Em face ao aumento do preço de energia e combustíveis fósseis o conceito de biorrefinaria vem sendo foco de atenção das indústrias de celulose e papel. Esse conceito visa a obtenção de co-produtos a partir de um processo industrial pré-estabelecido sendo necessários alguns ajustes e investimentos. A possibilidade de recuperação do metanol contido no licor negro traz ao setor de celulose e papel o conceito de biorrefinaria florestal. O metanol celulósico contido no licor negro de fábricas de celulose e papel é o principal composto orgânico volátil responsável por mais de 90 % das emissões nessas fábricas. De forma semelhante aos compostos reduzidos de enxofre a formação do metanol ocorre durante a polpação alcalina em digestores, mas seu potencial para recuperação é desconhecido. Por isso, este trabalho teve como finalidade quantificar o metanol presente nos licores negros industriais provenientes de processo de polpação kraft convencional. Os licores negros industriais foram cedidos por fábricas brasileiras de celulose e papel. Para a quantificação desse álcool um método analítico foi otimizado e validado. Além disso, realizou-se o estudo de formação do metanol em licor negro durante a polpação alcalina para verificação dos parâmetros que determinam a concentração desse álcool no licor. O método otimizado mostrouse adequado à análise de metanol em licor negro e com potencial para amostras de condensados. A quantidade de metanol determinada em licor negro industrial mostrou-se passível de recuperação e sua formação durante a polpação foi influenciada pela intensidade da deslignificação do processo. / Given the rising price of energy and fossil fuels the concept of bio-refinery has been the focus of attention from the pulp and paper industries. This concept aims to achieve by-products from a pre-established industrial process which requires adjustments and investments. The recoverability of methanol contained in black liquor brings to the pulp and paper business sector the concept of forest bio-refinery. The cellulosic methanol contained in black liquor from pulp and paper mills is the main volatile organic compound responsible for more than 90% of emissions in these processing plants. Similarly to reduced sulfur compounds, the formation of methanol occurs during alkaline pulping in digesters but its potential for recovery is unknown. Therefore, this work aimed at quantifying the methanol present in industrial black liquor from conventional kraft pulping process. The black liquors were provided by Brazilian pulp and paper mills. To quantify this alcohol, an analytical method was optimized and validated. Moreover, we carried out a study on formation of methanol in black liquor during the alkaline pulping to specify the parameters to determine the concentration of this alcohol in the black liquor. The optimized method was adequate for the analysis of methanol in black liquor and showed potential to evaluate samples of condensates. The amount of methanol in black liquor has shown to be able to be recovered and its formation during pulping was influenced by the intensity of the delignification process.

A proposta desta pesquisa foi avaliar a utilização de um sistema combinado de filtro anaeróbio (FAN) com filtro aeróbio (FAE) submerso ligados em série, ambos usando espuma de poliuretano como meio suporte e com fluxo ascendente, como alternativa para remoção matéria orgânica (DQO) e compostos nitrogenados em efluentes de refinarias de petróleo, além da redução da toxicidade do efluente ao micro crustáceo Mysidopsis juniae. O experimento durou 324 dias e foi divido em duas etapas. Inicialmente, o sistema foi operado por 129 dias sem recirculação entre os filtros e nesta etapa houve acréscimo de 12% nas concentrações de amônia no FAN e remoção de 80% no FAE. Quando se usou bicarbonato de sódio para alcalinizar o afluente ao sistema para manter o pH no FAE na neutralidade e alcalinidade acima de 107 mg\'CA\'CO IND.3\'/L, pôde-se alcançar remoções de amônia próxima a 100%. Quanto à remoção de DQO, o filtro anaeróbio removeu 40% e o aeróbio 65%. Em síntese, na primeira etapa o sistema removeu 80% de DQO, 89% de amônia e 35% de nitrogênio. A segunda etapa durou 195 dias e houve recirculação do efluente do filtro aeróbio para o filtro anaeróbio. Nesta etapa, o pH foi mantido na neutralidade e a recirculação foi feita de duas formas. A primeira com recirculação direta entre os filtros a uma razão (R) de reciclo de 2,0 resultou em 43% de remoção de amônia no FAN e 97% no FAE e com esta forma de reciclo houve 62,6% de remoção de nitrogênio total no sistema. A segunda forma de recirculação foi direcionar parte do efluente do filtro aeróbio ao reservatório do afluente ao sistema com R igual a 1,0 resultando em produção de amônia no FAN em 10% e remoção no FAE de, aproximadamente, 100%. Independentemente da forma de recirculação a remoção de DQO foi de 67% e 56% no filtro anaeróbio e aeróbio, respectivamente. A remoção de nitratos no FAN foi de 93% e foi independente da forma de reciclo. Houve 42,5% de remoção de nitrogênio no sistema. Na segunda etapa obtiveram-se as melhores remoções de DQO, amônia e nitrogênio, porém, tanto o afluente quanto o efluente final apresentou CL50 de 0,83% ao microcrustáceo M. juniae, assim, ambas as formas do efluente estão em desacordo com a resolução CONAMA 357/05. Os gêneros Aeromonas, Serratia e Pseudomonas foram dominantes no FAE ao fim da pesquisa. / The purpose of this study was to evaluate the use of a combined system comprised of an anaerobic filter (ANF) and a submerged aerobic filter (SAF) connected in series, both using polyurethane foam as support media and operated in a upflow mode, as an alternative for removing organic matter (COD) and nitrogen compounds in effluents from oil refineries, as well as reducing effluent toxicity to micro crustacean Mysidopsis juniae. The experiment lasted 324 days and was divided into two stages. Initially, the system was operated for 129 days without recirculation between the filters. During this stage, there was an increase of 12% on the ammonia content in the ANF followed by a removal of 80% in the SAF. When sodium bicarbonate was used to alkalize the influent to maintain the pH in the ANF close to neutral and alkalinity above 107 mg\'CA\'CO IND.3\'/L, the removal efficiency of ammonia reached values close to 100%. Regarding to COD removal, the ANF removed 40% and SAF removed 65%. In summary, in the first stage of the research the system removed 80% of COD, 89% of ammonia and 35% of nitrogen. The second stage lasted 195 days and there was a recirculation line from the SAF to the ANF. In this step, the pH was maintained close to neutral and recirculation was done in two different ways. In the first, the recirculation flow was conducted from the SAF direct to the ANF at a rate of 2.0, which resulted in 43% removal of ammonia in the ANF and 97% in the SAF. Moreover, with this form of recycling 62.6% of the total nitrogen was removed from the system. The second way was to direct part of the effluent of the SAF to the tank that contained the influent of the ANF. In this case, the recirculation rate was 1.0, and resulted in a production of 10% of ammonia in the ANF and removal of approximately 100% in the SAF. Independently of the way used for recirculation, the COD removal efficiencies was 67% and 56% in ANF and SAF, respectively. The removal of nitrate in the ANF was 93% and was independent of the form of recycling. There was a 42.5% removal of nitrogen in the system. In the second stage occurred the best removals of COD, ammonia and nitrogen. However, both the affluent and the effluent had LC50 of 0.83% to microcrustacean M. juniae. Therfore, both forms of the effluent are in disagreement with the Brazilian law Resolução CONAMA 357/05. The Aeromonas, Serratia and Pseudomonas were dominant in the SAF at the end of research.

Through the Global Gas Flaring Reduction (GGFR) initiative a substantial amount of effort and international attention has been focused on the reduction of gas flaring since 2002 (Elvidge et al., 2009). Nigeria is rated as the second country in the world for gas flaring, after Russia. In an attempt to reduce and eliminate gas flaring the federal government of Nigeria has implemented a number of gas flaring reduction projects, but poor governmental regulatory policies have been mostly unsuccessful in phasing it out. This study examines the effects of pollution from gas flaring using multiple satellite based sensors (Landsat 5 TM and Landsat 7 ETM+) with a focus on vegetation health in the Niger Delta. Over 131 flaring sites in all 9 states (Abia, Akwa Ibom, Bayelsa, Cross Rivers, Delta, Edo, Imo, Ondo and Rivers) of the Niger Delta region have been identified, out of which 11 sites in Rivers State were examined using a case study approach. Land Surface Temperature data were derived using a novel procedure drawing in visible band information to mask out clouds and identify appropriate emissivity values for different land cover types. In 2503 out of 3001 Landsat subscenes analysed, Land Surface Temperature was elevated by at least 1 ℃ within 450 m of the flare. The results from fieldwork, carried out at the Eleme Refinery II Petroleum Company and Onne Flow Station, are compared to the Landsat 5 TM and Landsat 7 ETM+ data. Results indicate that Landsat data can detect gas flares and their associated pollution on vegetation health with acceptable accuracy for both Land Surface Temperature (range: 0.120 to 1.907 K) and Normalized Differential Vegetation Index (sd ± 0.004). Available environmental factors such as size of facility, height of stack, and time were considered. Finally, the assessment of the impact of pollution on a time series analysis (1984 to 2013) of vegetation health shows a decrease in NDVI annually within 120 m from the flare and that the spatio-temporal variability of NDVI for each site is influenced by local factors. This research demonstrated that only 5 % of the variability in δLST and only 12 % of the variability in δNDVI, with distance from the flare stack, could be accounted for by the available variables considered in this study. This suggests that other missing factors (the gas flaring volume and vegetation speciation) play a significant role in the variability in δLST and δNDVI respectively.

A cultura da cana-de-açúcar tem grande relevância na economia brasileira. A agroindústria sucroenergética origina uma grande quantidade de sub-produtos, como o bagaço e a palha. Vários estudos têm sido conduzidos no intuito de utilizálos como matéria-prima para a obtenção de diversos produtos, como o etanol celulósico, energia e diversos compostos de interesse industrial. As biomassas lignocelulósicas, como o bagaço da cana, são compostas principalmente de celulose, hemicelulose e lignina, sendo que a proporção de cada componente é dependente de diversos fatores. No caso da cana, há variedades que apresentam diferentes teores de fibra e, ao pensar em utilizar o material residual para geração de produtos de maior valor agregado, é muito importante conhecer a composição dessa fibra. A celulose é um polímero de glicose unido por ligações glicosídicas ?1-4, rígida e muito resistente à hidrólise. A hemicelulose é um polímero de baixa massa molecular composta por pentoses, hexoses, e/ou ácidos urônicos e mais susceptível à hidrólise quando comparada à celulose, uma vez que apresenta menor grau de polimerização. Por fim, a lignina é uma substância hidrofóbica, com estrutura tridimensional e amorfa, altamente ramificada e sintetizada a partir de três precursores, o álcool coniferílico, o álcool sinapílico e o álcool p-cumarílico. Vários compostos de interesse têm sido descobertos nas biomassas lignocelulósicas, neste contexto surgem as biorrefinarias, onde são obtidos produtos de elevado valor agregado e energia por rotas bioquímicas ou termoquímicas e de maneira sustentável. A classificação proposta no trabalho objetiva padronizar posteriores discussões relacionadas à classificação da fibra da cana e auxiliar os melhoristas na obtenção de novas variedades comerciais. O propósito do estudo foi avaliar a constituição da fibra de diversos genótipos de cana-de-açúcar com altos teores de fibra, propor um modelo para classificação da cana-de-açúcar de acordo com a composição dessa fibra e investigar o potencial dos genótipos analisados para uso em biorrefinarias na obtenção de produtos como etanol de segunda geração, polietileno verde e xilitol. Os resultados obtidos indicaram que o genótipo 196 foi o que apresentou a maior porcentagem de celulose (54,18 %) e o 192 foi o que apresentou a menor quantidade desse componente (26,47 %). Em relação à hemicelulose, o genótipo 77 foi o que apresentou o maior (25,97 %) teor e o 167 (16,71 %) o menor. Por fim, o genótipo 166 (27,13 %) foi o que apresentou maior quantia de lignina em sua composição e o 27 (17,7 %) a menor. Em relação à classificação, a maior parte dos genótipos analisados foram classificados como C2H4L4, ou seja, apresentam de 40 a 50 % de celulose, de 20 a 25 % de hemicelulose e de 20 a 25 % de lignina na composição da fibra. No contexto de biorrefinarias, o genótipo 196 mostrou maior potencial para obtenção do etanol celulósico e do polietileno verde, uma vez que apresentou maior teor de celulose na fibra. Para obtenção do xilitol, o genótipo 77 se mostrou mais promissor, pois demonstrou possuir maior quantidade de hemicelulose em sua composição. / Sugarcane farming plays an important role in the Brazilian agribusiness. The agro-industrial energy sector generates a number of by-products, such as bagasse and straw. Several studies were conducted to investigate the use of bagasse and straw as raw material for the production of various products, such as cellulosic ethanol, energy and several compounds for industrial use. The lignocelullosic biomasses, such as sugarcane bagasse, are composed primarily of cellulose, hemicellulose and lignin, and the content of each component depends on several factors. There are varieties of sugarcane plants with different fiber contents and to use the residual material to generate high value-added products, it is very important to know the fiber composition. Cellulose is a glucose polymer linked by glycosidic ?1- 4 bonds, rigid and very resistant to hydrolysis. Hemicellulose is a low-molecularweight polymer composed of pentoses, hexoses and/or uronic acids and more susceptible to hydrolysis when compared to cellulose, since it has a lower polymerization degree. Finally, lignin is a hydrophobic substance, with threedimensional and amorphous structure, highly branched and synthesized from three precursors, coniferyl alcohol, sinapyl alcohol and P-Coumaryl alcohol. Several compounds of interest have been discovered in lignocelullosic biomasses, and biorefineries are important to produce high value-added products and energy by biochemical or thermochemical routes in a sustainable way. The classification proposed in this study aims to standardize further discussions on the classification of the sugarcane fibers and helps plant breeders to obtain new commercial varieties. The purpose of this study was to evaluate the fiber composition of several sugarcane genotypes with high fiber contents; propose a model for sugarcane classification according to the fiber composition of the cultivar and investigate the potential of the genotypes analyzed to be used bio-refineries to obtain products such as the secondgeneration ethanol, green polyethylene and xylitol. There were investigated an access group of 207 genotypes. We used high-performance liquid chromatography to characterize cellulose and hemicellulose, and spectrophotometry to analyze the lignin content. The results showed that genotype 192 had the highest cellulose content (54,18 %) and 196 had the lowest (26,47 %). Genotype 77 showed the highest hemicellulose content (25,97 %) and 167 had the lowest (16,71%). Genotype 166 showed the highest lignin content (27,13 %) in its composition and 27 had the lowest (17,7 %). Most of the analyzed genotypes were classified as C2H4L4, that is, containing 40-50 % of cellulose, 20-25 % of hemicellulose and 20-25 % of lignin in the fiber composition. For the bio-refineries, genotype 192 showed the greatest potential for the production of cellulosic ethanol and green polyethylene due to its higher cellulose content in the fiber. To obtain xylitol, genotype 77 was more promising, because of the higher hemicellulose content in its composition.

Thesis (MSc)--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: Landfarming is a widely used method for the disposal of contaminants in the petrochemical industry. It involves ploughing the contaminants into the top soil layer allowing biological breakdown. A historically landfarmed site was identified at a South African petrol refinery. The refinery used to dispose so-called American Petroleum Institute (API) -sludge onto a landfarming site. API-sludge consisted of a mixture of oil and water soluble contaminants originating from a process of separating refinery waste from reusable water and oil. Landfarming on this site was discontinued after excessive quantities of sludge were ploughed into the soil over time and it became obvious that effective biodegradation could not take place. An environmental assessment had to be carried out to assess to what extent the soil has recovered from the contamination and after remediation was done over time. Bioassays together with chemical analyses were executed to determine the level of pollutants in the soil and to assess the integrated effects of their bioavailable fractions. The landfarming site of the refinery was divided into two sections namely, a more contaminated north-site and less contaminated south-site. Soil samples were collected from both sites as well as from an off-site (control site). The soils were analysed physically, chemically and used in the bioassays. Two additional control soils were also used, OECD-soil and LUFA2.2 soil. Chemical analysis of the site soils showed the presence of heavy metals and high levels of diesel range organic hydrocarbons. The north-site had higher levels of contaminants compared to the south-site. Three species of soil organisms were used in standardised tests: Eisenia andrei, Enchytraeus doerjesi and Folsomia candida were exposed to the respective soils to study their survival, growth, reproduction success and avoidance behavior. Exposures to both site-soils were not acutely toxic to any organisms. F. candida had a decrease in juvenile production in both north- and south-site soils (289.42 ± 58.62 and 253.33 ± 122.94 respectively) compared to the control soil (479.89 ± 30.42). E. doerjesi showed an increase in produced juveniles exposed to north- and south-site soil (339.75 ± 76.92 and 414.00 ± 17.78 ) compared to control soil (57 ± 34.39). E. andrei had similar cocoon production when exposed to south-site soil than in off-site soil (19.00 ± 5.3 and 18.5 ± 9.7 respectively) but significantly less in north-site soil (1.25 ± 0.7). Only E. doerjesi showed avoidance of north-site soil. To determine the sensitivity of the organisms to the API-sludge, they were exposed to concentration series of API-sludge-spiked control soils. The effect concentrations were calculated as the concentration of API-sludge that will decrease the studied endpoints by 50% of the control soil (EC50). The EC50s varied for each species exposed in the different control soils showing that the toxicity of the API-sludge is to a certain extent dependent on the physical soil properties of the substrate. The reproduction of F. candida were most sensitive to the API-sludge in off-site soil (EC50 = 90 mg/kg) and the E. doerjesi the least sensitive in LUFA2.2 soil (EC50 = 36000 mg/kg). Five plant species were exposed to API-sludge-spiked potting soil and the germination success, early growth rate and biomass were studied. The plants were not as sensitive to API-sludge as the soil animals. Lettuce and grass were affected the most by API-sludge and beans were the most resilient species. With the addition of low levels API-sludge to the substrate, the growth rate of beans was stimulated. This study showed that the south-site has been successfully remediated and most soil organisms exposed to these soils were not affected by the levels of toxicants present. However, exposures to north-site soil still had negative effects on soil organisms. It is recommended that hydrocarbon contamination should be further remediated in the north-site soil before landfarming should be allowed to continue. / AFRIKAANSE OPSOMMING: Ploegverwerking is ‘n algemene remediëringsmetode vir die verwerking van afvalmateriaal in petrochemiese industrieë. Dit behels die inploeg van toksiese afvalmateriaal in die boonstegrondlaag sodat dit biologies afgebreek kan word. ‘n Voorbeeld van ‘n histories ploegverwerkte grondstuk is geidentifiseer by ‘n Suid-Afrikaanse olieraffinadery. Die raffinadery het in die verlede van die grondstuk gebruik gemaak om sogenaamde Amerikaanse Petroleum Instituut-slik (API-slik) daarin te ploeg. Die API-slik bestaan uit ‘n mengsel van olie- en wateroplosbare kontaminante afkomstig van die proses waardeur die raffinadery se afvalprodukte van hernubare water en olie geskei word. Nadat oormatige konsentrasies slik in die grond ingewerk is en bioremediasie nie meer doeltreffend kon voortgaan nie, is die ploegverwerking gestaak. ‘n Omgewingimpakstudie moes uitgevoer word om te bepaal tot watter mate die grond herstel het nadat remediasie oor tyd uitgevoer is. Toksisiteitstoetse en chemiese analises is uitgevoer om die vlakke van besoedeling sowel as die biobeskikbare fraksie daarvan in die grond te bepaal. Die ploegverwerkte area van die raffinadery is in twee verdeel naamlik, ‘n meer gekontamineerde noordelike area en ‘n minder gekontamineerde suidelike area. Grondmonsters is van die onderskeie areas asook van ‘n ongekontamineerde veld (as kontrole) naby die ploegverwerkte area versamel Die gronde is fisies- en chemies geanaliseer en toksisiteitstoetse is uitgevoer. Twee addisionele kontolegronde is ook tydens die blootstellings gebruik naamlik, OECD- en LUFA2.2-grond. Die chemiese analises van die ploegverwerkte toetsgronde het getoon dat daar steeds swaarmetale en hoë vlakke van dieselgekoppelde organiese koolwaterstowwe in die gronde teenwoordig is. Kontaminante was in hoër konsentrasies teenwoordig in die grond van die noordelike gebied as in dié van die suidelike gebied. Drie spesies van grondorganismes is gebruik tydens standaard toksisitetitstoetse. Eisenia andrei, Enchytraeus doerjesi en Folsomia candida is blootgestel aan die onderskeie toets- en kontrolegronde waarna hul oorlewing, groei, voortplantingsukses en vermydingsreaksies bestudeer is. Blootstellings aan die ploegverwerkte toetsgronde het geen akute toksisiteit vir enige van die spesies getoon nie. F. candida se juveniele produksie was laer in beide noordelike- en suidelike toetsgronde (289.42 ± 58.62 en 253.33 ± 122.94 onderskeidelik) as in die kontolegrond (479.89 ± 30.42). E. doerjesi blootstellings het ‘n toename in juveniele getalle getoon in die noordelike- en suidelike toetsgronde (339.75 ± 76.92 en 414.00 ± 17.78) in vergelyking met die ongekontamineerde kontolegrond (57 ± 34.39). Kokonproduksie by E. andrei was soorgelyk in die suidelike toetsgrond en ongekontamineerde kontrolegronde (19.00 ± 5.3 en 18.5 ± 9.7 onderskeidelik) maar beduidend minder as in noordelike toetsgrond (1.25 ± 0.7). Slegs E. doerjesi het ‘n beduidende vermydingsreaksie vir die noordelike toetsgronde getoon. Om die sensitiwiteit van die organismes aan vars API-slik te bestudeer, is hulle blootgestel aan konsentrasiereekse van API-slik in die onderskeie kontrolegronde. Die effektiewe konsentrasie (EK50) is bereken as die konsentrasie van API-slik wat die bestudeerde eindpunte met 50% sal verminder in vergelyking met die kontrolegrond Die EK50-waardes vir al die spesies het verskil na blootstelling aan die onderskeie kontrolegronde. Dus, die toksisiteit van die API-slik is tot ‘n sekere mate ook afhanklik van die fisiese grondeienskappe van die blootsellingssubstraat. Die voortplanting van F. candida was die gevoeligste eindpunt vir die blootstelling aan API-slik in kontolegrond (EK50 = 90 mg/kg) en E. doerjesi was die minste gevoelig in LUFA2.2 grond (EK50 = 36000 mg/kg). Vyf plantspesies is ook blootgestel aan API-slikgekontamineerde potgrond en die saadontkiemingssukses, vroeë groeikoers en biomassa is bestudeer. Alhoewel plante nie so sensitief was vir die API-slik soos die gronddiere nie, was blaarslaai en gras die meeste geaffekteer tydens die blootstellings. Boontjies was die ongevoeligste en met die toevoeging van lae konsentrasies API-slik (2.5% API-slik), is hul groeikoers selfs gestimuleer. Uit die studie was dit duidelik dat die suidelike deel van die grondstuk meer suksesvol as die noordelike geremidieer is en dat meeste grondorganismes wat daaraan bloot gestel is nie geaffekteer is deur die vlakke van kontaminasie wat steeds teenwoordig is in die grond nie. Die toetsgronde uit die noordelike deel het egter steeds negatiewe effekte op die grondorganismes gehad. Dit word voorgestel dat die koolwaterstof kontaminasie verder geremidieër behoort te word in die noordelike deel van die grondstuk voordat verdere ploegverwerking van die afval daar gedoen word.

Thesis (PhD)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: During the last 30 years I have been involved in the theory and practice of thermal engineering and in particular, in the areas of air-cooled heat exchangers and cooling towers for the power, refrigeration, process and petrochemical industries in South Africa and internationally. During this period, I have authored and co-authored more than 120 papers that were published in technical journals or presented at conferences nationally or internationally. Most of these papers are included in a manuscript entitled "Air-cooled Heat Exchangers and Cooling Towers", in which Ipresent a systematic approach to the thermal performance evaluation and design of industrial air-cooled heat exchangers and cooling towers. This original publication also includes the relevant practice applicable to the design of cooling systems, based on my experience as a consultant to industry. Design offices throughout the world presently follow our design methods, or at least employ many of our research results. Our work has furthermore contributed to the development of improved cooling system designs (e.g. new dephlegmator header designs), components (e.g. single-row flattened finned tubes) and product improvement and quality control (e.g. performance testing and measurement of thermal contact resistance between fin and tube during production). Many of our research findings have found application in the modification of existing cooling systems. The manuscript has also been used as reference work during the presentation of short courses to practising engineers and consultants in industry and to engineering graduates at the University of Stellenbosch. A two-volume edition of this manuscript was published by PennWell Corp., Tulsa, Oklahoma, USA in 2004. / AFRIKAANSE OPSOMMING: Gedurende die laaste 30 jaar was ek betrokke by die teorie en praktyk van lugverkoelde warmteoordraers en koeltorings vir die kragopwekkings-, verkoelings-, proses- en petro-chemiesenywerhede in Suid-Afrika sowel as in die buiteland. Gedurende hierdie periode was ek outeur en mede-outeur van meer as 120 publikasies wat in tegniese tydskrifte, of by plaaslike of oorsese konferensies aangebied is. Die meeste van hierdie publikasies vorm deel van 'n manuskrip getiteld "Air-cooled Heat Exchangers and Cooling Towers" waarin ek 'n sistematiese benadering tot die bepaling van die termiese vermoë en ontwerp van industriële lugverkoelde warmteoordraers en koeltorings aanbied. Hierdie oorspronklike publikasie bevat ook die relevante praktyk wat van toepassing is op verkoelingsaanlegte. Ontwerpkantore wêreldwyd volg tans hierdie ontwerpsmetodes, of gebruik ten minste baie van ons navorsingsresultate. Ons werk het verder bygedra tot die ontwikkeling van verbeterde verkoelingsaanlegte (bv. nuwe deflegmatore), komponente (bv. enkelbuisry platvinbuise ) en verbeterde produkte en kwaliteitskontrole (bv. toetsing van verkoelingsvermoë oftermiese kontakweerstand tussen vin en buis gedurende produksie). Baie van ons bevindinge het toepassing gevind in die modifikasie van verkoelingsaanlegte. Die manuskrip is ook as verwysing gebruik gedurende die aanbieding van kort kursusse aan ingenieurs in die praktyk en aan nagraadse studente aan die Universiteit van Stellenbosch. 'n Twee-volume uitgawe van die manuskrip is deur PennWell Corp., Tulsa, Oklahome, VSA in 2004 gepubliseer.

Durante muitos anos tem-se usado a técnica de programação linear (Linear programming- LP) para abordar o problema do planejamento da produção em refinarias de petróleo. Esta técnica é baseada na linearização do comportamento não linear dos processos num conjunto particular de condições operacionais. Contudo, modelos lineares não são uma boa representação da operação dos processos de refino, pois estes envolvem diferentes operações físicas (separação de fases, mistura de correntes intermediárias, etc.) e químicas (reações de craqueamento, reações de hidrotratamento, etc.) caracterizadas pelo seu comportamento não linear. Como conseqüência, os resultados (plano de operação) de modelos de planejamento da produção baseados na técnica de programação linear são de difícil implementação na operação. Por outro lado, recentes avanços na capacidade de cálculo dos computadores, assim como nas ferramentas matemáticas (algoritmos de otimização) utilizadas para solucionar os modelos de planejamento da produção, permitem a implementação de modelos não lineares de processos em modelos de planejamento da produção. Este trabalho é focado na formulação de modelos de processos adequados (boa aproximação da operação e baixo custo computacional) para o planejamento da produção em refinarias de petróleo. Inicialmente, é abordada a formulação de um modelo empírico para unidade de destilação o qual foi validado com sucesso usando um simulador rigoroso de processos. A seguir, um modelo empírico para uma unidade de craqueamento catalítico fluidizado (FCC) foi gerado e validado a partir de dados obtidos num simulador rigoroso de processo da PETROBRAS. Estes modelos empíricos superam as limitações dos modelos lineares e não lineares para unidades de destilação e unidades de FCC previamente propostos por outros autores. Em seguida, os modelos empíricos desenvolvidos foram implementados no planejamento da produção (para um único período) de duas refinarias: uma de pequena escala (só duas unidades de processo) e uma de média escala (com 7 unidades de processo). Os modelos de planejamento resultaram em dois problemas de programação não linear que foram resolvidos usando três solvers (CONOPT 3, IPOPT e MINOS) disponíveis na plataforma computacional GAMS (General Algebraic Modeling System). Os modelos de planejamento da produção foram resolvidos com sucesso num tempo computacional inferior a um segundo (CPU time < 1 s) pelos solvers. / For many years production planning problems in the petroleum refineries have been addressed using the linear programming (LP) technique. This technique is based on linear process models (linearization of nonlinear process behavior at a particular set of operating conditions). Nevertheless, the linear process models are not suitable for refinery process modeling, since refinery processes involve both physical (phase separations, blending operations, etc.) and chemical operations (cracking reactions, hydrotreating reactions, etc.) that are characterized by their nonlinear nature. Due to this fact, the results (operating plans) from production planning models based on the linear programming technique are operationally not reliable. On the other hand, recent advances in the computer hardware and in the mathematical tools (optimization algorithms) used for the solution of production planning problems, allow the implementation of nonlinear process models in the production planning models. This work deals with the formulation of non linear empirical process models for petroleum refinery planning. Firstly, the formulation of non linear empirical process model for refinery process is addressed. Two processes were studied: distillation and fluid catalytic cracking (FCC). An empirical model for crude distillation units was developed and successfully validated using rigorous simulations carried out in HYSYS® and the empirical model for a FCC unit was developed and successfully validated using a rigorous FCC simulator from PETROBRAS. These empirical models overcome the limitations of both linear and nonlinear empirical models for crude distillation and FCC units previously developed by others authors. Subsequently, the empirical models developed in this work were successfully implemented in the production planning model for two refineries: a small scale refinery (with two process units) and a medium scale refinery (with 7 process units). The production planning models resulted in two nonlinear programming problems that were solved using three different solvers (CONOPT 3, IPOPT and MINOS) available in GAMS (General Algebraic Modeling System) platform. The computational time for the solution of the production planning models were less than 1 second (CPU time < 1 s).

Thesis submitted in partial fulfilment of the requirements for the degree Master of Technology: Chemical Engineering in the Faculty of Engineering at the Cape Peninsula University of Technology 2013 / In South Africa, the Department of Environmental Affairs (DEA) under the National Environmental Management Act, 1998 (Act 107 of 1998) (“NEMA”) sets out a series of environmental management principles that apply to the interpretation and application of all legislation that may affect the environment. Since 1998, various specific environmental statutes that fall under the NEMA framework have been promulgated, including the National Environmental Management: Air Quality Act, Act 39 of 2004 (NEM: AQA).NEM:AQA provides norms and standards for all technical aspects of air quality management. The National Framework (Sections 7 and 8 of NEM:AQA) must provide mechanisms, systems and procedures to promote holistic and integrated air quality management through pollution prevention and minimisation at source, and through impact management with respect to the receiving environment, from local scale to international issues. Among other measures, the NEM:AQA (Section 9) requires the establishment of Ambient Air Quality Standards and Emission Standards. These standards were promulgated in December 2009 and March 2010 respectively. Air quality monitoring stations, which sample and analyse pollutant concentrations continuously, are a common method of assessing air quality in a region. But a few continuous monitors located in source given region or airshed are inadequate for assessing compliance with ambient air quality standards – they are only able to monitor concentrations at a fixed site, not through the entire region of impact. In contrast, the ambient air quality standards are applicable everywhere. Air quality models estimate ground level ambient concentrations throughout the modelling domain, and in principle (subject to proper validation) provide better estimates of area-wide concentrations and hence the basis for assessing compliance with air quality standards. The United States Environmental Protection Agency (US EPA) approved atmospheric air dispersion models AERMOD and CALPUFF were used in this thesis to predict the ground level concentrations of SO2 emitted from Chevron Refinery (Cape Town), for the year 2010. The modelling is validated by comparing measured ambient concentrations with modelled concentrations. The results showed AERMOD-modelled annual average values for 2010, based on refinery emissions only, are in good agreement with monitored values at the Table View and Bothasig sites, predicting the monitored values by -11% and +17% respectively. The 24-hr average values similarly are in good agreement with monitored values, on average over-predicting by 9% at Table View, although the fit of the day-to-day modelled vs monitored values is comparatively poor (R2=0.32); at the Bothasig site the corresponding values are - 36% and R2= 0.089. The AERMOD-modelled isopleths imply that the 2010 annual average concentrations exceeded the South African Standard of 50 μg/m3 in a small area in the immediate vicinity of the refinery. The hourly and 24-hourly average standard concentrations of 350μg/m3 and 125μg/m3 respectively are exceeded in significantly larger areas. The allowable exceedences for hourly and 24-hourly averages are also exceeded, implying that the hourly and 24-hourly standards were exceeded. CALPUFF-modelled average values for 2010, based on refinery emissions only, are in comparatively poor agreement with monitored values at the Table View and Bothasig sites, under-predicting the monitored values by -20% and -61% respectively. Since the AERMOD-modelled concentrations are in far better agreement with monitored concentrations, only AERMOD was used for further analysis. The Emission Standards promulgated in March 2010 included emission limit values for sulphur dioxide emitted from oil refineries. If the actual 2010 emission rates were adjusted downwards to match the emission standards (to be complied with from 1 April 2015), AERMOD modelling indicates that the annual, 24-hourly and hourly Ambient Air Quality Standards would not be exceeded. Based on this case study, the current Emission Standard for SO2 emissions from existing crude oil refineries is therefore coherent with the Ambient Air Quality Standards. Regulatory air dispersion modelling practices in South Africa are being standardised for model applications regulatory purposes and to ensure that dispersion modelling practices are undertaken in a compatible form to ensure that results from one dispersion model study can be compared directly to those from another. In this study both AERMOD and CALPUFF modelling complied with the draft South African guidelines for Air Quality Modelling, yet the CALPUFF- modelled outputs differed significantly from the monitored values. This emphasizes the importance of the inclusion of modelling validation in guidelines for modelling for regulatory purposes. The 2012 draft regulation should be amended to make validation of regulatory dispersion modelling compulsory rather than optional as per the draft.

Durante muitos anos tem-se usado a técnica de programação linear (Linear programming- LP) para abordar o problema do planejamento da produção em refinarias de petróleo. Esta técnica é baseada na linearização do comportamento não linear dos processos num conjunto particular de condições operacionais. Contudo, modelos lineares não são uma boa representação da operação dos processos de refino, pois estes envolvem diferentes operações físicas (separação de fases, mistura de correntes intermediárias, etc.) e químicas (reações de craqueamento, reações de hidrotratamento, etc.) caracterizadas pelo seu comportamento não linear. Como conseqüência, os resultados (plano de operação) de modelos de planejamento da produção baseados na técnica de programação linear são de difícil implementação na operação. Por outro lado, recentes avanços na capacidade de cálculo dos computadores, assim como nas ferramentas matemáticas (algoritmos de otimização) utilizadas para solucionar os modelos de planejamento da produção, permitem a implementação de modelos não lineares de processos em modelos de planejamento da produção. Este trabalho é focado na formulação de modelos de processos adequados (boa aproximação da operação e baixo custo computacional) para o planejamento da produção em refinarias de petróleo. Inicialmente, é abordada a formulação de um modelo empírico para unidade de destilação o qual foi validado com sucesso usando um simulador rigoroso de processos. A seguir, um modelo empírico para uma unidade de craqueamento catalítico fluidizado (FCC) foi gerado e validado a partir de dados obtidos num simulador rigoroso de processo da PETROBRAS. Estes modelos empíricos superam as limitações dos modelos lineares e não lineares para unidades de destilação e unidades de FCC previamente propostos por outros autores. Em seguida, os modelos empíricos desenvolvidos foram implementados no planejamento da produção (para um único período) de duas refinarias: uma de pequena escala (só duas unidades de processo) e uma de média escala (com 7 unidades de processo). Os modelos de planejamento resultaram em dois problemas de programação não linear que foram resolvidos usando três solvers (CONOPT 3, IPOPT e MINOS) disponíveis na plataforma computacional GAMS (General Algebraic Modeling System). Os modelos de planejamento da produção foram resolvidos com sucesso num tempo computacional inferior a um segundo (CPU time < 1 s) pelos solvers. / For many years production planning problems in the petroleum refineries have been addressed using the linear programming (LP) technique. This technique is based on linear process models (linearization of nonlinear process behavior at a particular set of operating conditions). Nevertheless, the linear process models are not suitable for refinery process modeling, since refinery processes involve both physical (phase separations, blending operations, etc.) and chemical operations (cracking reactions, hydrotreating reactions, etc.) that are characterized by their nonlinear nature. Due to this fact, the results (operating plans) from production planning models based on the linear programming technique are operationally not reliable. On the other hand, recent advances in the computer hardware and in the mathematical tools (optimization algorithms) used for the solution of production planning problems, allow the implementation of nonlinear process models in the production planning models. This work deals with the formulation of non linear empirical process models for petroleum refinery planning. Firstly, the formulation of non linear empirical process model for refinery process is addressed. Two processes were studied: distillation and fluid catalytic cracking (FCC). An empirical model for crude distillation units was developed and successfully validated using rigorous simulations carried out in HYSYS® and the empirical model for a FCC unit was developed and successfully validated using a rigorous FCC simulator from PETROBRAS. These empirical models overcome the limitations of both linear and nonlinear empirical models for crude distillation and FCC units previously developed by others authors. Subsequently, the empirical models developed in this work were successfully implemented in the production planning model for two refineries: a small scale refinery (with two process units) and a medium scale refinery (with 7 process units). The production planning models resulted in two nonlinear programming problems that were solved using three different solvers (CONOPT 3, IPOPT and MINOS) available in GAMS (General Algebraic Modeling System) platform. The computational time for the solution of the production planning models were less than 1 second (CPU time < 1 s).

Orientador: Arnaldo César da Silva Walter / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-16T10:20:38Z (GMT). No. of bitstreams: 1 FuriniFilho_Roberto_D.pdf: 3479141 bytes, checksum: c428ec14603c147e72b2236cbdb4f7c1 (MD5) Previous issue date: 2010 / Resumo: A conexão entre o desempenho das empresas de petróleo e as mudanças climáticas, tomando por base a literatura disponível, constitui-se numa relação pouco estudada, apesar de fundamental quando se discutem as condições de adaptação e mitigação do aquecimento global. Este trabalho trata da análise das ações tomadas em relação às mudanças climáticas por quatro grandes empresas de petróleo escolhidas (BP - British Petroleum, Shell e Statoil), escolhidas devido às suas posições estratégicas nos mercados locais e internacionais, bem como pela Petrobras, de forma a se estabelecer uma análise comparativa entre essas empresas. Para tanto foram investigadas as questões científicas das mudanças climáticas, sem se esquecer de seus críticos, assim como a relação entre energia e mudanças climáticas segundo os cenários do Energy Information Administration - EIA (do governo dos EUA) para o ano de 2008. São analisados também os cenários de contextualização, baseados nos seguintes documentos: Energy Technology Perspectives 2008, da Agência Internacional de Energia (IEA), que reporta cenários de mitigação das emissões de gases de efeito estufa tendo como horizonte 2050; documentos de campanha dos então candidatos Barack Obama e Joe Binden, atualmente presidente e vice dos EUA, respectivamente; documentos da União Européia (Directives EU) e do governo da Califórnia (California Air Resources Board), Um quadro comparativo permite verificar e concluir se as ações das empresas de petróleo estão de acordo com os cenários previstos e quais ações devem ser tomadas pela Petrobras buscando um posicionamento em seu planejamento estratégico. Uma das principais contribuições deste trabalho está em posicionar as empresas estudadas diante das mudanças climáticas, respondendo a quatro perguntas fundamentais formuladas no início do estudo / Abstract: Only modest literature data are available on the connection between the performance of oil companies and the climate changes, although this connection is crucial when discussing the conditions for adaptation and mitigation to global warming changes. This investigation report deals with the analysis of the actions taken in relation to climate change by four major oil companies BP - British Petroleum, Shell and Statoil, selected due to their strategic positions in the local and international markets, and also by Petrobras, in order to establish a comparison among these companies. The scientific issues of climate changes are investigated herein, but not forgetting of its their critics, as well as the relationship between energy and climate change scenarios according to the Energy Information Administration - EIA (the U.S. government) for the year 2008. The contextual scenarios of this investigation are also analyzed based on the following documents: Energy Technology Perspectives 2008, the International Energy Agency (IEA), which reports emissions scenarios for mitigation of greenhouse gases with the horizon in 2050, documents the campaign of the candidates Barack Obama and Joe Binden, documents of the European Union (EU Directives) and the government of California (California Air Resources Board), A comparative table allows someone to verify and conclude if the actions taken by the oil companies are complying with the envisaged scenarios and what actions should be taken by Petrobras in order to seek a position in its strategic planning. One of the main contributions of this work is to rank the studied companies by taking into account the climate changes. This ranking answers four key questions prepared at the beginning of the study / Doutorado / Planejamento de Sistemas Energeticos / Doutor em Planejamento de Sistemas Energéticos