Reflexo dos gastos em P&D e inovação no valor de mercado das empresas químicas brasileiras

O objetivo desta dissertação é estudar a relevância dos gastos em P&D e Inovação no valor de mercado das empresas da indústria química brasileira. Este foi um tema de grande debate na reestruturação da indústria petroquímica e que resultou na criação da Braskem, a primeira petroquímica integrada brasileira. As justificativas para a referida integração vertical foram a maior capacidade para investimentos em P&D e o aumento do valor das empresas para poderem competir conforme os moldes internacionais. Por outro lado, economistas debatiam sobre o poder de monopólio da nova empresa e, consequentemente, o possível aumento de preços para o consumidor final. Desta forma, foram analisados nesse estudo os dados da indústria química brasileira de 1996 a 2008, obtidos no Anuário da Indústria Química Brasileira. Os modelos foram estimados utilizando estimadores de efeito fixos e aleatórios para um painel de dados não balanceado. A estimação por efeitos fixos foi escolhida, tanto para a estimação do modelo aditivo,quanto para o modelo multiplicativo. Acredita-se que o modelo multiplicativo, além de mais geral, seja o mais adequado para a modelagem de interesse, uma vez que ele trata as diferenças entre o porte das empresas consideradas por meio da linearização, e conseqüente suavização, do modelo. A elasticidade estimada dos gastos em P&D e inovação, com relação aos valores de mercado das empresas, indicou relacionamento positivo entre estes gastos e o aumento de valor das empresas. O coeficiente de 0,26 indica que um aumento de 1% nos gastos com P&D geram, em média, um aumento de 0,26% no valor de mercado destas empresas.

Modelos de gestão da inovação: um estudo de casos em empresas brasileiras do setor petroquímico

A inovação consiste em desafio premente para inúmeras organizações, de diferentes portes e missões. Dada sua relevância para as organizações públicas e privadas, de portes variados, assim como para as economias locais, regionais, nacionais e internacionais, a gestão da inovação constitui o cerne deste estudo de casos múltiplos. A gestão da inovação e seu alinhamento com a estratégia organizacional pode representar um diferencial competitivo significativo. Através de uma visão sistêmica sobre a gestão da inovação, é possível que as organizações gerem benefícios e externalidades que poderão atender a diversos atores envolvidos e públicos interessados no processo, tais como colaboradores, parceiros de negócios, fornecedores, usuários, clientes e agências do governo. A partir desta perspectiva, a estratégia de inovação é considerada uma abordagem central no que diz respeito à estratégia empresarial. Nossa intenção na realização desta pesquisa é compreender a complexidade e o valor de processos de inovação em organizações e seus efeitos enquanto consequências de estratégias deliberadas e emergentes. Esta pesquisa propõe um modelo referencial a ser utilizado pelos gestores para o mapeamento de processos de variados graus de complexidade, com vistas a prestar suporte na gestão da inovação de produtos, processos e administrativa, de forma estruturada, com especial ênfase ao modelo do funil de inovação e sua interface com tecnologias de informação, assim como em processos organizacionais e interorganizacionais, que podem contemplar parcerias externas em inovação aberta. Foram desenvolvidos três estudos de caso, os quais formam a base deste modelo referencial. Todos os casos abrangem empresas do setor petroquímico brasileiro, sendo um caso de empresa de grande porte, a Braskem S.A., e dois casos de empresas de pequeno porte, respectivamente a Hausthene Poliuretanos Ltda. e a Prorevest Revestimentos de Poliuretanos e Peças Especiais Ltda. O modelo referencial proposto busca identificar as condições necessárias – os determinantes da inovação – que possibilitam a gestão da inovação em produtos, processos e em gestão, e seus possíveis resultados.

Avaliação da eficiência de pratos valvulados com downcomer e pratos dualflow em colunas de destilação industriais

O principal objetivo deste trabalho é estabelecer caminhos apropriados para a estimativa da eficiência de pratos valvulados com downcomer e pratos dualflow em colunas de destilação industriais. O conhecimento da eficiência tem importância fundamental no projeto e na avaliação do desempenho de colunas de destilação. Pesquisando a literatura, pôde ser identificada uma árvore de alternativas para compor o modelo de eficiência de prato, dependendo dos modelos de transferência de massa, do modelo de distribuição das vazões de líquido e vapor sobre o prato, do modelo de arraste de líquido, do modelo de equilíbrio da mistura multi-componente, dos modelos de propriedades físicas, do modelo da altura da espuma sobre o prato e da definição de eficiência. Neste trabalho, diferentes métodos para a predição da eficiência em pratos valvulados e pratos dualflow foram compostos e comparados contra dados de três colunas de destilação industriais sob diferentes condições operacionais. Os modelos foram inseridos no simulador Aspen Plus 12.1, em linguagem Fortran, junto com dados geométricos dos pratos, propriedades dos fluidos e dados de operação das colunas de destilação industriais. Para cada coluna foi escolhido o melhor pacote termodinâmico pela verificação dos perfis de temperatura e composições de topo e fundo obtidos via simulação contra os valores reais correspondentes das colunas de destilação industriais. Foi feita uma modificação no parâmetro da fração de furos que estão em jetting no modelo hidráulico da dispersão acima do prato de Garcia (1999). Essa modificação produziu resultados melhores na predição da fração de furos em jetting e eficiência dos pratos dualflow e resultados similares aos de Garcia (1999) para a eficiência dos pratos valvulados.

Estimação e compensação de não linearidades inerentes aos atuadores dos processos industriais

The oscillations presents in control loops can cause damages in petrochemical industry. Canceling, or even preventing such oscillations, would save up to large amount of dollars. Studies have identified that one of the causes of these oscillations are the nonlinearities present on industrial process actuators. This study has the objective to develop a methodology for removal of the harmful effects of nonlinearities. Will be proposed an parameter estimation method to Hammerstein model, whose nonlinearity is represented by dead-zone or backlash. The estimated parameters will be used to construct inverse models of compensation. A simulated level system was used as a test platform. The valve that controls inflow has a nonlinearity. Results and describing function analysis show an improvement on system response

Controle preditivo neural aplicado à processos petroquímicos

A pesquisa tem como objetivo desenvolver uma estrutura de controle preditivo neural, com o intuito de controlar um processo de pH, caracterizado por ser um sistema SISO (Single Input - Single Output). O controle de pH é um processo de grande importância na indústria petroquímica, onde se deseja manter constante o nível de acidez de um produto ou neutralizar o afluente de uma planta de tratamento de fluidos. O processo de controle de pH exige robustez do sistema de controle, pois este processo pode ter ganho estático e dinâmica nãolineares. O controlador preditivo neural envolve duas outras teorias para o seu desenvolvimento, a primeira referente ao controle preditivo e a outra a redes neurais artificiais (RNA s). Este controlador pode ser dividido em dois blocos, um responsável pela identificação e outro pelo o cálculo do sinal de controle. Para realizar a identificação neural é utilizada uma RNA com arquitetura feedforward multicamadas com aprendizagem baseada na metodologia da Propagação Retroativa do Erro (Error Back Propagation). A partir de dados de entrada e saída da planta é iniciado o treinamento offline da rede. Dessa forma, os pesos sinápticos são ajustados e a rede está apta para representar o sistema com a máxima precisão possível. O modelo neural gerado é usado para predizer as saídas futuras do sistema, com isso o otimizador calcula uma série de ações de controle, através da minimização de uma função objetivo quadrática, fazendo com que a saída do processo siga um sinal de referência desejado. Foram desenvolvidos dois aplicativos, ambos na plataforma Builder C++, o primeiro realiza a identificação, via redes neurais e o segundo é responsável pelo controle do processo. As ferramentas aqui implementadas e aplicadas são genéricas, ambas permitem a aplicação da estrutura de controle a qualquer novo processo

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Métricas de desempenho para sistema de alarmes de processos industriais

The evolution of automation in recent years made possible the continuous monitoring of the processes of industrial plants. With this advance, the amount of information that automation systems are subjected to increased significantly. The alarms generated by the monitoring equipment are a major contributor to this increase, and the equipments are usually deployed in industrial plants without a formal methodology, which entails an increase in the number of alarms generated, thus overloading the alarm system and therefore the operators of such plants. In this context, the works of alarm management comes up with the objective of defining a formal methodology for installation of new equipment and detect problems in existing settings. This thesis aims to propose a set of metrics for the evaluation of alarm systems already deployed, so that you can identify the health of this system by analyzing the proposed indices and comparing them with parameters defined in the technical norms of alarm management. In addition, the metrics will track the work of alarm management, verifying if it is improving the quality of the alarm system. To validate the proposed metrics, data from actual process plants of the petrochemical industry were used

Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Estudo da remoção de Ba2+, Ni2+, Cd2+, Cu3+, Cr3+, Sr2+, Zn2+ por eletrocoagulação em água associada à produção de petróleo

Among the waste generated in the petrochemical industry water associated with oil production is the most important. It is considered one of the great challenges due to the presence of considered toxic chemicals present in this composition. The presence of these substances difficult to reuse the water associated with the enhanced recovery processes, so that prior to their reuse or disposal, treatment is necessary. This paper aimed to study the removal efficiency of chemical species: Ba2+, Ni2+, Cd2+, Cu2+, Cr3+, Sr2+ and Zn2+, present in the composition of the water associated with oil production by electrocoagulation. The evaluation of removal of these chemical species was performed by laboratory tests using electrochemical batch reactors and continuous flow. Initial tests were performed with electrocoagulation of synthetic wastewater in batch reactor using iron electrode. Results of removal of Zn2+ and Ni2+ were 78 % and 59 % respectively. While the percentage of removed Ba2+ was 19 % by 30 minutes of treatment and by applying current of 1.10 A. The tests were performed on effluent batch reactor applying the electrochemical technique with stainless steel electrodes 304, the objective was to remove part of the dispersed oil and also of organic compounds in the effluent. Under the experimental conditions used, the maximum result was obtained TOG was 60 % and TOC was approximately 50 % compared to the initial concentration. In the experiments carried out in continuous reactor, with effluent semisynthetic, have been used electrodes of iron and aluminum and the results were 100 % removal of Cd2+, Cu2+, Cr3+ and Zn2+ and 77 % of Sr2+. These percentages were only attainable through the use of the iron electrode. However, when the electrode was replaced by aluminum, there was a reduction in the percentage of removal to 65 %, using the same flow rate and current. Therefore according to the results obtained using the iron electrode was more effective in removing these metals and the conditions of lower current and lower flow rate was satisfactory, as observed in the experimental design adopted

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Síntese, caracterização e avaliação catalítica do silicoaluminofosfato SAPO-11 sulfatado

Due to environmental restrictions around the world, clean catalytic technology are of fundamental importance in the petrochemical industry and refineries. Creating the face of this a great interest in replacing the liquid acids for solid acids, so as molecular sieves have been extensively studied in reactions involving the acid catalysis to produce chemical substances with a high potential of quality. Being the activity of the catalysts involved in the reaction attributed to the acid character of them involved for the Lewis and Brönsted acid sites. Based on this context, this study aimed to prepare catalysts acids using a molecular sieve silicoalumino-phosphate (SAPO-11) synthesized in hidrotermical conditions and sulphated with sulphuric acid at different concentrations, using to it the method of controlled impregnating. The samples resulting from this process were characterized by x-ray difratometry (DRX), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TG-DTG) and determination of total acidity (by n-butilamin adsorption). The results show that the synthesis method used was efficient in the formation of AEL structure of SAPO-11 and when being incorporated the sulfate groups in this structure the acidity of the material was increased, pointing out that to very high concentrations of acid there is a trend of decrease the main peaks that form the structure. Finally they were tested catalytictly by the reaction model of conversion of m-xylene which showed favorable results of conversion for this catalyst, showing to be more selective of cracking products than isomerization, as expected, in order that for the o-xylene selectivity there was no positive change when to sulfate a sample of SAPO-11, while for light gases of C1-C4 this selectivity was remarkably observed

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products