Este trabalho tem como objetivo aplicar a técnica de encapsulamento, conhecida também como solidificação/estabilização, em um solo contaminado com crescentes quantidades do resíduo industrial borra oleosa ácida, utilizando como agente encapsulante o cimento Portland CP-V ARI. O programa experimental consistiu na realização de estudos pré e pós-tratamento, analisando fisicamente o solo através de ensaios de caracterização geotécnica, compactação, resistência à compressão simples, durabilidade e condutividade hidráulica. Quimicamente foram realizados ensaios de lixiviação em coluna e análises químicas e físico-químicas do lixiviado. Devido às elevadas temperaturas detectadas no momento das misturas de solo/cimento e borra oleosa ácida, foram realizados ensaios para o monitoramento da temperatura e o tempo de hidratação do cimento. Os resultados apontam que quanto maior a quantidade de borra oleosa ácida presente no solo tratado, maior é a temperatura de hidratação do cimento e mais rápido atinge o pico máximo, resultando em menor resistência à compressão simples e maior perda de massa. Em amostras sem cimento, a condutividade hidráulica diminui com o aumento de borra oleosa ácida, quando adicionado cimento a condutividade hidráulica inicialmente diminui com o acréscimo de borra oleosa ácida, mas volta a aumentar com quantidades maiores de contaminante. A técnica de encapsulamento mostrou-se eficiente quanto à redução dos metais pesados, devido, principalmente, ao aumento do pH e a precipitação de tais elementos. Porém não se mostrou eficiente quanto ao sulfato, condutividade elétrica e demanda química de oxigênio. / The objective of this study is applying the encapsulation technique, also known as solidification/stabilization, in soil contaminated with increasing amounts of acidic oily sludge industrial residues, using Portland cement CP-V ARI as the encapsulating agent. The experimental program consisted of studies pre and post-treatment, in which the soil was physically analyzed through geotechnical characterization testings, compactation, unconfined compressive strength, duration and hydraulic conductivity tests. In chemical terms, column leach testings were conducted, along with chemical and physical-chemical analyses of the leachete. Due to the high temperatures detected upon mixing soil/cement and the acidic oily sludge, tests were conducted to monitor the temperature and the hydratation rate of the cement. The results show that the greater the amount of acidic oily sludge in the treated soil, the higher the temperature necessary to hydrate the cement and the faster it reaches the maximum peak, which results in less unconfined compressive strength and greater mass loss. In samples without cement, the hydraulic conductivity reduced upon increasing the amount of acidic oily sludge. When cement is added, the hydraulic conductivity initially decreases with the acidic oily sludge, but it increases again with greater amounts of the substance. The encapsulation technique proved to be efficient in the reduction of heavy metals, due mainly to the pH increase and the precipitation of such components. However, the technique did not prove to be efficient in relation to sulphate, and to the electrical conductivity and the chemical oxygen demand.

Este trabalho tem como objetivo aplicar a técnica de encapsulamento, conhecida também como solidificação/estabilização, em um solo contaminado com crescentes quantidades do resíduo industrial borra oleosa ácida, utilizando como agente encapsulante o cimento Portland CP-V ARI. O programa experimental consistiu na realização de estudos pré e pós-tratamento, analisando fisicamente o solo através de ensaios de caracterização geotécnica, compactação, resistência à compressão simples, durabilidade e condutividade hidráulica. Quimicamente foram realizados ensaios de lixiviação em coluna e análises químicas e físico-químicas do lixiviado. Devido às elevadas temperaturas detectadas no momento das misturas de solo/cimento e borra oleosa ácida, foram realizados ensaios para o monitoramento da temperatura e o tempo de hidratação do cimento. Os resultados apontam que quanto maior a quantidade de borra oleosa ácida presente no solo tratado, maior é a temperatura de hidratação do cimento e mais rápido atinge o pico máximo, resultando em menor resistência à compressão simples e maior perda de massa. Em amostras sem cimento, a condutividade hidráulica diminui com o aumento de borra oleosa ácida, quando adicionado cimento a condutividade hidráulica inicialmente diminui com o acréscimo de borra oleosa ácida, mas volta a aumentar com quantidades maiores de contaminante. A técnica de encapsulamento mostrou-se eficiente quanto à redução dos metais pesados, devido, principalmente, ao aumento do pH e a precipitação de tais elementos. Porém não se mostrou eficiente quanto ao sulfato, condutividade elétrica e demanda química de oxigênio. / The objective of this study is applying the encapsulation technique, also known as solidification/stabilization, in soil contaminated with increasing amounts of acidic oily sludge industrial residues, using Portland cement CP-V ARI as the encapsulating agent. The experimental program consisted of studies pre and post-treatment, in which the soil was physically analyzed through geotechnical characterization testings, compactation, unconfined compressive strength, duration and hydraulic conductivity tests. In chemical terms, column leach testings were conducted, along with chemical and physical-chemical analyses of the leachete. Due to the high temperatures detected upon mixing soil/cement and the acidic oily sludge, tests were conducted to monitor the temperature and the hydratation rate of the cement. The results show that the greater the amount of acidic oily sludge in the treated soil, the higher the temperature necessary to hydrate the cement and the faster it reaches the maximum peak, which results in less unconfined compressive strength and greater mass loss. In samples without cement, the hydraulic conductivity reduced upon increasing the amount of acidic oily sludge. When cement is added, the hydraulic conductivity initially decreases with the acidic oily sludge, but it increases again with greater amounts of the substance. The encapsulation technique proved to be efficient in the reduction of heavy metals, due mainly to the pH increase and the precipitation of such components. However, the technique did not prove to be efficient in relation to sulphate, and to the electrical conductivity and the chemical oxygen demand.

Este trabalho tem como objetivo aplicar a técnica de encapsulamento, conhecida também como solidificação/estabilização, em um solo contaminado com crescentes quantidades do resíduo industrial borra oleosa ácida, utilizando como agente encapsulante o cimento Portland CP-V ARI. O programa experimental consistiu na realização de estudos pré e pós-tratamento, analisando fisicamente o solo através de ensaios de caracterização geotécnica, compactação, resistência à compressão simples, durabilidade e condutividade hidráulica. Quimicamente foram realizados ensaios de lixiviação em coluna e análises químicas e físico-químicas do lixiviado. Devido às elevadas temperaturas detectadas no momento das misturas de solo/cimento e borra oleosa ácida, foram realizados ensaios para o monitoramento da temperatura e o tempo de hidratação do cimento. Os resultados apontam que quanto maior a quantidade de borra oleosa ácida presente no solo tratado, maior é a temperatura de hidratação do cimento e mais rápido atinge o pico máximo, resultando em menor resistência à compressão simples e maior perda de massa. Em amostras sem cimento, a condutividade hidráulica diminui com o aumento de borra oleosa ácida, quando adicionado cimento a condutividade hidráulica inicialmente diminui com o acréscimo de borra oleosa ácida, mas volta a aumentar com quantidades maiores de contaminante. A técnica de encapsulamento mostrou-se eficiente quanto à redução dos metais pesados, devido, principalmente, ao aumento do pH e a precipitação de tais elementos. Porém não se mostrou eficiente quanto ao sulfato, condutividade elétrica e demanda química de oxigênio. / The objective of this study is applying the encapsulation technique, also known as solidification/stabilization, in soil contaminated with increasing amounts of acidic oily sludge industrial residues, using Portland cement CP-V ARI as the encapsulating agent. The experimental program consisted of studies pre and post-treatment, in which the soil was physically analyzed through geotechnical characterization testings, compactation, unconfined compressive strength, duration and hydraulic conductivity tests. In chemical terms, column leach testings were conducted, along with chemical and physical-chemical analyses of the leachete. Due to the high temperatures detected upon mixing soil/cement and the acidic oily sludge, tests were conducted to monitor the temperature and the hydratation rate of the cement. The results show that the greater the amount of acidic oily sludge in the treated soil, the higher the temperature necessary to hydrate the cement and the faster it reaches the maximum peak, which results in less unconfined compressive strength and greater mass loss. In samples without cement, the hydraulic conductivity reduced upon increasing the amount of acidic oily sludge. When cement is added, the hydraulic conductivity initially decreases with the acidic oily sludge, but it increases again with greater amounts of the substance. The encapsulation technique proved to be efficient in the reduction of heavy metals, due mainly to the pH increase and the precipitation of such components. However, the technique did not prove to be efficient in relation to sulphate, and to the electrical conductivity and the chemical oxygen demand.

Oily wastewater produced from petroleum and petrochemical refining processes is one of the gravest environmental threats. Oil waste ending up in sewers and dumps each year is equal to 25 times the amount of crude oil spilled in the Exxon Valdez accident (1989). Oil/Water separation covers a broad spectrum of industrial process operations. There are many techniques employed depending on each situation. The byproduct of water recovery from oily wastewater is a sludge rich in oil, surfactants and particles (oily sludge). The oily sludge still contains significant amounts of waters, which need to be recovered prior to its disposal. The use of polyelectrolytes for the flocculation of the emulsified oil and its separation from the aqueous phase is usually one of the steps of the wastewater as well as oily sludge treatment process. The efficiency of polyelectrolytes as floculants is quite often evaluated via trial and error and the appropriate polymer is selected according to the case. Even in scientific investigations it is rather common to use industrial oily sludge samples. The industrial oily sludge is characterized and treated by polyelectrolytes. Nevertheless industrial oily sludge is quite complicated and variable to be approximated by a model. For the systematic study of polyelectrolytes efficiency a stable, realistic and well-defined oily sludge model is necessary. In the present work an oily sludge model was successfully developed and characterized. The model consists on water, oil (kerosene), surfactant (sodium dodecyl sulphate, SDS) and clay particles (Blauton). The emulsifying efficiency of the surfactant and the clay were studied independently. The interactions between the surfactant and the clay including adsorption of the former on the later and cation exchange reactions were investigated. The four components were finally combined to form a series of emulsions varying the relative amounts of the emulsifiers for the highest stability to be encountered. Having concluded on the composition of the oily sludge model the efficiency of various polyelectrolytes was evaluated. Commercial natural (chitosans), synthetic (PolyDADMACs) polyelectrolytes and oilbreaks as well as lab-scale semi-synthetic polymers (modified chitosans) were tested. The flocculation efficiency was determined based on the amount and quality of water that was recovered as well as on the floc stability, size and sedimentation speed. The recovered water was characterized according to the environmental protection agency (EPA). The analysis included measurements on: total organic carbon (TOC), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total suspended solids (TSS) and pH. Selection of the appropriate flocculant also depends on the type of flocs formed in combination to the treatment following the flocculation. When filtration or centrifugation is used as a post-flocculation process the appropriate polymers are those that form large and porous flocs, as the case of the modified chitosans AG95 and AG97. Clarification devices on the other hand require dense flocs as these produced by the use of PolyDADMACs, commercial chitosans, oilbreaks and modified chitosans GA35, GA41 and AG79. Regarding the water quality, some of the polymers used that have low values of COD, TOC and BOD5, may not need the secondary treatment (biological) prior to discharge, such as P187K (PolyDADMAC) and GA41 (modified chitosan). The others require a biological treatment for the regulation limits to be reached. The pH values of modified chitosans (except of AG97), lab-scale PolyDADMACs and an oilbreak (OCAA) are all in range of the regulation limits. The applicability of biopolymers as flocculants for oil sludge dewatering is a relatively new field of investigation. As a consequence of the growing demand for environmentally friendly technologies as well as renewable resources the interest on natural flocculants has increased. The aminopolysaccharide chitosan and its modified derivatives have outstanding properties such as biocompability, biodegradability, hydrophilicity, adsorption, flocculating ability and antibacterial properties. These natural polymers derived from the sea-food industry waste products would be very useful as residue oil adsorbents in any oily wastewater and can be among the most promising candidates as a replacement of the synthetic flocculants. / Ölhaltiges Abwasser, das bei Erdöl- und petrolchemischen Raffinierungsprozessen entsteht, ist eine der größten Umweltgefahren. Dieses Altöl landet jedes Jahr in der Kanalisation und in Deponien. Es handelt sich dabei um die 25-fache Menge an Rohöl, die beim Unfall der Exxon Valdez (1989) ausgeflossen ist. Die Öl/Wasser-Trennung überspannt ein breites Spektrum industrieller Prozesse. Es gibt viele Techniken, die abhängig von jeder Situation eingesetzt werden. Das Nebenprodukt bei der Abtrennung von Wasser aus ölhaltigen Abwässern ist ein Schlamm (Ölschlamm), der reich an Öl, Tensiden und Partikeln ist. Der Ölschlamm enthält noch bedeutende Mengen an Wasser, die vor ihrer Entsorgung verwertet werden müssen. Die Verwendung von Polyelektrolyten zur Ausflockung des emulgierten Öls und seine Trennung von der wässrigen Phase ist in der Regel einer der Schritte zur Behandlung von Abwässern sowie ölhaltigen Schlämmen. Die Effizienz von Polyelektrolyten als Flockungsmittel wird ganz häufig über Versuch und Fehler bewertet, und das passende Polymer wird entsprechend dem jeweiligen Fall ausgewählt. Sogar in wissenschaftlichen Untersuchungen ist es eher üblich, industrielle Ölschlamm-Proben zu verwenden. Der industrielle Ölschlamm wird charakterisiert und mit Polyelektrolyten behandelt. Dennoch ist der industrielle Ölschlamm ziemlich kompliziert und variabel und muss durch ein Modell angenähert werden. Für die systematische Untersuchung der Effizienz von Polyelektrolyten als Flockungsmittel ist ein stabiles, realistisches und klar definiertes Ölschlamm-Modell notwendig. In der vorliegenden Arbeit wurde ein Ölschlamm-Modell erfolgreich entwickelt und charakterisiert. Das Modell besteht aus Wasser, Öl (Kerosin), Tensid (Natriumdodecylsulfat, SDS) und Tonteilchen (Blauton). Die Emulgiereffizienz des Tensids und des Tons wurden unabhängig voneinander untersucht. Die Wechselwirkungen zwischen dem Tensid und dem Ton, die sowohl die Adsorption des Ersteren auf dem Letzteren einschließen als auch einen Kationenaustausch, wurden untersucht. Die vier Komponenten des Ölschlamm-Modells wurden schließlich kombiniert und es wurde eine Reihe von Emulsionen hergestellt, bei denen die relativen Mengen der Emulsionsmittel verändert wurden, um eine möglichst hohe Stabilität zu erreichen. Nachdem ein geeignetes Ölschlamm-Modell zur Verfügung stand, wurde die Effizienz der verschiedenen Polyelektrolyte als Flockungsmittel bewertet. Kommerzielle natürliche (Chitosane), synthetische (PolyDADMACs) Polyelektrolyte und Oilbreaks sowie Labor-semi-synthetische Polymere (modifizierte Chitosane) wurden getestet. Die Flockungseffizienz wurde sowohl basierend auf der Menge und Qualität des Wassers, das zurückgewonnen wurde, als auch bezogen auf die Flockenstabilität, die Flockengröße und die Sedimentationsgeschwindigkeit bestimmt. Das zurückgewonnene Wasser wurde entsprechend der Vorschriften der Behörde für Umweltschutz (EPA) charakterisiert. Die Analysen enthielten die Bestimmung des gesamten organischen Kohlenstoffs (TOC), des chemischen Sauerstoffbedarf (CSB), des biochemischen Sauerstoffbedarfs (BSB5), des Gesamtgehalts an suspendierten Partikeln (TSS) und die Bestimmung des pH. Die Auswahl geeigneter Flockungsmittel hängt auch von der Art der gebildeten Flocken, in Kombination mit der Behandlung, die den Flockungsprozess folgt, ab. Wenn als Postflockungsprozess Filtration oder Zentrifugation folgen, sollten Polymere verwendet werden, die große und poröse Flöckchen bilden, wie im Fall der modifizierten Chitosane AG95 und AG97. Andererseits verlangen Geräte zur Klärung von Abwässern dichte Flocken, wie solche, die beim Einsatz von PolyDADMACs, kommerziellen Chitosanen, Oilbreaks und den modifizierten Chitosanen GA35, GA41 und AG79 entstehen. In Bezug auf die Wasserqualität erhält man mit einigen der verwendeten Polymere so niedrige Werte von CSB, TOC und BSB5, dass wie im Falle von P187K (PolyDADMAC) und GA41 (modifiziertes Chitosan) keine biologische Sekundärbehandlung notwendig ist. Im Falle der anderen Polymere ist eine biologische Behandlung nötig, um die vorgeschriebenen Grenzen zu erreichen. Die pH-Werte der modifizierten Chitosane (außer der AG97), der im Labor hergestellten PolyDADMACs und des Oilbreak OCAA sind alle in Bereich der vorgeschriebenen Grenzen. Die Anwendbarkeit von Biopolymeren als Flockungsmittel für die Ölschlammentwässerung ist ein relativ neuer Forschungsbereich. Als Folge der wachsenden Nachfrage nach umweltfreundlichen Technologien sowie erneuerbarer Ressourcen hat das Interesse an natürlichen Flockungsmitteln zugenommen. Das Aminopolysaccharidchitosan und dessen modifizierte Produkte haben hervorragende Eigenschaften wie Biokompatibilität, Biodegradierbarkeit, Hydrophilie, Adsorption, die Fähigkeit zur Flockung und antibakterielle Eigenschaften. Diese natürlichen Polymere, die aus Meeresfrüchte-Industrieabfallprodukten gewonnen werden, sollten als Restöl-Adsorbentien bei der Aufarbeitung jedes ölhaltigen Abwassers sehr nützlich sein und können zu den vielversprechendsten Kandidaten als Ersatz der synthetischen Flockungsmittel werden.

Made available in DSpace on 2014-12-17T14:09:17Z (GMT). No. of bitstreams: 1 CiceroSL_TESE.pdf: 5334902 bytes, checksum: 41714ced8f45a82dbc84b8d2449a7bee (MD5) Previous issue date: 2014-03-21 / The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery / A borra oleosa (BO) de petr?leo ? uma mistura complexa de hidrocarbonetos, impurezas org?nicas, inorg?nicas e ?gua. Um dos grandes problemas encontrados atualmente na ind?stria de petr?leo ? o gerenciamento (acondicionamento, armazenamento, transporte e destino) de res?duos. Os nanomateriais (catalisadores) mesoporosos e microporosos s?o considerados promissores em processos de refino de petr?leo e como adsorventes para prote??o ambiental. O objetivo deste trabalho foi estudar a BO de petr?leo oriunda do processamento prim?rio (bruta e tratada) e res?duo de v?cuo, com aplica??o de an?lise termogravim?trica, t?cnica de pir?lise t?rmica e catal?tica com nanomateriais, visando a produ??o de derivado de petr?leo. As borras extra?das em um equipamento soxhlet foram analisadas por an?lise elementar, cromatografia em camada fina, termogravimetria (TG) e pir?lise acoplado a um cromatogr?fico gasoso/espectro de massa (Py-GC/MS). Os catalisadores AlMCM-41 e AlSBA-15 foram sintetizados com uma raz?o molar de s?licio/alum?nio de 50 (Si/Al = 50), usando tetraetilortossilicato (TEOS) como fonte de sil?cio e pseudobuhemita (AlOOH) como a fonte de alum?nio. Os catalisadores indicam que os materiais apresentaram estrutura hexagonal, ?rea espec?fica de 783,6 m2/g para o AlMCM-41, 600 m2/g para o AlSBA-15.1 e 377 m2/g para o AlSBA-15.2). A BO extra?da apresentou de 65 a 95% de componentes org?nicos (?leo), de 5 a 35% de componentes inorg?nicos (sais e ?xidos) e diferentes composi??es dos derivados. Os catalisadores tipo AlSBA-15 apresentaram melhor desempenho na obten??o dos derivados de petr?leo, aumentando em 20% a produ??o de querosene e gas?leo leve. O potencial energ?tico da BO foi elevado, pois ela pode ser utilizada como combust?vel e processada com outras cargas pesadas do petr?leo para a produ??o de diferentes derivados de petr?leo

Oily wastewater produced from petroleum and petrochemical refining processes is one of the gravest environmental threats. Oil waste ending up in sewers and dumps each year is equal to 25 times the amount of crude oil spilled in the Exxon Valdez accident (1989). Oil/Water separation covers a broad spectrum of industrial process operations. There are many techniques employed depending on each situation. The byproduct of water recovery from oily wastewater is a sludge rich in oil, surfactants and particles (oily sludge). The oily sludge still contains significant amounts of waters, which need to be recovered prior to its disposal. The use of polyelectrolytes for the flocculation of the emulsified oil and its separation from the aqueous phase is usually one of the steps of the wastewater as well as oily sludge treatment process. The efficiency of polyelectrolytes as floculants is quite often evaluated via trial and error and the appropriate polymer is selected according to the case. Even in scientific investigations it is rather common to use industrial oily sludge samples. The industrial oily sludge is characterized and treated by polyelectrolytes. Nevertheless industrial oily sludge is quite complicated and variable to be approximated by a model. For the systematic study of polyelectrolytes efficiency a stable, realistic and well-defined oily sludge model is necessary. In the present work an oily sludge model was successfully developed and characterized. The model consists on water, oil (kerosene), surfactant (sodium dodecyl sulphate, SDS) and clay particles (Blauton). The emulsifying efficiency of the surfactant and the clay were studied independently. The interactions between the surfactant and the clay including adsorption of the former on the later and cation exchange reactions were investigated. The four components were finally combined to form a series of emulsions varying the relative amounts of the emulsifiers for the highest stability to be encountered. Having concluded on the composition of the oily sludge model the efficiency of various polyelectrolytes was evaluated. Commercial natural (chitosans), synthetic (PolyDADMACs) polyelectrolytes and oilbreaks as well as lab-scale semi-synthetic polymers (modified chitosans) were tested. The flocculation efficiency was determined based on the amount and quality of water that was recovered as well as on the floc stability, size and sedimentation speed. The recovered water was characterized according to the environmental protection agency (EPA). The analysis included measurements on: total organic carbon (TOC), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total suspended solids (TSS) and pH. Selection of the appropriate flocculant also depends on the type of flocs formed in combination to the treatment following the flocculation. When filtration or centrifugation is used as a post-flocculation process the appropriate polymers are those that form large and porous flocs, as the case of the modified chitosans AG95 and AG97. Clarification devices on the other hand require dense flocs as these produced by the use of PolyDADMACs, commercial chitosans, oilbreaks and modified chitosans GA35, GA41 and AG79. Regarding the water quality, some of the polymers used that have low values of COD, TOC and BOD5, may not need the secondary treatment (biological) prior to discharge, such as P187K (PolyDADMAC) and GA41 (modified chitosan). The others require a biological treatment for the regulation limits to be reached. The pH values of modified chitosans (except of AG97), lab-scale PolyDADMACs and an oilbreak (OCAA) are all in range of the regulation limits. The applicability of biopolymers as flocculants for oil sludge dewatering is a relatively new field of investigation. As a consequence of the growing demand for environmentally friendly technologies as well as renewable resources the interest on natural flocculants has increased. The aminopolysaccharide chitosan and its modified derivatives have outstanding properties such as biocompability, biodegradability, hydrophilicity, adsorption, flocculating ability and antibacterial properties. These natural polymers derived from the sea-food industry waste products would be very useful as residue oil adsorbents in any oily wastewater and can be among the most promising candidates as a replacement of the synthetic flocculants. / Ölhaltiges Abwasser, das bei Erdöl- und petrolchemischen Raffinierungsprozessen entsteht, ist eine der größten Umweltgefahren. Dieses Altöl landet jedes Jahr in der Kanalisation und in Deponien. Es handelt sich dabei um die 25-fache Menge an Rohöl, die beim Unfall der Exxon Valdez (1989) ausgeflossen ist. Die Öl/Wasser-Trennung überspannt ein breites Spektrum industrieller Prozesse. Es gibt viele Techniken, die abhängig von jeder Situation eingesetzt werden. Das Nebenprodukt bei der Abtrennung von Wasser aus ölhaltigen Abwässern ist ein Schlamm (Ölschlamm), der reich an Öl, Tensiden und Partikeln ist. Der Ölschlamm enthält noch bedeutende Mengen an Wasser, die vor ihrer Entsorgung verwertet werden müssen. Die Verwendung von Polyelektrolyten zur Ausflockung des emulgierten Öls und seine Trennung von der wässrigen Phase ist in der Regel einer der Schritte zur Behandlung von Abwässern sowie ölhaltigen Schlämmen. Die Effizienz von Polyelektrolyten als Flockungsmittel wird ganz häufig über Versuch und Fehler bewertet, und das passende Polymer wird entsprechend dem jeweiligen Fall ausgewählt. Sogar in wissenschaftlichen Untersuchungen ist es eher üblich, industrielle Ölschlamm-Proben zu verwenden. Der industrielle Ölschlamm wird charakterisiert und mit Polyelektrolyten behandelt. Dennoch ist der industrielle Ölschlamm ziemlich kompliziert und variabel und muss durch ein Modell angenähert werden. Für die systematische Untersuchung der Effizienz von Polyelektrolyten als Flockungsmittel ist ein stabiles, realistisches und klar definiertes Ölschlamm-Modell notwendig. In der vorliegenden Arbeit wurde ein Ölschlamm-Modell erfolgreich entwickelt und charakterisiert. Das Modell besteht aus Wasser, Öl (Kerosin), Tensid (Natriumdodecylsulfat, SDS) und Tonteilchen (Blauton). Die Emulgiereffizienz des Tensids und des Tons wurden unabhängig voneinander untersucht. Die Wechselwirkungen zwischen dem Tensid und dem Ton, die sowohl die Adsorption des Ersteren auf dem Letzteren einschließen als auch einen Kationenaustausch, wurden untersucht. Die vier Komponenten des Ölschlamm-Modells wurden schließlich kombiniert und es wurde eine Reihe von Emulsionen hergestellt, bei denen die relativen Mengen der Emulsionsmittel verändert wurden, um eine möglichst hohe Stabilität zu erreichen. Nachdem ein geeignetes Ölschlamm-Modell zur Verfügung stand, wurde die Effizienz der verschiedenen Polyelektrolyte als Flockungsmittel bewertet. Kommerzielle natürliche (Chitosane), synthetische (PolyDADMACs) Polyelektrolyte und Oilbreaks sowie Labor-semi-synthetische Polymere (modifizierte Chitosane) wurden getestet. Die Flockungseffizienz wurde sowohl basierend auf der Menge und Qualität des Wassers, das zurückgewonnen wurde, als auch bezogen auf die Flockenstabilität, die Flockengröße und die Sedimentationsgeschwindigkeit bestimmt. Das zurückgewonnene Wasser wurde entsprechend der Vorschriften der Behörde für Umweltschutz (EPA) charakterisiert. Die Analysen enthielten die Bestimmung des gesamten organischen Kohlenstoffs (TOC), des chemischen Sauerstoffbedarf (CSB), des biochemischen Sauerstoffbedarfs (BSB5), des Gesamtgehalts an suspendierten Partikeln (TSS) und die Bestimmung des pH. Die Auswahl geeigneter Flockungsmittel hängt auch von der Art der gebildeten Flocken, in Kombination mit der Behandlung, die den Flockungsprozess folgt, ab. Wenn als Postflockungsprozess Filtration oder Zentrifugation folgen, sollten Polymere verwendet werden, die große und poröse Flöckchen bilden, wie im Fall der modifizierten Chitosane AG95 und AG97. Andererseits verlangen Geräte zur Klärung von Abwässern dichte Flocken, wie solche, die beim Einsatz von PolyDADMACs, kommerziellen Chitosanen, Oilbreaks und den modifizierten Chitosanen GA35, GA41 und AG79 entstehen. In Bezug auf die Wasserqualität erhält man mit einigen der verwendeten Polymere so niedrige Werte von CSB, TOC und BSB5, dass wie im Falle von P187K (PolyDADMAC) und GA41 (modifiziertes Chitosan) keine biologische Sekundärbehandlung notwendig ist. Im Falle der anderen Polymere ist eine biologische Behandlung nötig, um die vorgeschriebenen Grenzen zu erreichen. Die pH-Werte der modifizierten Chitosane (außer der AG97), der im Labor hergestellten PolyDADMACs und des Oilbreak OCAA sind alle in Bereich der vorgeschriebenen Grenzen. Die Anwendbarkeit von Biopolymeren als Flockungsmittel für die Ölschlammentwässerung ist ein relativ neuer Forschungsbereich. Als Folge der wachsenden Nachfrage nach umweltfreundlichen Technologien sowie erneuerbarer Ressourcen hat das Interesse an natürlichen Flockungsmitteln zugenommen. Das Aminopolysaccharidchitosan und dessen modifizierte Produkte haben hervorragende Eigenschaften wie Biokompatibilität, Biodegradierbarkeit, Hydrophilie, Adsorption, die Fähigkeit zur Flockung und antibakterielle Eigenschaften. Diese natürlichen Polymere, die aus Meeresfrüchte-Industrieabfallprodukten gewonnen werden, sollten als Restöl-Adsorbentien bei der Aufarbeitung jedes ölhaltigen Abwassers sehr nützlich sein und können zu den vielversprechendsten Kandidaten als Ersatz der synthetischen Flockungsmittel werden.