Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1994. / Vita. Abstract. Includes bibliographical references (leaves 65-68). Also available via the Internet.

Waste oil emulsions are generated in several manufacturing processes. Such emulsions not only affect the efficacy of wastewater treatment but also influence the water quality of the effluent. Therefore, these waste oil emulsions that have to be treated before being released into the environment. Many processes have been developed for demulsifying such materials and microwave irradiation has been shown to be most effective in this respect. It does not require the addition of chemicals and the oil recovered from the emulsion can be reused. With microwave irradiation, there are two main mechanisms occurring simultaneously. One is the rapid increase of temperature which reduces the viscosity of the emulsion. The other is molecular rotation, which neutralizes the Zeta potential because of the rearrangement of electrical charges surrounding the water droplets. Hence, water droplets coalesce and result in the separation of the emulsion. Addition of inorganic salts has also been shown to improve the efficiency of microwave irradiation in demulsification owing to an increase in solvent conductivity, which accelerates the heating rate. This process is termed salt-assisted microwave irradiation. In the present study, we propose that NaCl and artificial seawater can be an economical source of cations required in salt-assisted microwave demulsification. Our experiments included batch tests of emulsion characteristics and the effects of microwave operating conditions on demulsification rate and separation efficiency of three oil-in-water (O/W) emulsions (mineral oil, vegetable oil, and mineral-oil/vegetable-oil mix). First study was aimed to examine the demulsification of an O/W cutting oil emulsion with the addition of NaCl under microwave irradiation. This work investigates the effect of a set of operating variables, including irradiation time, irradiation power, dosage of NaCl, settling time, pH and the initial oil concentration, on the separation efficiency in the treatment of an oil in water (O/W) type cutting oil emulsion by microwave assisted demulsification. As a result of a series of batch demulsification tests a set of optimum operating conditions was found, consisting of 2 min of microwave irradiation at 280 W, the addition of 14 g/L of NaCl, 60 min settling time, and at a pH of 9.5. A separation efficiency of 93.8% was obtained with these conditions for 50 mL of cutting oil emulsion with an initial oil content of 10 g/L. The objective of the second study was to examine the demulsification of an O/W cutting oil emulsion, an olive oil emulsion, and a 1:1 cutting-oil/olive-oil emulsion mix, using a proposed process termed as seawater-assisted microwave irradiation demulsification. We conducted batch demulsification tests on 50-mL aliquots with an initial oil content of 10 g/L, and found that the separation efficiencies of a cutting oil emulsion, an olive oil emulsion, and a cutting-oil/olive-oil mix reached 93.1%, 92.6%, and 93.2%, respectively, using our optimum operating conditions, which were 40 sec of microwave irradiation at 700 W, a 60 min settling time, and addition of 12%, 32%, and 20% (all v/v) of artificial seawater, respectively. Using this set of operating conditions, a decrease in solution pH was found to significantly increase the demulsification efficiency after addition of inorganic acid, whereas an increase in the concentration of surfactant, sodium dodecyl sulfate (SDS), resulted in a decrease in efficiency. In addition, our test data were explored using a stepwise regression method, yielding a multi-variable equation. This empirical equation was able to describe separation efficiency rather well, after exclusion of tests showing separation efficiency below 40% and temperature higher than the boiling point. This study could provide essential information related to O/W emulsions using salt-assisted microwave demulsification.

No description available.

No description available.

No description available.

Research currently being conducted at Virginia Tech has produced a viable pesticide wastewater clean-up procedure using biologically based materials. The system consists of two steps. First, pesticide laden wastewater is mixed with a lignocellulosic sorbent such as peat moss in a demulsification and sorption step. Second, the wastewater filtered rinsate is then passed through a packed column containing the same sorbent in a column sorption and filtration step. Although the system yielded adequate results and performed the tasks commensurate with its design, the original batch demulsification and sorption phase of the process had several operational problems. Namely, the system was large and not very portable, the recirculation system was not very reliable, and the entire step one process was laborious and time consuming to execute. These problems and limitations prompted the redesign of the step one process into a new, more efficient system. The new system consists of a steel frame similar to the old system. However, the new frame is smaller, lighter, more portable, and one person can easily operate and maneuver the new system. In addition, the new system provides a safer work environment for the operator. The frame surrounds the barrel and liner like a cage so that if the hand winch or the cable fails when lifting the liner out of the barrel, the operator is protected. The recirculation system has been automated such that it 1s self priming, and turns off when all the rinsate contained between the inner liner and outer barrel has been pumped dry. The come-a-long has been replaced with a hand wench that makes loading and unloading of the inner liner easier. Finally, the same pump that is used to recirculate the rinsate is used to transfer the rinsate onto the column for the second sorption and filtration step. There is now no need for additional pumps. After the system was designed and developed, it was tested on two pesticides, atrazine and metolachlor, to determine if the new system yielded results comparable to the old system. The atrazine concentration in the rinsate was reduced from an initial 721 mg/kg (ppm) in step one to 2 mg/kg in the step two column sorption and filtration phase. This represents an atrazine reduction of 99.72% over the entire two step process. The metolachlor concentration in the rinsate was reduced from an initial 704 mg/kg in step one to 30 mg/kg in the step two column sorption and filtration phase. This represents a metolachlor reduction of 95.74% over the entire two step process. The percent reduction of pesticide from the rinsate in the new system is comparable to the 99% reductions obtained using the old system. / Master of Science

Spent oil based drilling fluid and cutting wastes are global liabilities due to their hazardous hydrocarbon content which impacts negatively on flora, fauna, and global carbon footprint. The formulation of two demulsifiers to ensure chemically enhanced phase separation of this waste into oil, water and solid components was successfully carried out in addition to recycling the solid phase into PA6 nanocomposite materials. Initial characterisation of the untreated waste was carried out by Fourier Transform Infra Red (FTIR) for total petroleum hydrocarbon (TPH) analysis, Inductively coupled plasma optical emission spectrometry (ICPOES) for quantitative elemental analysis and Energy dispersive xray analysis (EDXA) for qualitative elemental composition amongst other characterisation methods. The analysis showed that the sample had a high hydrocarbon load of 662,500mg/kg and a high heavy metal load for Pb of 122mg/kg. No As, Cd, Hg were detected. The demulsifier formulations were composed of isopropanol, sodium dodecyl sulphate, poloxamer, sodium chloride, chitosan in 0.2M acetic acid and deionised water for demulsifier S4 and addition of phosphoric acid for demulsifier S3. Hydrocarbon reduction on the extracted solid phase nanofiller S3 and nanofiller S4 was 98.6% and 98.5% respectively after demulsification. The demulsified spent oil based drilling fluid solid extracts were below OSPAR regulation of < 1% oil on cutting by weight. However, recycling of the recovered solid was carried out in order to achieve environmentally sustainable management of the waste in Polyamide 6 (PA6) nanocomposite manufacture/fabrication. The formulation of different blends of PA6 nanocomposite materials from untreated, demulsifier treated and thermally treated drilling fluid and cuttings was successfully achieved. Nanocomposite leaching test showed Pb immobilisation. The flexural and compressive - modulus and strength of the PA6 were markedly improved in the presence of the nanofillers and glass fibre. This was attributed to the reinforcement, exfoliating, stiffening, rigidity effect of the nanofillers. S6 (untreated drilling fluid) nanofillers significantly improved the mechanical properties of PA6. This was attributed to the increased interfacial bonding between the fillers and the polymer matrix as a result of the petroleum hydrocarbon present in the sample. The Thermogravemetric analysis (TGA) results showed that nanocomposites PA6/S3 and PA6/S3/GF30 had improved the thermal stability of PA6 by 13.6% and 38.8% respectively compared to PA6/S2 and PA6/S2/GF30 (simulated commercial nanocomposite materials) that improved PA6 by 9.7% and 35.8% respectively.

A reação entre resinas epóxi e polialquileno glicóis gera um aduto de elevado peso molecular que pode ter aplicações em diferentes segmentos, tais como polímeros usados na composição base de fluidos de têmpera, viscosificantes para lubrificantes e desemulsificantes de petróleo. As condições envolvendo a formação destes adutos possuem referências limitadas na literatura aberta e basicamente envolvem um polialquileno glicol com diferentes funcionalidades, tipicamente duas hidroxilas reagindo com os grupos epóxi presentes na resina epóxi que tipicamente possui funcionalidade igual a dois, a uma temperatura ao redor de 120°C na presença de catalisador de hidróxido de potássio (KOH). O presente trabalho avaliou a formação destes adutos considerando um delineamento experimental de resolução III onde as variáveis de controle foram temperatura, velocidade de agitação do meio reacional, velocidade de adição de resina epóxi, concentração de catalisador e relação molar entre a resina epóxi e o polialquileno glicol. Ao total onze experimentos foram realizados de acordo com o planejamento experimental e incluindo triplicata para avaliação do erro experimental. Diferenças significativas nas características físico químicas dos produtos obtidos tais como viscosidade, teor de epóxi residual e de performance de desemulsificação foram encontradas. Dois produtos apresentaram gelificação. Com um bom nível de confiabilidade estatística pode-se dizer que o peso molecular ponderal médio é influenciado principalmente pelo teor de catalisador seguido da temperatura e proporção molar entre resina epóxi e polialquileno glicol nesta ordem de importância. Com menor nível de significância a conversão é influenciada positivamente com respeito ao incremento do teor de catalisador e da temperatura e pela redução na proporção molar entre resina epóxi e polialquileno glicol. Apesar de terem sido atingidos elevados níveis de conversão de resina epóxi na maioria dos experimentos, pelas analises de GPC foi observado uma grande proporção de polialquileno glicol livre residual nos produtos. Pode-se observar também uma fraca correlação estatística positiva entre a qualidade da separação petróleo-água com respeito à conversão e ao peso molecular numérico médio dos produtos. / The reaction between epoxy resins and polyalkylene glycols generates an adduct of high molecular weight that may have applications in several sectors such as polymers for metal quenchant fluids, demulsifiers and viscosifiers for lubricating oil. The conditions involving the formation of these adducts have limited references in the open literature and basically it involves a polyalkylene glycol having different functionalities, typically two hydroxyl groups reacting with the epoxy groups present in the epoxy resin with typical functionality equal to two at a temperature around 120°C and in the presence of catalyst, potassium hydroxide (KOH). This study evaluated the formation of these adducts considering a resolution III experiment design where the controllable variables were temperature, stirring speed of the reaction medium, rate of addition of epoxy resin, catalyst concentration and molar ratio between the epoxy resin and polyalkylene glycol . In total eleven experiments were carried out according to the experimental design, including three replications at the center point to evaluate the experimental error. Significant differences in chemical and physical characteristics such as viscosity, residual epoxy content and performance of demulsification were found between the synthesized materials. Two products showed gelation. With a good level of statistical reliability it can be considered that the weight average molecular weight is mainly influenced by the amount of catalyst followed by temperature and mole ratio of epoxy resin to polyalkylene glycol in this order of importance. With lower significance level conversion is influenced positively with respect to the increment of the catalyst amount and temperature and by the decrease in molar ratio of epoxy resin and polyalkylene glycol. Despite achieving high levels of conversion of epoxy resin in most of the experiments, by GPC analysis it was observed a large proportion of free residual polyalkylene glycol in the products. It can be observed also a slight positive statistical correlation between the quality of oil-water separation with respect to conversion and number average molecular weight of the products.

A reação entre resinas epóxi e polialquileno glicóis gera um aduto de elevado peso molecular que pode ter aplicações em diferentes segmentos, tais como polímeros usados na composição base de fluidos de têmpera, viscosificantes para lubrificantes e desemulsificantes de petróleo. As condições envolvendo a formação destes adutos possuem referências limitadas na literatura aberta e basicamente envolvem um polialquileno glicol com diferentes funcionalidades, tipicamente duas hidroxilas reagindo com os grupos epóxi presentes na resina epóxi que tipicamente possui funcionalidade igual a dois, a uma temperatura ao redor de 120°C na presença de catalisador de hidróxido de potássio (KOH). O presente trabalho avaliou a formação destes adutos considerando um delineamento experimental de resolução III onde as variáveis de controle foram temperatura, velocidade de agitação do meio reacional, velocidade de adição de resina epóxi, concentração de catalisador e relação molar entre a resina epóxi e o polialquileno glicol. Ao total onze experimentos foram realizados de acordo com o planejamento experimental e incluindo triplicata para avaliação do erro experimental. Diferenças significativas nas características físico químicas dos produtos obtidos tais como viscosidade, teor de epóxi residual e de performance de desemulsificação foram encontradas. Dois produtos apresentaram gelificação. Com um bom nível de confiabilidade estatística pode-se dizer que o peso molecular ponderal médio é influenciado principalmente pelo teor de catalisador seguido da temperatura e proporção molar entre resina epóxi e polialquileno glicol nesta ordem de importância. Com menor nível de significância a conversão é influenciada positivamente com respeito ao incremento do teor de catalisador e da temperatura e pela redução na proporção molar entre resina epóxi e polialquileno glicol. Apesar de terem sido atingidos elevados níveis de conversão de resina epóxi na maioria dos experimentos, pelas analises de GPC foi observado uma grande proporção de polialquileno glicol livre residual nos produtos. Pode-se observar também uma fraca correlação estatística positiva entre a qualidade da separação petróleo-água com respeito à conversão e ao peso molecular numérico médio dos produtos. / The reaction between epoxy resins and polyalkylene glycols generates an adduct of high molecular weight that may have applications in several sectors such as polymers for metal quenchant fluids, demulsifiers and viscosifiers for lubricating oil. The conditions involving the formation of these adducts have limited references in the open literature and basically it involves a polyalkylene glycol having different functionalities, typically two hydroxyl groups reacting with the epoxy groups present in the epoxy resin with typical functionality equal to two at a temperature around 120°C and in the presence of catalyst, potassium hydroxide (KOH). This study evaluated the formation of these adducts considering a resolution III experiment design where the controllable variables were temperature, stirring speed of the reaction medium, rate of addition of epoxy resin, catalyst concentration and molar ratio between the epoxy resin and polyalkylene glycol . In total eleven experiments were carried out according to the experimental design, including three replications at the center point to evaluate the experimental error. Significant differences in chemical and physical characteristics such as viscosity, residual epoxy content and performance of demulsification were found between the synthesized materials. Two products showed gelation. With a good level of statistical reliability it can be considered that the weight average molecular weight is mainly influenced by the amount of catalyst followed by temperature and mole ratio of epoxy resin to polyalkylene glycol in this order of importance. With lower significance level conversion is influenced positively with respect to the increment of the catalyst amount and temperature and by the decrease in molar ratio of epoxy resin and polyalkylene glycol. Despite achieving high levels of conversion of epoxy resin in most of the experiments, by GPC analysis it was observed a large proportion of free residual polyalkylene glycol in the products. It can be observed also a slight positive statistical correlation between the quality of oil-water separation with respect to conversion and number average molecular weight of the products.

[pt] Emulsões podem ser formadas durante o processo de exploração dos reservatórios de petróleo. Essas emulsões podem trazer diversos prejuízos, como mudanças nas características dos óleos e problemas no bombeamento. Diante disso, aditivos químicos capazes de promover a desestabilização de emulsões de petróleo são importantes para otimizar o processo produtivo e mitigar os problemas causados. Há diversos estudos dedicados à avaliação de substâncias para atuar como desemulsificantes. Porém, a compreensão de como a estrutura química dos aditivos está correlacionada com as características físico-químicas dos óleos e emulsões ainda é escasso. Esse trabalho tem como objetivo entender como as características dos aditivos estão relacionadas com as particularidades de óleos parafínicos e asfaltênicos. Para isso, três óleos brasileiros foram usados para preparar e caracterizar emulsões água-óleo e avaliar sua estabilidade após o uso de diferentes aditivos. As emulsões preparadas com esses óleos apresentaram grandes diferenças nas propriedades reológicas. Entre elas, a viscosidade e gelificação em um dos óleos parafínicos, o que pode impactar diretamente na eficiência de desemulsificação devido à dificuldade de incorporação dos aditivos no bulk da emulsão. A estabilidade das emulsões foi estudada por testes de envelhecimento em diferentes condições de temperatura sem e com adição de diferentes aditivos: surfactantes, polímeros, ácidos orgânicos e inorgânicos e álcoois. De forma geral, aditivos anfifílicos com grupos aniônicos apresentaram melhor eficiência desemulsificante para todos os óleos. A aromaticidade, a acidez e o volume molecular dos aditivos também foram características importantes para a desemulsificação, porém, dependem da temperatura. Confirmou-se que a escolha de um desemulsificante para emulsões de petróleo depende da composição dos óleos e das características reológicas das emulsões formadas. Para emulsões de óleos parafínicos a temperatura foi determinante na eficiência de desemulsificação, enquanto para o óleo asfaltênico, a acidez influenciou mais. / [en] Emulsions can be formed during the exploration process of oil reservoirs. These emulsions, when unwanted, can bring several losses, such as loss of oil and changes in its characteristics and problems in pumping. Therefore, the development of chemical additives capable of promoting the destabilization of oil emulsions is important to optimize the production process and mitigate the problems caused. In the literature, there are several studies dedicated to the evaluation of substances to act as demulsifiers. However, the understanding of how the chemical structure of additives is correlated with the physicochemical characteristics of oils and emulsions is still scarce. This work aims to understand how the characteristics of the substances are related to the particularities of oils and their emulsions to better understand how demulsification occurs and also to propose additives with greater efficiency for the systems studied. To this end, three Brazilian oils were used to prepare water-oil emulsions and to evaluate the demulsifying capacity of different chemical additives. The stability of the emulsions was studied by aging tests under different temperature conditions without and with the addition of the different additives: surfactants, polymers, organic and inorganic acids and alcohols. The tests were carried out under different conditions to evaluate the effect of temperature mainly due to the high paraffin content in some oils. The characterization of the emulsions (without additives) showed large differences in rheological properties between the systems prepared with oils. These include viscosity, thixotropy and gelation in one of the paraffinic oils, which can directly impact the demulsification efficiency due to the difficulty of incorporating the additives into the emulsion bulk. From the aging tests, it was generally observed that amphiphilic substances with high interfacial activity and with anionic groups showed better demulsifying efficiency for all oils. The aromaticity, acidity and molecular volume of the additives were also important characteristics for demulsification, but they are temperature dependent. Finally, it was concluded that in general, the choice of a demulsifier for petroleum emulsions depends on the composition of the oils and the rheological characteristics of the emulsions formed. For paraffinic oil emulsions, the temperature was decisive for the demulsification efficiency, whereas, for the others, the acidity proved to be more decisive.