A emissão de poluentes em megacidades e áreas industriais pode ter fortes impactos no clima e na saúde. Nos últimos anos tem sido crescente a preocupação com emissões atmosféricas contendo partículas nanométricas, cuja presença, juntamente com compostos orgânicos voláteis, óxidos de nitrogênio e outros, pode resultar na formação de uma série de substâncias gasosas poluentes e na formação de aerossóis. Medições mais precisas da concentração e distribuição de tamanho de fuligem são importantes, não só do ponto de vista ambiental, mas também para a saúde humana. O objetivo deste trabalho foi determinar a distribuição de tamanho de partículas na chaminé de uma refinaria em Cubatão. Para isso foi utilizada uma abordagem baseada nos métodos de inversão, tradicionalmente usados para calcular parâmetros de aerossóis atmosféricos, ao contexto dos aerossóis de tochas industriais. Os resultados se mostraram consistentes com a literatura científica, sendo possível determinar alguns parâmetros da distribuição do tamanho de partículas provenientes da chama de uma tocha industrial utilizando um sistema lidar de três comprimentos de onda com um nível de discrepância aceitável. Um estudo do expoente de Angström foi realizado com o objetivo de validar o algoritmo de inversão desenvolvido neste trabalho. Os resultados deste estudo mostraram que os dados experimentais corroboram com as curvas teóricas e, portanto, o algoritmo pode ser utilizado como ferramenta para a medição de emissões atmosféricas provenientes de tochas industriais. O desenvolvimento deste projeto representará um passo importante, não somente do ponto de vista tecnológico, mas principalmente como recurso para tratar de problemas de emissões que futuramente poderão surgir, dentre as medidas voltadas ao controle de mudanças climáticas. / The emission of pollutants in megacities and industrial areas can have strong impacts on climate and health. In recent years there has been a growing concern about air emissions containing nanometric particles whose presence, together with volatile organic compounds, nitrogen oxides, and others, can result in the formation of a series of gaseous pollutants and aerosol. More accurate measurements of the concentration and size distribution of soot are important not only from an environmental point of view, but also to human health. The objective of this study was to determine the particle size distribution in the chimney of a refinery in Cubatao. For this it used an approach based on inversion methods traditionally used to calculate parameters of atmospheric aerosols, the context of aerosols of industrial torches. The results were consistent with the scientific literature, it is possible to determine some parameters of size distribution of particles from an industrial torch flame using a system handling three wavelengths with an acceptable level of mismatch. A study by the Angstrom exponent was carried out in order to validate the inversion algorithm developed in this work. The results of this study showed that corroborate experimental data with the theoretical curves and thus the algorithm can be used as a tool for measuring atmospheric emissions from industrial torches. The development of this project will be an important step, not only from a technological point of view, but rather as a resource to address emission problems that may arise in the future, among the measures aimed at controlling climate change.

A emissão de poluentes em megacidades e áreas industriais pode ter fortes impactos no clima e na saúde. Nos últimos anos tem sido crescente a preocupação com emissões atmosféricas contendo partículas nanométricas, cuja presença, juntamente com compostos orgânicos voláteis, óxidos de nitrogênio e outros, pode resultar na formação de uma série de substâncias gasosas poluentes e na formação de aerossóis. Medições mais precisas da concentração e distribuição de tamanho de fuligem são importantes, não só do ponto de vista ambiental, mas também para a saúde humana. O objetivo deste trabalho foi determinar a distribuição de tamanho de partículas na chaminé de uma refinaria em Cubatão. Para isso foi utilizada uma abordagem baseada nos métodos de inversão, tradicionalmente usados para calcular parâmetros de aerossóis atmosféricos, ao contexto dos aerossóis de tochas industriais. Os resultados se mostraram consistentes com a literatura científica, sendo possível determinar alguns parâmetros da distribuição do tamanho de partículas provenientes da chama de uma tocha industrial utilizando um sistema lidar de três comprimentos de onda com um nível de discrepância aceitável. Um estudo do expoente de Angström foi realizado com o objetivo de validar o algoritmo de inversão desenvolvido neste trabalho. Os resultados deste estudo mostraram que os dados experimentais corroboram com as curvas teóricas e, portanto, o algoritmo pode ser utilizado como ferramenta para a medição de emissões atmosféricas provenientes de tochas industriais. O desenvolvimento deste projeto representará um passo importante, não somente do ponto de vista tecnológico, mas principalmente como recurso para tratar de problemas de emissões que futuramente poderão surgir, dentre as medidas voltadas ao controle de mudanças climáticas. / The emission of pollutants in megacities and industrial areas can have strong impacts on climate and health. In recent years there has been a growing concern about air emissions containing nanometric particles whose presence, together with volatile organic compounds, nitrogen oxides, and others, can result in the formation of a series of gaseous pollutants and aerosol. More accurate measurements of the concentration and size distribution of soot are important not only from an environmental point of view, but also to human health. The objective of this study was to determine the particle size distribution in the chimney of a refinery in Cubatao. For this it used an approach based on inversion methods traditionally used to calculate parameters of atmospheric aerosols, the context of aerosols of industrial torches. The results were consistent with the scientific literature, it is possible to determine some parameters of size distribution of particles from an industrial torch flame using a system handling three wavelengths with an acceptable level of mismatch. A study by the Angstrom exponent was carried out in order to validate the inversion algorithm developed in this work. The results of this study showed that corroborate experimental data with the theoretical curves and thus the algorithm can be used as a tool for measuring atmospheric emissions from industrial torches. The development of this project will be an important step, not only from a technological point of view, but rather as a resource to address emission problems that may arise in the future, among the measures aimed at controlling climate change.

A kinetic study of the pyrolysis of municipal solid waste (MSW) was carried out bythermogravimetric analysis (TGA). Different runs were performed at heating rates of 5, 10and 150C/min. The effect of the N2, CO2 and O2 gas with different combination in theprocess was also evaluated. The results show that the most weight loss was obtained whenthe MSW was treated at a temperature interval of (20-750)0C which led to a weigh loss of95%. The kinetic study of the pyrolysis process showed also the gas mixture used in theprocess effect also the activation energy of the process and the presence of the CO2 in theincreased the activation energy (Ea) to 56 kJ/mol. Higher concentration of CO2 in the processlead to increase in the activation energy which is not optimal for the reaction. The treated andthe untreated samples were incubated and the biological activity was observed. The resultsshow that the pretreated samples did not have any biological activity. From these results itcould be concluded that the thermal pretreatment could be an alternative way for of waste forlong period of time, which could have significant impact in i.e. for transportation anddurability during storage. / Program: Högskoleingenjörsutbildning i kemiteknik

nÃo hà / A dissertaÃÃo investiga o processo de tomadas de decisÃes nos Governos do Estado do Cearà que se seguiram à derrocada dos âcoronÃisâ, a tradicional elite do poder que governara durante o regime militar. As decisÃes de construir uma refinaria (Refinaria do Nordeste â Renor) e um porto localizado em um distrito industrial (Complexo Industrial e PortuÃrio do PecÃm â CIPP) foram utilizadas como estudos de caso para interpretar o processo. O CIPP à uma obra cujos recursos sÃo em sua maior parte de responsabilidade da UniÃo e a Renor, nele localizada, serà construÃda com capital privado. Apesar disso, em ambos os empreendimentos tem sido determinante a participaÃÃo do Governo Estadual, ocorrendo durante o segundo mandato do governador Tasso Jereissati (1995-98) a resoluÃÃo de encaminhar a construÃÃo dos dois empreendimentos. A revisÃo de literatura sobre processo decisÃrio revelou uma polarizaÃÃo entre uma visÃo pluralista do poder, defensora da idÃia de encontrarem-se os interesses dos eleitores representados nas decisÃes polÃticas dos governantes, e uma concepÃÃo elitista, para a qual uma elite dominante concentra o poder de decisÃo. A pesquisa traÃou um perfil da estrutura de poder no Governo do Estado do Cearà e investigou a origem das idÃias que levaram à construÃÃo do CIPP e à busca por investimentos privados para construÃÃo de uma refinaria. Procurou-se identificar mudanÃas nas idÃias sobre desenvolvimento que guiaram o processo decisÃrio. O Governo do Cearà espera que a infra-estrutura do CIPP, juntamente com a refinaria e uma siderÃrgica, tambÃm em construÃÃo, sejam um atrativo para a instalaÃÃo de pÃlos petroquÃmico e metal-mecÃnico, ampliando e diversificando a pauta de exportaÃÃes e aumentando a participaÃÃo do Cearà no PIB brasileiro. Os instrumentos de coleta de dados mais importantes foram entrevistas com os atores sociais envolvidos no processo decisÃrio e a leitura de diversas entrevistas jà publicadas, documentos oficiais e artigos de jornais.

As refinarias de petróleo utilizam grandes quantidades de água em seus processos e por isso são impelidas a desenvolver fortes programas de redução de seu consumo. O objetivo do presente estudo é a aplicação de metodologia de otimização em problemas de alocação ótima e reuso de água em refinaria de petróleo. Diferentemente dos enfoques tradicionais que buscam tratar os efluentes gerados para atender às legislações ambientais ou para algum tipo de reuso na planta, a metodologia utilizada avalia os processos que usam água, questionando as causas da geração do efluente. Essa abordagem envolve o levantamento de dados industriais, análise dos processos de produção, identificação de oportunidades para aplicar as estratégias de otimização da alocação de água: racionalização, reuso e/ou reciclagem do efluente e, em seguida, a otimização da rede de água. Visando obter uma rede de água que seja aplicável na indústria, desenvolveu-se um procedimento específico baseado em regras heurísticas que representam as restrições reais dos processos. Através deste procedimento, o consumo de água fresca atingido é próximo do valor ótimo encontrado na literatura. As redes de água geradas são simples, com poucas interconexões e, consequentemente, os investimentos necessários para implementação são menores. / Oil refineries consume a large amount of water in their processes and because of that they are urged to develop strong programs to reduce their water consumption. The aim of this study is to apply an water optimization methodology in an oil refinery. Unlike traditional approaches that only search for treating the effluents in order to meet environmental legislation or to reuse in the plant, this methodology evaluates the processes that use water, questioning the causes of the wastewater generation. This approach involves the industrial data collection, analysis of production processes, identification of opportunities to optimize water use: rationalization, reuse and/or recycling of the effluent and, lastly, the water network optimization. Looking for a water network that is applicable in the industry, in this study it was also developed a specific optimization procedure based on heuristic rules representing the constraints of the actual processes. Through this procedure, freshwater consumption was found to be close to that of the theories found in the literature. The water networks generated are simple, with few interconnections and, consequently, the investments required to implement them are small.

The biodesulfurization 4S-pathway is a promising complementary enzymatic approach to remove sulfur from recalcitrant thiophenic derivatives in petroleum products that remain from conventional hydrodesulfurization method without diminishing the calorific value of oil. The final step of this pathway involves the carbon-sulfur bond cleavage from HBPS, and the production of the final products 2-hydroxybiphenyl (HBP) and sulfite, has been recognized as the rate-limiting step, partially as a result of product inhibition. However, the mechanisms and factors responsible for product inhibition in the last step have not been fully understood. In this work, we proposed a computational investigation using molecular dynamic simulations and free energy calculations on 2’-hydroxybiphenyl-2-sulfinate (HBPS) desulfinase (DszB) with different bound ligands as well as different solvent conditions to develop a fundamental understanding of the molecular-level mechanism responsible for product inhibition. Based on available crystal structures of DszB and biochemical characterization, we proposed a “gate” area close to substrate binding site of DszB is responsible for ligand egress and plays a role in product inhibition. We have conducted biphasic molecular dynamic simulations to evaluate the proposed gate area functionality. Non-bonded interaction energy analysis shows that hydrophobic residues around the gate area produce van der Waals interactions inhibiting translocation through the gate channel, and therefore, the molecules are easily trapped inside the binding site. Umbrella sampling molecular dynamics was performed to obtain the energy penalty associated with gate conformational change from open to close, which was 2.4 kcal/mol independent of solvent conditions as well as bound ligands. Free energy perturbation calculations were conducted for a group of six selected molecules bound to DszB. The selections were based on functional group representation and to calculate binding free energies that were directly comparable to experimental inhibition constants, KI. Our work provides a fundamental molecular-level analysis on product inhibition for the biodesulfurization 4S-pathway.

The objective of the work reported in this thesis was to design and implement an ecological effects environmental monitoring program which would: 1) Collect baseline biological information on sessile epibiotic fouling communities from an area adjacent to a petroleum refinery located on Corio Bay, Victoria, to allow comparison with results of future monitoring for the assessment of long term temporal water quality trends. 2) Detect and — if possible - estimate the magnitude of any influence on epibiotic fouling communities within the Corio Bay marine ecosystem attributable to operations at the Shell Petroleum Refinery. 3) Investigate the extent of thermal stratification and rate of dispersal of the petroleum refinery main cooling-water outfall plume (discharging up to 350,000 tonnes of warmed seawater per day), and its effect on epibiotic communities within the EPA-defined mixing zone. A major component of the work undertaken was the design and development of artificial-substrate biological sampling stations suitable for use under the conditions prevailing in Corio Bay, and the development of appropriate quantitative underwater photographic sampling techniques to fulfil the experimental criteria outlined above. Experimental and other constraints imposed on the design of the stations precluded the simple suspension of frames from jetties or pylons, a technique widely used in previous work of this type. Artificial substrate panels were deployed along three radial transects centred within and extending beyond the petroleum refinery main cooling-water mixing zone. Identical substrate panels were deployed at a number of control sites located throughout Corio Bay, each chosen for differences in their degree of exposure to such factors as water movement, depth, shipping traffic and/or comparable industrial activity. The rate of colonisation (space utilisation) and the development of epibiotic fouling communities on artificial substrate panels was monitored over two twelve-month sampling periods using quantitative underwater photographic sampling techniques. Sampling was conducted at 4-8 week intervals with the rate of panel colonisation and community structure determined via coverage measurements. Various species of marine algae, polychaete tubeworms, hydroids, barnacles, simple and colonial ascidians, sponges, bivalve molluscs and encrusting bryozoans were all detected growing on panels. Communities which established on panels within the cooling-water mixing-zone and those at control sites were compared using statistical procedures including agglomerative hierarchical cluster analysis. A photographic sample archive has been established to allow comparison with similar future studies.

<p>In this thesis, a computer program that in a simple way can calculate the performance of control loops at the refinery Preemraff Lysekil has been created. The computer program has been adapted to the environment at Preemraff Lysekil. Theories for evaluation has been studied in aspect of reliability and of automatic implementation. The evaluation has been carried out from data collected directly from control loops at the refinery and from simulated control loops with implemented errors. </p><p>Among the studied methods are Harris index and Stattin´s oscillation index. According to the literature the Harris index is the most used for measure of control performance, but the results show that it does not work as a single measure at Preemraff Lysekil. However Stattin´s oscillation index works well and can be used for detection of oscillations. Statistic measures like variance, IAE, ISE and a method based on histogram are also studied. All the statistical measures are simple to implement and are rather accurate. Several tests on control loops has been carried out and it has been shown that it ís enough to use the method based on histograms and Stattins oscillation index to get a good picture of the performace of the control loops at Preemraff Lysekil. </p><p>The work has resulted in a MATLAB tool that evaluates the control loops and can be run at any time. The tool first calculates Stattin´s oscillation index. The loops that are oscillating are marked. In the next step, the method based on histograms is used and a list with the worst performing loops at the top is created.</p>

Mitigation of climate change and energy security are major driving forces for increased biomass utilization. The pulp and paper industry consumes a large proportion of the biomass worldwide including bark, wood residues, and black liquor. Due to the fact that modern mills have established infrastructure for handling and processing biomass, it is possible to lay foundation for future gasification based bio-refineries to poly-produce electricity, chemicals or bio-fuels together with pulp and paper products. There is a potential to export electricity or bio-fuels by improving energy systems of existing chemical pulp mills by integrating gasification technology. The present study investigates bio-fuel alternatives from the dry black liquor gasification (BLG) system with direct causticization and direct methane production from the catalytic hydrothermal gasification (CHG) system. The studied systems are compared with bio-fuel alternatives from the Chemrec BLG system and the improvements in the energy systems of the pulp mill are analyzed. The results are used to identify the efficient route based on system performance indicators e.g. material and energy balances to compare BLG systems and the conventional recovery boiler system, potential biofuel production together with biomass to biofuel conversion efficiency, energy ratios, potential CO2 mitigation combining on-site CO2 reduction using CO2 capture and potential CO2 offsets from biofuel use, and potential motor fuel replacement. The results showed that the dry BLG system for synthetic natural gas (SNG) production offers better integration opportunities with the chemical pulp mill in terms of overall material and energy balances. The biofuel production and conversion efficiency are higher in the CHG system than other studied configurations but at a cost of larger biomass import. The dry BLG system for SNG production achieved high biomass to biofuel efficiency and considerable biofuel production. The energy ratio is significant in the dry BLG (SNG) system with less biomass demand and considerable net steam production in the BLG island. The elimination of the lime kiln in the dry BLG systems resulted in reduced consequences of incremental biomass import and associated CO2 emissions. Hydrogen production in the dry BLG system showed the highest combined CO2 mitigation potential i.e. on-site CO2 capture potential and CO2 offset from biofuel replacing fossil fuel. The results also showed that the motor fuel replacement potential with SNG as compressed natural gas (CNG) replacing gasoline in the transport sector is significantly high in countries with large pulp industry. / QC 20120528

Naphthenic acids (NAs) are carboxylic acids found in crude oil and petroleum products. The objectives of the research presented here were to: a) assess the occurrence and fate of NAs in crude oil and refinery wastewater streams; b) evaluate the biotransformation potential and inhibitory effects of NAs under nitrifying, denitrifying and methanogenic/fermentative conditions; c) investigate the factors affecting NA biotransformation under aerobic conditions and the microbes involved; and d) assess the toxicity of individual model NAs using quantitative structure-activity relationships (QSAR) and examine the effect of structure on NA biotransformation potential. NAs are ubiquitous in refinery wastewater streams and the desalter brine was found to be the main source of NAs in refinery wastewater. A commercial NA mixture was not biodegraded under nitrate-reducing or methanogenic/fermentative conditions. NAs were degraded under aerobic conditions by an NA-enriched culture; however, a residual fraction was not degraded under all conditions studied. The results indicated that NAs are not inherently recalcitrant and the residual fraction was due to the individual NA concentrations being below the minimum substrate concentrations at which they are no longer degraded. A fraction of the NA mixture was completely mineralized to carbon dioxide, with the remaining portion biotransformed to more oxidized intermediates. Overall, the results indicated that NAs were degraded under aerobic conditions; however, biological treatment of NA-bearing wastewater will not completely remove NA concentrations and thus, biological treatment must be combined with physical/chemical treatment to achieve complete NA removal.