L’électrocoagulation est une technique de traitement des eaux usées basée sur la dissolution d’anode sacrificielle de fer ou d’aluminium. Ces métaux se dissolvent sous formes de cations Fe2+ puis Fe3+ et Al3+ qui vont former des hydroxydes de métal qui entraînent par adsorption les impuretés de l’effluent en diminuant le potentiel Zêta de ces impuretés. Le réacteur électrochimique utilisé est constitué de deux électrodes métalliques (Fe ou Al) planes et parallèles qui laissent passer entre elles l’effluent à traiter. Des densités de courant de 50 à 200 A/m2 ont été appliquées pour traiter les trois effluents. L’un est un effluent directement issu d’une usine textile (effluent « usine »). Un second provient du flux d’entrée de la station d’épuration du site qui collecte les effluents de plusieurs usines (effluent « station »). Le troisième est un effluent artificiel de tannerie, créé en ajoutant 200 ppm de chrome VI à l’effluent « station ». Pour chaque expérience, la densité de courant et le temps de traitement vont déterminer la charge électrique et la concentration en métal dissous atteinte. L’influence de ces quatre paramètres sur l’élimination de la DCO, de l’absorbance, de la turbidité, du COT et du chrome hexavalent a été étudiée. L’évolution au cours du temps d’autres paramètres de l’EC tels que le pH, la tension, le rendement faradique et la dissolution métallique ont été étudiés afin de comprendre leur rôle dans le procédé. Le traitement a permis d’avoir un abattement maximal de DCO de 82% et 80% pour l’effluent « station » traité respectivement avec les électrodes de fer et d’aluminium ; 75 et 67% pour l’effluent « usine » traité respectivement avec les électrodes de fer et d’aluminium. L’abattement du chrome est de 100% avec les électrodes de fer mais tombe à 70% avec celles en aluminium. Des modèles d’élimination de la DCO et de l’absorbance ont été établis pour chaque matériau d’électrode utilisé. Le modèle d’élimination du chrome VI a été établi à partir du traitement avec les électrodes de fer. Une étude de la spéciation des espèces a permis de déterminer les pH optimaux de coagulation-floculation pour chaque métal impliqué (Al, Fe, Cr). La compétitivité entre l’abattement de la pollution organique et du Chrome a aussi été étudiée pour chaque type d’électrode / Electrocoagulation (EC) is a water treatment technology that relies on the electrochemical sacrificial anodes (in Fe or Al) dissolution. This metal dissolve themselves in Al3+ and Fe2+ cations that later oxidise to Fe3+ ions. These cations form metal hydroxides that adsorb the impurities of the effluent while decreasing the zeta potential. The electrochemical reactor used consists on two plane parallel metal electrodes with recirculation of the effluent to be treated between them. Current densities from 50 to 200 A/m2 were imposed to treat each effluent. Three effluents were used in this study. The first one is an effluent sampled at the outlet of a textile plant (« plant »). The second one is a mixture of several effluents coming from different plant and collected at the inlet of the wastewater treatment (« treatment plant »). The last one is a wastewater tannery plant simulated by addition of 200 ppm Chromium VI in the treatment plant effluent. For each experience the current density and the time of treatment rule the electrical charge and the concentration in dissolved metal reached. The influence of these four parameters on the elimination of COD, absorbance, turbidity, COT and hexavalent chromium content has been studied. Parameters e.g. potential, faradic yield, metal dissolution and pH have also been continuously monitored to better understand their role on EC process. The results show that DCO abatement reached 80 and 82% for treatment plant effluent, respectively with iron and aluminium electrodes; and 75 and 67% for plant effluent, respectively with iron and aluminium electrodes. The chromium treatment yields 100 % abatement with Fe electrodes whereas it is only 70% using Al electrodes. Models have been developed for COD and absorbance removal for the two electrode materials. Model for chromium (VI) treatment has been established considering all reactions occurring for iron EC. Metal speciation study allowed us to determine the optimal pH of coagulation –flocculation for each metal involved in the treatment (Al, Fe, Cr). Competition between organic pollution removal and chromium elimination has been also investigated for each electrode material

Este estudo teve como objetivo avaliar o desempenho de 2 reatores anaeróbios de fluxo ascendente e manta de lodo (UASB), em escala de bancada, tratando licor negro diluído, durante 635 dias de operação contínua. Durante a Fase I os reatores foram alimentados com licor negro diluído, enriquecido com nutrientes essenciais, simulando os efluentes de uma indústria de pasta celulósica não branqueada. Durante a Fase II, um dos reatores foi alimentado com o mesmo substrato mais uma mistura de cinco compostos organoclorados, simulando os efluentes de uma indústria de pasta celulósica branqueada. O aumento da taxa de carregamento orgânico, na Fase I, de 0,40 kg DQO/dia m3 para 0,70 kg DQO/dia m3 não provocou diminuição da eficiência de remoção de DQO. Por outro lado, o aumento da taxa de carregamento hidráulico de 0,50 m3/dia m3 para 1,00 m3/dia m3 provocou diminuição de aproximadamente 10% na eficiência média de remoção de DQO no reator 1 e em torno de 12% no reator 2. A adição de 15,00 mg/L dos compostos organoclorados, não influenciou significativamente o desempenho do reator. A eficiência média de remoção de DQO na Fase II foi de 82% no reator de controle e de 79% no reator de tratamento. As eficiências médias de remoção dos compostos organoclorados foram de: 99,9% para o 2-clorofenol, 97,5% para o 2,4- diclorofenol, 95,8% para o 2,6-diclorofenol, 98,9% para o 2,4,6-triclorofenol e 92,8% para o tetraclorocatecol. / This research was conducted to assess the performance of two bench scale upflow anaerobic sludge blanket (UASB) reactors used for the treatment of diluted black liquor, over 635 days of continuous operation. During Phase I of the study both reactors were fed with the diluted black liquor enriched with essential nutrients. This substrate simulated the wastewater from unbleached cellulose pulp plant. Progressing in the research, during Phase II, one of the reactors was fed with the same substrate plus a mixture of five chlorinated organic compounds to simulate the wastewater from a bleached pulp plant. The increase in the organic loading rate, during Phase I, from 0.40 kg COD/m3.day to 0.70 kg COD/m3.day did not result in a decrease in the COD removal efficiency. On the other hand, the increase in the hydraulic loading rate from 0.50 m3/day.m3 to 1.00 m3/day.m3 resulted in a decrease of approximately 12 percent points in the average COD removal efficiency in the reactor 1 and approximately 12 percent points in the reactor 2. The addition of 15 mg/L of chlorinated organic compounds did not have a significant influence in the reactor performance in this research. The removal efficiency of COD during the second phase reached 82% in the control reactor and 79% in the treatment reactor. The average removal efficiencies for the chlorinated organic compounds were: 99.9% for 2-chlorophenol; 97.5% for the 2,4-dichlorophenol; 95.8% for the 2,6- dichlorophenol; 98.9% for the 2,4,6-trichlorophenol and 92.9% for the tetrachlorocatechol.

Uma das abordagens para minimizar o volume de captação de água potável e o descarte de efluentes é o reuso da água dentro da unidade industrial através de técnicas avançadas de tratamento como o sistema de osmose reversa, porém esse sistema exige um afluente com uma baixa quantidade de sólidos, além de outros requisitos. A água residuária utilizada nesse estudo é proveniente de uma empresa do ramo metal-mecânico que utiliza processos de coagulação-floculação-sedimentação como forma de remover os sólidos antes de um sistema de osmose reversa. A proposta deste trabalho foi avaliar três diferentes coagulantes (aluminato de sódio, cloreto férrico e uma mistura de dois coagulantes comerciais, Procytrat 100A e Procytrat 300) em processos de coagulação-floculação e separação de sólidos da fase líquida por sedimentação e flotação por ar dissolvido e também comparar os custos aproximados dos processos envolvidos. Foram realizados ensaios em testes de jarros e flotateste e com os dados obtidos construíram-se diagramas de coagulação-floculação e escolhidas as regiões de maior remoção de sólidos. Através das regiões escolhidas, foram feitas as comparações de eficiência de remoção e custos para cada coagulante estudado. Verificou-se que os diagramas de coagulação-floculação-sedimentação foram os que apresentaram as regiões de maior área com turbidez remanescente menor que 2%, principalmente para os coagulantes cloreto férrico e a mistura Procytrat 100A + Procytrat 300, chegando a alcançar valores próximos a 0,5%. A opção mais econômica foi alcançada com custo de cloreto férrico, na dosagem de 200 mg/L, pH igual a 8,3 e turbidez remanescente igual a 0,6%, de R$0,47/\'M POT.3\' de água tratada. Os diagramas de coagulação-floculação-flotação apresentaram regiões de turbidez remanescente com áreas bem mais reduzidas se comparadas aos diagramas de coagulação-floculação-sedimentação, sendo que não foram atingidos valores de turbidez remanescente menores que 1,5%. Os menores valores de turbidez remanescente para o processo de flotação foram encontrados utilizando-se como coagulante a mistura Procytrat 100A + Procytrat 300, sendo a opção mais econômica alcançada para pH igual a 3,3, dosagem de 60 mg/L e turbidez remanescente igual a 1,6%, com custo de R$0,33/\'M POT.3\' de água tratada. De um modo geral, para todos os coagulantes testados, as regiões escolhidas nos diagramas de coagulação-floculação-flotação, cujos valores de turbidez remanescente foram menores, estavam concentradas em valores de pH baixos (3,2 a 5,5), dosagens de coagulante reduzidas (10 a 80 mg/L) e dosagens de alcalinizante também reduzidas (0 a 60 mg/L de Ca(\'OH)IND.2\'). Esse comportamento foi contrário ao apresentado pelos diagramas coagulação-floculação-sedimentação cujos valores de turbidez remanescente foram menores em valores de pH mais altos (6,5 a 8,5), maiores dosagens de coagulante (40 a 380 mg/L) e altas dosagens de alcalinizante (100 a 400 mg/L de Ca(\'OH)IND.2\'). / One approach to minimize the consumption of drinking water and effluent disposal is the reuse of water within the plant through advanced treatment techniques such as reverse osmosis system, however, this system requires an affluent with a low amount of solids and other requirements. The wastewater used in this study comes from a metalworking company that uses coagulation-flocculation-sedimentation process as a way to remove the solids before a reverse osmosis system. The purpose of this study was to evaluate three different coagulants (sodium aluminate, ferric chloride and a mixture of two commercial coagulants, Procytrat 100A and Procytrat 300) in the process of coagulation-flocculation and separation of solids from the liquid phase by sedimentation and dissolved air flotation and also compare the approximate costs of the processes involved. Jar tests and flotatests were performed and the coagulation-flocculation diagrams were built. In the coagulation-flocculation diagrams were selected areas of higher solids removal. Through the chosen regions, comparisons were made of removal efficiency and cost study for each coagulant. It was found that the diagrams of coagulation-flocculation-sedimentation presented the areas of higher turbidity remaining area with less than 2%, mainly for the coagulants ferric chloride and the mixture Procytrat 100A + Procytrat 300, reaching values close to 0.5 %. The most economical option was achieved at a cost of ferric chloride at a dosage of 200 mg/L, pH 8.3, and the remaining turbidity equal to 0.6%, from R$ 0.47/\'M POT.3\' treated water. The diagrams of coagulation-flocculation-flotation showed regions with turbidity remaining areas much reduced compared to the diagrams of coagulation-flocculation-sedimentation, and the turbidity remaining values were more than 1.5%. The lower values of turbidity remaining for the flotation process were found using the mixture Procytrat 100A + Procytrat 300, and the most economical option was reached for a pH of 3.3, dosage of 60 mg/L and remaining turbidity equal to e 1.6%, at a cost of R$ 0.33/\'M POT.3\' of treated water. In general, for all coagulants tested, the selected regions in the diagrams of coagulation-flocculation-flotation, whose remaining turbidity values were lower, were concentrated in low pH values (3.2 to 5.5), dosages of coagulant reduced (10 to 80 mg/L) and dosages of alkaline also reduced (0 to 60 mg/L of Ca(\'OH)IND.2\'). This behavior was contrary to the diagrams presented by coagulation-flocculation-sedimentation whose remaining turbidity values were lower in higher pH values (6.5 to 8.5), larger amounts of coagulant (40 to 380 mg/L) and high doses of alkaline (100 to 400 mg/L Ca(\'OH)IND.2\').

Um sistema de tratamento constituído de um reator anaeróbio de mistura completa e um reator anaeróbio compartimentado (ABR) foi operado durante 140 dias para estudar os efeitos do pré-tratamento das águas residuárias de uma indústria química, por carvão ativado em pó (CAP), e suas implicações nos processos de nitrificação e desnitrificação. Utilizou-se, no pré-tratamento do resíduo, duas concentrações de carvão ativado em pó. Para aplicação de 10 mg/l de CAP a remoção de DQO foi de 60% e a de NTK foi de 50%. Nesta fase, os processos de remoção de nitrogênio foram plenamente viabilizados. Para 5 mg/l de CAP a remoção de DQO foi de 44% e a remoção de NTK 46%, neste período se observou inibição por metais pesados e acúmulo de nitrito no sistema. / A treatment system composed of both an aerobic complete-mix reactor and a anaerobic baftled reactor (ABR) was operated for 140 days to study the effects of the treatment of wastewater chemical industry by powdered activate carbon (PAC) and its implications in nitrification - denitrification processes. In the residue preliminary treatment, two concentrations of PAC were used. For the application of 10 mg/l of CAP the removal of COD was 60% and the removal of TKN was 50%. In this phase, the processes of nitrogen removal were possible to be completely carried out. For 5 mg/l of CAP, the removal of COD was 44% and the removal of TKN 46%. In this period, the inhibition by heavy metaIs and nitrite accumulation in the system was observed.

A Casa da Moeda do Brasil (CMB) é uma empresa nacional, com mais de 300 anos de experiência na produção de valores e impressos de segurança. A produção de cédulas, realizada pelo Departamento de Cédulas (DECED), consiste de três etapas de impressão, off-set, calografia e tipografia, seguida de acabamento e embalagem semi-automatizado. A impressão calcográfica consome solução de limpeza, composta de soda cáustica e óleo sulfonado, para limpeza do cilindro de impressão, gerando um efluente líquido saturado de tinta. Este efluente apresenta baixa biodegradabilidade, apresentando uma relação DBO / DQO de aproximadamente 1:4. Em termos de tratabilidade, as estações de tratamento de efluentes (ETE) apresentam uma configuração convencional, por via biológica, demonstram pouca eficiência na degradação da matéria orgânica deste efluente. Com compostos recalcitrantes, torna-se necessária a inclusão de uma etapa terciária que permita sua degradação por via química, permitindo o descarte do efluente com características menos danosas ao ambiente. Neste trabalho, aplicou-se a reação de Fenton no efluente do DECED por sua capacidade de converter a matéria orgânica em gás carbônico e água ou, caso seja utilizado em pré-tratamentos, torna-os biodegradáveis. Foram estudadas diferentes condições para medir a influência de diferentes parâmetros na eficiência da reação. A reação de Fenton consiste na geração de radicais hidroxil (HO), por diferentes rotas, em quantidades suficientes para a degradação de matéria orgânica. Esses radicais são gerados a partir de peróxido de hidrogênio (H2O2) em reações com diferentes precursores como ozônio (O3), luz UV (ultravioleta), ultra-som e sais de ferro. No presente trabalho restringiu-se às reações com sais de ferro. Dentre os resultados obtidos, verificou-se o tempo mínimo para reação em 10 minutos. A relação entre íons ferro e peróxido de hidrogênio é menor do que a literatura normalmente sugere, 1:2, contra 1:3. Como a solução de sulfato ferroso é muito instável, passando os íons ferrosos a férricos, utilizou-se a adição direta do sal. Em escala industrial, a solução de sulfato ferroso deve ser preparada em poucas quantidades para que tenha baixo tempo de estocagem, a fim de não ser degradada. A temperatura, na faixa estudada (de 20C à 45C), é um parâmetro que tem pouca influência, pois a redução da eficiência da reação foi pequena (de 99,0% para 94,9%). O ferro utilizado na reação não se demonstrou uma nova fonte de transtornos para o ambiente. Nas condições utilizadas, a concentração de ferro residual esteve próxima ao limite permitido pela legislação no efluente tratado, necessitando apenas de alguns ajustes para a correção do problema / The Brazilians Mint (CMB) is a national enterprise, with more than 300 years of experience in the production of values and security printings. The production of banknotes, carried out by the Departamento de Cédulas (DECED), consists of three printing stages: off-set, intaglio and typography, followed by finishing and semiautomated packing. The intaglio impression consumes cleaning solution, composed by caustic soda and sulfonated castor oil, for cleaning of the printing cylinder, producing an ink saturated wastewater. This wastewater presents low biodegradability, showing a BOD / COD ratio of approximately 1:4. In terms of treatability, the effluent treatment stations (ETS) has presented a conventional configuration, for biological means, has showed a low efficiency in the organic matter degradation of this effluent. With recalcitrant compounds, its necessary the inclusion of a tertiary stage that allows its degradation by chemical means, allowing discarding it with less harmful characteristics to the environment. In this work, the Fenton reaction was applied in the DECED industrial wastewater due to its capacity of converting the organic matter into carbonic gas and water or, if it is used in pay-treatment, turn them into biodegradable (AGUIAR et al., 2007). Different conditions have been studied to measure the influence of different parameters in the reaction efficiency. The Fenton reaction consists in the hidroxyl radicals (HO) generation, by different means, in sufficient quantities for the organic matter degradation. These radicals are produced from of peroxide hydrogen (H2O2) in reactions with different precursors like ozone (O3), UV light, ultrasound and iron salts (GOGATE and PANDIT, 2004). Here we restricted ourselves to the reactions with iron salts. Among the obtained results, it has been verified the minimun time for reaction in 10 minutes. The ratio between iron ions and hydrogen peroxide is lower than suggests the literature (1:2), against (1:3). Since the ferrous sulphate solution is very unstable, because the ferrous ions turn into ferric ions, straight addition of the salt was used. In industrial scale, the ferrous sulfate solution must be prepared in little quantities so that it has low time of stock, in order to not be degraded. The temperature, in the studied range, is a parameter that has little influence, since the efficiency reduction of the reaction was low. The iron used in the reaction did not demonstrate itself a new source of damages for the environment. In the used conditions, the iron concentration was near to maximum limit allowed by the legislation in the effluent treatment, just needing some adjustments to sort out the problem

Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2018-04-04T11:53:17Z No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-04T13:25:36Z (GMT) No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-04T13:25:36Z (GMT). No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-02-28 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Water is an essential natural resource for life that is compromised by the release of emerging contaminants, including synthetic hormones. These compounds can be released directly through industrial effluents and indirectly through domestic sewage. Monitoring emergent contaminants (ECs) in the aquatic environment has become a priority as they pose risks to human health and the environment because of their ability to deregulate the endocrine system. Thus, verification analyzes of the emerging contaminants produced by the pharmaceutical industries are required. The most common analytical methods for analysis of this class of compounds involve the use of liquid or gas chromatography coupled to tandem mass spectrometry (MS / MS) with procedures for the preparation of long samples and long chromatographic runs. In this study, a methodology was developed for the analysis of emerging contaminants in raw and treated industrial wastewater from a local industry's hormone production line by an environmental ionization technique known as Paper Spray Ionization (PSI). Here, we have proposed an analytical approach based on the use of waxed papers. Analyzes of the synthetic hormones levonorgestrel and algestone acetophenide occurred by adding the sample to a triangular paper that was moistened with methanol solution (0.1% formic acid). The paper was fixed at the input of the mass spectrometer through a metal clip which provided a voltage to the paper. The analytical curves presented a linear correlation coefficient above 0.99. For the hormone levonorgestrel the intra-day and inter-day precision ranged from 0.5 to 5.3%, accuracy ranged from -7.0 to 4.2% while recovery ranged from 82.2 to 101.3%. For the hormone algestone acetophenide the intra-day and inter-day precision ranged from 0.9 to 10.7%, accuracy ranged from -7.7 to 8.9% while recovery ranged from 88.4 to 101.6%. The levonorgestrel hormone was also analyzed with the classic LC-MS method, showing consistent results between the two approaches, thus confirming the reliability of the proposed method. / A água é um recurso natural essencial para vida que ultimamente está comprometido pela descarga de contaminantes emergentes, dentre os quais, hormônios sintéticos. Esses compostos podem ser lançados diretamente através de efluentes industriais e indiretamente através de esgoto doméstico. O monitoramento de contaminantes emergentes (ECs) no ambiente aquático tem se tornado uma prioridade, visto que eles apresentam riscos para a saúde humana e para meio ambiente devido a sua capacidade de desregular o sistema endócrino. Dessa forma, é necessário análises de verificação dos contaminantes emergentes produzidos pelas indústrias farmacêuticas. Os métodos analíticos mais comuns para análises dessa classe de compostos envolvem o uso de cromatografia líquida ou gasosa, acoplado a espectrometria de massas tandem (MS/MS) com procedimentos de preparos de amostras demorados e longas corridas cromatográficas. Neste trabalho desenvolveu-se uma metodologia para análise de contaminantes emergentes em água residual industrial bruta e tratada de uma linha de produção de hormônios de uma indústria local, por uma técnica de ionização ambiente conhecida como Paper Spray Ionization (PSI), cuja principal vantagem é o preparo mínimo de amostra. Neste trabalho, a técnica de PSI com papel contendo barreiras de parafinas foi empregada para análise de hormônios em águas residuárias. As análises dos hormônios sintéticos levonorgestrel e algestona acetofenida ocorreram através da adição da amostra sobre um papel triangular que foi umedecido com solução de metanol (0,1% de ácido fórmico). O papel foi fixado na entrada do espectrômetro de massas através de um clipe metálico que forneceu uma voltagem ao papel. As curvas analíticas apresentaram coeficiente de correlação linear acima de 0,99. Para o hormônio levonorgestrel a precisão intra-dias e inter-dias variou de 0,5 a 5,3%, a exatidão variou de -7,0 a 4,2% enquanto a recuperação variou de 82,2 a 101,3%. Para o hormônio algestona acetofenida a precisão intra-dias e inter-dias variou de 0,9 a 10,7%, a exatidão variou de -7,7 a 8,9% enquanto a recuperação variou de 88,4 a 101,6%. O hormônio levonorgestrel também foi analisado com o método clássico LC-MS, mostrando resultados consistentes entre as duas abordagens, confirmando assim a confiabilidade do método proposto.

Η επιλογή της καλύτερης διαθέσιμης τεχνολογίας για την επεξεργασία βιομηχανικών αποβλήτων που προέρχονται από μια δεδομένη πηγή απαιτεί μια καλά δομημένη και περιεκτική μεθοδολογία για συστηματική αποτίμηση των εναλλακτικών τεχνολογιών. Μια κατάλληλη μεθοδολογία για την επιλογή ενός ολοκληρωμένου συστήματος διαχείρισης βιομηχανικών απόβλητων από περιβαλλοντική και οικονομική άποψη αναπτύσσεται και εφαρμόζεται σε μια βιομηχανία γάλακτος. Προκειμένου να επιλεγεί το πιο φιλικό προς το περιβάλλον και το περισσότερο οικονομικό ολοκληρωμένο σύστημα επεξεργασίας, διαφορετικές τεχνολογίες επεξεργασίας βιομηχανιών αποβλήτων εξετάστηκαν. Τα συστήματα επεξεργασίας αποτελούνται από εναλλακτικές διεργασίες προεπεξεργασίας, τεχνολογίες βιολογικής επεξεργασίας (αερόβιες και αναερόβιες) και την επεξεργασία της ιλύος. Αναπτύχθηκε ένα μοντέλο τύπου ριζόχαρτου που υπολογίζει την κατανάλωση των υλικών, της ενέργειας, των κύριων αναλωσίμων και τις εκπομπές που συνδέονται με τις φάσεις οικοδόμησης και λειτουργίας των εναλλακτικών τεχνολογιών επεξεργασίας. Στη συνέχεια χρησιμοποιήθηκε η μεθοδολογία της Ανάλυσης Κύκλου Ζωής (ΑΚΖ) για να υπολογιστούν ποσοτικά οι πιθανές περιβαλλοντικές επιπτώσεις σε κάθε περίπτωση. Οι επιλογές που βασίζονται στην αναερόβια χώνευση αναδείχθηκαν ότι είναι περισσότερο φιλικές προς το περιβάλλον και οδηγούν σε λιγότερες εκπομπές. / The selection of the best available technology for the treatment of industrial wastewater originating from a given source requires a well structured and comprehensive methodology for the systematic evaluation of the alternative technologies. A suitable methodology for the selection of an integrated system of management of industrial wastewater from the environmental and economic viewpoints is developed and applied to a milk industry. In order to select the environmentally friendlier and most economic integrated treatment system, different industrial wastewater treatment technologies were considered. The treatment systems consisted of alternative pretreatment processes, biological treatment technologies (aerobic and anaerobic) and sludge treatment. A spreadsheet model that calculates the consumption of materials, energy, main consumables and emissions associated with both the construction and operation phases of the alternative treatment technologies was constructed. The Life Cycle Assessment (LCA) methodology was then used to quantify the potential environmental impacts in each case. Options based on anaerobic digestion were found to be the most environmentally friendly leading to fewer emissions.

The primary objective of wastewater treatment is the removal of pollutants to meet given legal effluent standards. To further reduce operators costs additional recovery of resources and energy is desired by industrial and municipal wastewater treatment. Hence the objective in early stage of planning of treatment facilities lies in the identification and evaluation of promising configurations of treatment units. Obviously this early stage of planning may best be supported by software tools to be able to deal with a variety of different treatment configurations. In chemical process engineering various design tools are available that automatically identify feasible process configurations for the purpose to obtain desired products from given educts. In contrast, the adaptation of these design tools for the automatic generation of treatment unit configurations (process chains) to achieve preset effluent standards is hampered by the following three reasons. First, pollutants in wastewater are usually not defined as chemical substances but by compound parameters according to equal properties (e.g. all particulate matter). Consequently the variation of a single compound parameter leads to a change of related parameters (e.g. relation between Chemical Oxygen Demand and Total Suspended Solids). Furthermore, mathematical process models of treatment processes are tailored towards fractions of compound parameters. This hampers the generic representation of these process models which in turn is essential for automatic identification of treatment configurations. Second, treatment technologies for wastewater treatment rely on a variety of chemical, biological, and physical phenomena. Approaches to mathematically describe these phenomena cover a wide range of modeling techniques including stochastic, conceptual or deterministic approaches. Even more the consideration of temporal and spatial resolutions differ. This again hampers a generic representation of process models. Third, the automatic identification of treatment configurations may either be achieved by the use of design rules or by permutation of all possible combinations of units stored within a database of treatment units. The first approach depends on past experience translated into design rules. Hence, no innovative new treatment configurations can be identified. The second approach to identify all possible configurations collapses by extremely high numbers of treatment configurations that cannot be mastered. This is due to the phenomena of combinatorial explosion. It follows therefrom that an appropriate planning algorithm should function without the need of additional design rules and should be able to identify directly feasible configurations while discarding those impractical. This work presents a planning tool for the identification and evaluation of treatment configurations that tackles the before addressed problems. The planning tool comprises two major parts. An external declarative knowledge base and the actual planning tool that includes a goal oriented planning algorithm. The knowledge base describes parameters for wastewater characterization (i.e. material model) and a set of treatment units represented by process models (i.e. process model). The formalization of the knowledge base is achieved by the Web Ontology Language (OWL). The developed data model being the organization structure of the knowledge base describes relations between wastewater parameters and process models to enable for generic representation of process models. Through these parameters for wastewater characterization as well as treatment units can be altered or added to the knowledge base without the requirement to synchronize already included parameter representations or process models. Furthermore the knowledge base describes relations between parameters and properties of water constituents. This allows to track changes of all wastewater parameters which result from modeling of removal efficiency of applied treatment units. So far two generic treatment units have been represented within the knowledge base. These are separation and conversion units. These two raw types have been applied to represent different types of clarifiers and biological treatment units. The developed planning algorithm is based on a Means-Ends Analysis (MEA). This is a goal oriented search algorithm that posts goals from wastewater state and limit value restrictions to select those treatment units only that are likely to solve the treatment problem. Regarding this, all treatment units are qualified according to postconditions that describe the effect of each unit. In addition, units are also characterized by preconditions that state the application range of each unit. The developed planning algorithm furthermore allows for the identification of simple cycles to account for moving bed reactor systems (e.g. functional unit of aeration tank and clarifier). The evaluation of identified treatment configurations is achieved by total estimated cost of each configuration. The planning tool has been tested on five use cases. Some use cases contained multiple sources and sinks. This showed the possibility to identify water reuse capabilities as well as to identify solutions that go beyond end of pipe solutions. Beyond the originated area of application, the planning tool may be used for advanced interrogations. Thereby the knowledge base and planning algorithm may be further developed to address the objectives to identify configurations for any type of material and energy recovery.

Abstract Lime precipitation has been used for the treatment of mine water for decades; however, the impact of precipitation conditions is not adequately known. In this thesis, four aspects related to the removal of sulphate from mine water by lime precipitation are considered: the effect of magnesium on lime precipitation, the utilisation of by-products in lime precipitation, enhancement of lime precipitation, and utilisation of the precipitate. Sulphate removal in the presence of magnesium at the commonly used lime precipitation treatment pH of 9.6 was found unefficient as magnesium was keeping the sulphate soluble in the form of magnesium sulphate. At higher treatment pH of 11.5, magnesium that was naturally present in the mine water was shown to precipitate as magnesium hydroxide, which could serve as seed crystals for gypsum or co-precipitate sulphate thus enhancing sulphate removal. Quicklime manufacturing generates by-products that, currently, have few applications. The by-products examined in this study were successfully applied for mine water neutralization replacing commercial lime products. These by-products were found to remove sulphate equally well from the mine water. However, differences between by-products were observed in the consumption, and produced sludge quantities and qualities. An enhanced lime precipitation method is the precipitation as ettringite, which was used to reduce the sulphate content in mine water to less than the value set as the drinking water guideline in Finland. Furthermore, the formed precipitate was found to remove arsenate from the model solution. / Tiivistelmä Vaikka kalkkisaostusta on käytetty kaivosten vesienkäsittelyyn useiden vuosikymmenten ajan, tieto olosuhteiden vaikutuksesta käsittelyn tehokkuuteen sulfaatin poiston osalta on puutteellista. Tämä väitöskirja käsittelee sulfaatinpoistoa kaivosvesistä kalkkisaostuksen avulla neljällä eri osa-alueella: magnesiumin vaikutus kalkkisaostukseen, kalkinpolton sivutuotteiden hyödyntäminen kalkkisaostuksessa, kalkkisaostuksen tehostaminen ja muodostuvan saostuman hyödyntäminen. Magnesiumin todettiin kokeellisesti ja laskennallisesti haittaavan sulfaatin poistoa kaivosvedestä kalkkisaostuksessa yleisesti käytetyssä pH:ssa 9.6 pitämällä sulfaattia liukoisessa muodossa magnesiumsulfaattina. Korkeammassa pH:ssa 11.5 puolestaan kaivosveden luontaisesti sisältämän magnesiumin havaittiin kokeellisesti ja laskennallisesti saostuvan magnesiumhydroksidina, joka voi toimia siemenkiteinä kipsille tai kerasaostaa sulfaattia ja siten tehostaa sulfaatin poistoa. Kalkinpolton sivutuotteina muodostuu jakeita, joille ei tällä hetkellä ole juurikaan käyttökohteita. Tässä työssä käytettiin kalkinpolton sivutuotteita korvaamaan kaupallista kalkkia kaivosveden neutraloinnissa. Sivutuotteet poistivat sulfaattia yhtä tehokkaasti kuin kaupalliset kalkkituotteet. Sivutuotteiden välillä havaittiin eroja niiden kulutuksessa sekä muodostuvan lietteen määrässä ja laadussa. Saostuksella ettringiittinä, joka on tehostettu versio perinteisestä kalkkisaostuksesta, saavutettiin sulfaattipitoisuuden lasku alle Suomessa juomavedelle käytetyn suositusarvon. Lisäksi havaittiin muodostuneen ettringiittisaostuman olevan potentiaalinen materiaali arsenaatin poistoon vedestä.

A indústria moveleira em geral e de piso de madeira é caracterizada por processos a seco. Em decorrência da limpeza e lavagem de maquinário e superfícies gera águas residuárias em baixos volumes porém altamente contaminadas com substâncias recalcitrantes de difícil tratamento. Com o objetivo de oferecer uma alternativa tecnológica de fácil operação (com uso mínimo de reagentes químicos), capaz de tratar tais águas, reduzir toxicidade e aumentar biodegradabilidade do efluente, viabilizando desta forma uma etapa subsequente de tratamento biológico, o presente trabalho conduziu ensaios de tratabilidade baseados em processos oxidativos avançados com águas residuárias provenientes de lavagens em uma indústria de piso de madeira em Nybro, Suécia, com DQO inicial de aproximadamente 45.000 mg/L e pH de 2,3-2,6. Após tratamento primário in situ com redução de 89% de DQO, os seguintes processos geradores de radicais OH foram testados em escala de laboratório: ozonização sem ajuste de pH (Etapa I); ozonização com ajuste de pH (Etapa II); e ozonização + UV-C com ajuste de pH (Etapa III). Os experimentos foram realizados em semi-batelada, utilizando-se um aparato com dois reatores conectados (de O3 e de UV), entre os quais foi mantido fluxo de recirculação em contracorrente com o gás. Para o desenho experimental, utilizou-se a metodologia de planejamento fatorial do tipo Delineamento Composto Central Rotacional (DCCR) utilizando-se como variáveis independentes, (i) vazão de recirculação entre os reatores (VR) com níveis variando de 0,3 a 3L/min; (ii) concentração de O3 na mistura gasosa injetada ([O3]) ou modo de dosagem cujos níveis variaram de 40 a 115 g/Nm3 e; (iii) pH inicial (Etapas II e III) com níveis que variaram de 3 a 11. A quantidade total de O3 fornecida até o final de cada ensaio foi fixada em 2 gramas de O3 para cada grama de DQO inicial (2:1). A eficiência de cada tratamento foi avaliada em função da redução de DQO, da remoção de COT e do consumo de O3. Para ozonização sem ajuste de pH foram alcançadas reduções de DQO e COT de 65 e 31% respectivamente. No tratamento com ajuste de pH sem UV, foram alcançadas reduções de DQO e COT de 85% e 43% com pHinicial = 7,0 enquanto que no tratamento com UV foi alcançada redução de DQO e COT de 93% e 56% respectivamente, com pHi = 9,38. Os resultados de respirometria com os efluentes dos tratamentos indicaram que a ozonização destas águas em pH baixo pode resultar na geração de subprodutos menos biodegradáveis. Entretanto, tais produtos não são gerados quando a ozonização é realizada em pH mais elevado (7,0), mesmo sem aplicação de UV, com doses de O3:DQOinicial menores que 1:1. O tratamento por ozonização pode, portanto, ser aplicado como uma etapa intermediária de tratamento das águas residuárias em questão, inclusive precedendo o tratamento biológico. / The wood-based industry (including the wooden floor production) is characterized by dry process but due to cleaning and washing of machineries and surfaces this industry generates low volumes of highly polluted and recalcitrant wastewater. The purpose of this study was to investigate a technological alternative, easy to operate, with minimum use of chemicals, capable to treat these wastewaters, reducing toxicity and increasing the biodegradability making it feasible the biological treatment of the effluents. In the present study, a number of treatability assays based on advanced oxidation processes (AOPs) were carried out to treat cleaning wastewater from a wooden floor industry in Nybro, Sweden, with an initial COD of approximately 45,000 mg/L and pH of 2.3-2.6. After an initial reduction of 89% of DQO through an in situ sedimentation step, the following processes generating free radicals OH were tested in lab-scale: Ozonation without pH adjustment (Phase 1); Ozonation with pH adjustment (Phase 2); and Ozonation + UV-C with pH adjustment (Phase 3). The experiments were performed in semibatch reactors using an apparatus with two connected reactors (O3 and UV); between them, the recirculation flow was kept in countercurrent with the gas flow. For the experimental design, the factorial planning of the type Central Composite Rotatable Design (DCCR) was applied with the following independent variables: (i) recirculation flow between reactors (VR) with levels varying from 0.3 to 3.0 L/min; (ii) concentration of O3 in the injected gaseous mixture ([O3]) or dose mode, with levels varying from 40 to 115 g/Nm3; (iii) initial pH (Phases 2 and 3) with levels varying from 3 to 11. The total amount of O3 supplied along the whole treatment was 2 grams of O3 per gram of initial COD (2:1). The efficiency of each treatment was based on the COD reduction, TOC removal and O3 consumption. Ozonation without pH adjustment, promoted a reduction of COD and COT of 65 and 31% respectively. Ozonation with pH adjustment to pHinitial = 7.0 reduced COD and TOC in 85% and 43% respectively. Ozonation, UV and pH adjustment to pHinitial = 9.38 reduced COD and TOC in 93% and 56% respectively. The results of the respirometry tests with the effluent from the AOP treatments without pH adjustment suggested that such treatment generates byproducts, which are even less biodegradable than those found in the wastewater before treatment. However, such products are not generated when ozonation is carried out in higher pH (7.0), even without UV and O3:DQOi doses lower than 1:1. The treatment with O3, can be useful as an intermediate treatment step for the studied wastewater, and be placed before biological treatment.