by increasing the melting point of the Dy source and the decreasing amount of RE rich liquid in the powder packs. The solid-liquid reaction is studied in which melt spun Nd2.7Fe14B1.4 ribbons are PVD coated with Dy-Fe eutectic composition and then thermally treated. The resulting microstructure from the reaction between Dy-Fe eutectic coating and Nd2.7Fe14B1.4 ribbon is interpreted as support for a proposed dissolution/reprecipitation process between solid and liquid phases. The estimate the diffusion coefficient and the effective diffusion length of Dy sources in Nd2.7Fe14B1.4 layered pellets and melt spun ribbons were obtained from the calculation of Fick's second law combined with EDS results from the experiment. The results indicate that the effective diffusion coefficient of Dy in the layered pellets is higher than the diffusion in ribbons due to its higher porosity than ribbons.

DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Tail gas catalyzed N2O decomposition over Fe-beta zeolite. On the promoting role of framework connected AlO6 sites in the vicinity of Fe by controlled dealumination during exchange

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.