This paper presents a comprehensive interface and electrochemical phenomena review of different anodes for SOFC. In this way, it was possible to select some mixed electronic and ionic conductor materials alternatives to the conventional anode, Ni-YSZ conductor. New materials must present a satisfactory electronic and ionic conductivity at intermediate temperatures, be able to operate under different types of hydrocarbon fuels without deactivation, present stability under redox cycles and thermal expansion compatible with the other materials. Among all new materials, Sr0.86Y0.08TiO3, a Y-doped strontium titanate (YST), presented the highest measured conductivity, of 82 S cm-1 at 800 °C. In addition, this material showed excellent stability time and coefficient of thermal expansion compatible with materials used as cathode, strontium-doped lanthanum manganite and electrolyte, yttria stabilized zirconia. SrTiO3 (ST) compounds synthesized by solid-state reaction method, calcined, and sintered to obtain undoped (ST), 4% (YST04) and 8% (YST08) of Y-dopant and as a heterojunction with yttria-stabilized zirconia (YST08/YSZ). It was observed that calcination under Ar/5%H2 atmosphere has increased the dopant maximum concentration in the SrTiO3 cubic crystal structure when compared to inert atmosphere. When the Y solubility limit was exceeded, a pyrochlore phase Y2Ti2O7 was formed on the intergranular region due to the deficiency of oxygen vacancies, especially in the presence of inert atmosphere.

Abstract Model Predictive Control, MPC and NMPC, and real-time optimization, RTO and D-RTO, are known to help plant operability through the mitigation of impacts caused by external disturbances. However, the usage of these tools in industry requires overcoming some challenges, for instance: accurate models of the process, particularly in regard to nonlinearities; suitable computational time for obtaining the solution of large-scale problems and model mismatch between the RTO or D-RTO and NMPC. In this paper, we present a methodology to obtain analytical model predictions based on a Hammerstein structure to represent the process nonlinearities, reducing the computational effort in real-time applications. Unlike most common approaches that transform NMPC internal models, described by differential-algebraic equations (DAE), into an approximate system of nonlinear algebraic (NLA) equations using, for instance, orthogonal collocation, in the proposed approach, the obtained NLA is an exact description of the original DAEs system. The proposed algorithm was applied to a non-isothermal CSTR (continuous stirred tank reactor) integrated with an optimization layer. The results show that the proposed structure presented a significant reduction in computational time without performance loss, when compared with the NMPC using a rigorous model. Moreover, the proposed strategy demonstrated good performance in tracking the targets sent by the optimization layer, without model mismatches between layers.

Abstract Several methods for computing the Gauss-Christoffel quadrature used for the adaptive characterization of continuous mixtures were compared as to their efficiency and robustness. Two mixtures with molar fraction distribution given by truncated gamma distributions were used. We analyzed the Product-Difference, the Golub-Welsch, the Long Quotient-Modified Difference and the Chebyshev algorithms using regular and generalized moments, when applicable. The robustness and computational efficiency of changes in the distribution variable and in the orthogonal polynomial family used to calculate the generalized moments were analyzed. The methods using generalized moments proved to be more robust than those that use regular moments. Although they are computationally more expensive, this cost increase is just around 20% for the Chebyshev algorithm. The resulting adaptive characterization was employed to solve the adiabatic vapor-liquid flash of these mixtures. The results showed that eight pseudocomponents were able to well represent the properties of the equilibrium streams, showing the high accuracy of this method.

ABSTRACT There is a continual desire around the world to reduce the sulphur content of diesel fuel to ultra-low levels (below 10 ppm) due to environmental concerns and the intention of improving air quality and lowering harmful exhaust emissions of diesel engines. In this work, a hydrodesulfurization unit fed with multiple diesel streams was addressed using a phenomenological mathematical model aiming to produce Ultra-Low Sulfur Diesel (ULSD). A three-phase model of a trickle-bed reactor was considered. A model-based predictive control strategy (MPC) was implemented with the objective of controlling the sulfur concentration at the exit of the reactor, manipulating the flow rates of the oils entering the system, the superficial velocity of the gas and the temperature of the load in the presence of disturbances in the concentration of organic sulfur compounds in the fed oils. It was observed that the control strategy reduced the contaminant content to the specification range of diesel S10.

O entendimento de como as propriedades reológicas afetam o comportamento dos polímeros nas operações de processamento, por meio de diferentes técnicas experimentais, é de fundamental importância para ser possível prever e avaliar a estrutura final destes materiais. Neste contexto, o objetivo deste trabalho é aplicar a técnica de birrefringência para diferenciar dois grades de poliestireno cristal. Foram realizados experimentos em um reômetro multipasse que permitiram a aquisição de imagens de birrefringência, que representam o campo de tensão do escoamento, e obteve-se a queda de pressão durante os experimentos. Ao se compararem os padrões de birrefringência dos dois poliestirenos foi possível distinguir os materiais e verificar que o escoamento da amostra de maior massa molar é mais complexo, com maior birrefringência e tensão mais elevada. Os resultados obtidos, além de contribuírem para a caracterização reológica, podem ser empregados no estudo comparativo de modelos constitutivos e desenvolvimento de códigos computacionais.

Polymers must go through processes that transform raw materials in a final product for consumption, and therefore it is crucial to understand how their rheological properties affect processability and final product quality. This study is aimed at applying the birefringence technique to differentiate two grades of general purpose polystyrene. Flow experiments were carried out using a multi-pass rheometer and flow-induced birefringence images and pressure profile were obtained. It was possible to distinguish between the different materials by examining their birefringence patterns. The flow of the higher molecular weight sample is more complex, with higher birefringence and tension. These data are important for the rheological characterization of the material and can be used in the validation of constitutive models in computational fluid dynamics.

The inadequacy of strategies used for the heterogeneization of metallocene catalysts is pointed out as one of the main causes of the lack of industrial employability of such polymerization catalysts. The main problems are the necessity of large quantity of MAO (cocatalyst) and the inability to control molecular mass distribution of the polymers. Based on this background, the main strategies for the heterogeneization of metallocenes are here reviewed. The advantages and disadvantages of each strategy are presented and discussed on theoretical and practical perspective. Considering the results reported on the different researches, outcomes of heterogeneization strategies are pointed out.

The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest.

É proposta neste trabalho uma nova metodologia para resolução das equações governantes de fluidos viscoelásticos, baseada no método dos volumes finitos, usando o arranjo co-localizado para as variáveis e malhas estruturadas. São utilizadas aproximações de alta ordem para os fluxos lineares e não-lineares médios nas interfaces dos volumes, e para os termos não-lineares que surgem da discretização das equações constitutivas. Nesta metodologia, os valores médios das variáveis nos volumes são usados durante todo o procedimento de resolução, e os valores pontuais são obtidos ao final, através da deconvolução dos valores médios. O sistema de equações discretizadas é resolvido de forma simultânea, pelo método de Newton. A metodologia é exemplificada para um problema clássico em mecânica de fluidos computacional, o escoamento stick-slip, usando como equação constitutiva o modelo de Oldroyd-B. As soluções obtidas apresentaram boa precisão, sendo livres de oscilações mesmo em regiões de grandes gradientes das variáveis.

In this work, a new methodology to solve the governing equations of viscoelastic fluid flows is proposed. This methodology is based on the finite-volume method with co-located arrangement of the variables, using high-order approximations for the linear and nonlinear average fluxes in the interfaces and for the nonlinear terms resulting from the discretization of the constitutive equations. In this methodology, the average values of the variable in the volumes are used during the resolution, and the point values are recovered in the post-processing step by deconvolution of the average values. The nonlinear equations, resulting from the discretization technique, are solved simultaneously, using the Newton's method. The solutions obtained are oscillation-free and accurate, as can be seen in the solution of the stick-slip flow, used as an illustrative example.