O objetivo deste trabalho foi investigar o desempenho de uma membrana comercial na remoção de um metal pesado (níquel) de efluentes sintéticos, por osmose inversa. Na primeira etapa foi realizada uma comparação com os resultados obtidos com soluções de alimentação contendo sais, como NaCl, NaNO3 e Ni(NO3)2.6 H2O, nas concentrações de 50, 100 e 200 ppm, e nas pressões de 10, 20 e 26 bar. Os resultados mostraram que a influência da concentração e da pressão aplicada ao sistema não afetaram as rejeições de forma significativa. Na segunda etapa, como os parâmetros não influíram significativamente na rejeição dos sais, optou-se, pela aplicação de uma pressão de operação de 10 bar, para avaliar a eficiência de remoção de níquel. A membrana utilizada, constituída de poliamida, modelo HR98PP e fornecida pela DOW/Filmtec, apresentou uma boa permeabilidade hidráulica. Os resultados mostraram que para todas as concentrações testadas, as rejeições de níquel ultrapassaram 96%, comprovando a boa seletividade deste tipo de membrana na rejeição do referido metal, com fluxos de permeado variando entre 4,78 e 5,55 L/h.m2 , sob pressão de operação de 10 bar. Para estudar o efeito do tamanho iônico na rejeição da membrana, o níquel foi complexado pela adição de um agente quelante na solução de alimentação. O agente escolhido foi o Na2EDTA, devido à formação de um complexo estável com o níquel e por ser um agente não prejudicial à saúde humana. Os resultados com adição de EDTA indicaram um aumento na rejeição de níquel, atingindo o índice máximo de 98,22 %, partindo-se de uma solução com 40,39 ppm de Ni2+, e confirmam que o processo de osmose inversa com a membrana HR98PP é altamente adequado para o tratamento de efluentes contendo níquel / The present work aim to investigate the performance of commercial membrane (HR98PP) at reverse osmosis process for nickel removal from synthetic effluents. The results was obtained by using salt solution of NaCl, NaNO3 and Ni(NO3)2.6 H2O at different feed concentration (50, 100 and 200 mg/L) and pressure (10, 20 and 26 bar), as drive-force of process. The membrane performance showed a good hydraulic permeability (Lp) and nickel removal at 10 bar. This condition was used to investigate the influence of EDTA, as chelate agent, on nickel rejection when a feed solution with lower Ni2+ concentration (≈ 40 mg/L) was prepared. The EDTA was chosen due to the stable complex formations and because this agent in not a prejucial element to human health and to environment. In this case, the HR98PP membrane was showed a high nickel rejection (≈ 98%), using feed solution containing 40,39 mg/L Ni2+. However, it is suitable for the wastewater nickel treatment

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-18T12:30:31Z No. of bitstreams: 1 ADEMIR MORAIS DE MEDEIROS - DISSERTAÇÃO (PPGEQ) 2017.pdf: 3204134 bytes, checksum: c8135684c13cdcbef03ebfe63c7a1c99 (MD5) / Made available in DSpace on 2018-10-18T12:30:31Z (GMT). No. of bitstreams: 1 ADEMIR MORAIS DE MEDEIROS - DISSERTAÇÃO (PPGEQ) 2017.pdf: 3204134 bytes, checksum: c8135684c13cdcbef03ebfe63c7a1c99 (MD5) Previous issue date: 2017-10-30 / Capes / A dessalinização é um processo bastante difundido e utilizado no mundo para o tratamento de águas de diversas fontes hídricas as quais necessitam de tratamento para tornar-se potável e assim promover a segurança hídrica e a manutenção da vida, embora pouco utilizada na proporção necessária, a dessalinização de águas no Nordeste Brasileiro vem se tornando uma técnica bastante requisitada devido sua eficiência no tratamento de águas. O objetivo desta pesquisa foi avaliar a qualidade do permeado de um sistema hibrido de membranas para fins de dessalinização de águas salobras com a remoção do gás carbônico por uma torre de resfriamento, avaliando o desempenho do processo de separação por membrana para tratamento de águas através de estudo avaliativo dos dados reais com os simulados ambos para o permeado da OI. Os dados teóricos são os resultados obtidos a partir de análises reais realizadas nas águas do presente trabalho, inseridos no SOFWARE ROSA® 8.0.3 e realizada as simulações. No presente trabalho utilizou-se a membrana polimérica de Osmose Inversa (BW30 4040) na simulação e nos experimentos de bancadas. A partir da simulação foi possível ajustar as pressões de operação para os seguintes valores: 6, 9, 11, e 13 bar, para água de superfície e 13 e 15 bar para água de poço. Avaliou-se a rejeição de sais (%RS) obtendo valores próximos de 98 % para o permeado. Estudou-se por meio de uma torre de resfriamento como um pós-tratamento, a remoção de CO2 que apresentou como efeito, a diminuição do pH do permeado. Verificou-se através de análises que após a torre de ocorreu uma remoção parcial média de dióxido de carbono de cerca 75 %. / Desalination is a widely used process in the world for the treatment of water from a variety of water sources, which requires treatment to become potable and thus promote water safety and life-support, although little used in the necessary proportion, to desalination of water in the Brazilian Northeast has become a highly requested technique due to its efficiency in water treatment. The objective of this research was to evaluate the permeate quality of a hybrid membrane system for desalination of brackish water with the removal of carbon dioxide by a cooling tower, evaluating the performance of the membrane separation process for water treatment through evaluation of the real data with the simulated ones for the RO permeate. Theoretical data are the results obtained from real analyzes performed in the waters of the present work, inserted in SOFWARE ROSA® 8.0.3 and the simulations were performed. In the present work the polymer membrane of Reverse Osmosis (BW304040) was used in the simulation and bench experiments. From the simulation it was possible to adjust the operating pressures to the following values: 6 bar 9 bar, 11bar, and 13 bar for surface water and 13 bar and 15 bar for well water. The salt rejection (% SR) was evaluated, obtaining values close to 98% for the permeate. It was studied by means of a cooling tower as a post-treatment, the removal of CO2 that had as effect, the decrease of the pH of the permeate. It was verified through analyzes that after the tower a mean partial removal of carbon dioxide of about 75% occurred.

O objetivo deste trabalho foi investigar o desempenho de uma membrana comercial na remoção de um metal pesado (níquel) de efluentes sintéticos, por osmose inversa. Na primeira etapa foi realizada uma comparação com os resultados obtidos com soluções de alimentação contendo sais, como NaCl, NaNO3 e Ni(NO3)2.6 H2O, nas concentrações de 50, 100 e 200 ppm, e nas pressões de 10, 20 e 26 bar. Os resultados mostraram que a influência da concentração e da pressão aplicada ao sistema não afetaram as rejeições de forma significativa. Na segunda etapa, como os parâmetros não influíram significativamente na rejeição dos sais, optou-se, pela aplicação de uma pressão de operação de 10 bar, para avaliar a eficiência de remoção de níquel. A membrana utilizada, constituída de poliamida, modelo HR98PP e fornecida pela DOW/Filmtec, apresentou uma boa permeabilidade hidráulica. Os resultados mostraram que para todas as concentrações testadas, as rejeições de níquel ultrapassaram 96%, comprovando a boa seletividade deste tipo de membrana na rejeição do referido metal, com fluxos de permeado variando entre 4,78 e 5,55 L/h.m2 , sob pressão de operação de 10 bar. Para estudar o efeito do tamanho iônico na rejeição da membrana, o níquel foi complexado pela adição de um agente quelante na solução de alimentação. O agente escolhido foi o Na2EDTA, devido à formação de um complexo estável com o níquel e por ser um agente não prejudicial à saúde humana. Os resultados com adição de EDTA indicaram um aumento na rejeição de níquel, atingindo o índice máximo de 98,22 %, partindo-se de uma solução com 40,39 ppm de Ni2+, e confirmam que o processo de osmose inversa com a membrana HR98PP é altamente adequado para o tratamento de efluentes contendo níquel / The present work aim to investigate the performance of commercial membrane (HR98PP) at reverse osmosis process for nickel removal from synthetic effluents. The results was obtained by using salt solution of NaCl, NaNO3 and Ni(NO3)2.6 H2O at different feed concentration (50, 100 and 200 mg/L) and pressure (10, 20 and 26 bar), as drive-force of process. The membrane performance showed a good hydraulic permeability (Lp) and nickel removal at 10 bar. This condition was used to investigate the influence of EDTA, as chelate agent, on nickel rejection when a feed solution with lower Ni2+ concentration (≈ 40 mg/L) was prepared. The EDTA was chosen due to the stable complex formations and because this agent in not a prejucial element to human health and to environment. In this case, the HR98PP membrane was showed a high nickel rejection (≈ 98%), using feed solution containing 40,39 mg/L Ni2+. However, it is suitable for the wastewater nickel treatment

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21308号 / 工博第4506号 / 新制||工||1701(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 清水 芳久, 教授 伊藤 禎彦 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Reverse osmosis (RO) is widely used for water reuse and desalination. Although RO membranes are known for their high salt rejection and practical permeate flux, their performance can be impaired by fouling, and their removal of some disinfection byproducts and their precursors (e.g., bromide, N-Nitrosodimethylamine [NDMA]) does not meet drinking water standards. RO membrane modifications have been widely studied to overcome these limitations. In this research, RO membranes were grafted with cationic polymers to induce a positive charge on the RO membrane surface. This modification aimed at enhancing the rejection of negatively charged bromide ions by removing them from solution by binding them to the membrane surface. The results showed that the modified (positively charged) RO membranes achieved lower rejection (82% rejection) for bromide ions compared to the unmodified ones (94.5% rejection). This behavior was likely a result of increased concentration polarization of the bromide ions at the membrane surface and/or increase in porosity of the modified membranes. Calculations based on the film theory indicate that the concentration of bromide ions at the surface of the modified membrane was 1371 ppm compared to 1307 ppm at the surface of the unmodified membrane. Evidently, the polymer attraction energy was not sufficient to keep the bromide ions attached to the membrane surface and prevent their diffusion across the membrane. Although the goal of the modification in the current study (i.e., enhancing removal of bromide ions) was not met, the permeate flux of the modified membrane was improved compared to the unmodified one. The literature suggests that increasing flux after modification is likely a result of increase in membrane pore size and hydrophilicity. In addition to the experimental work conducted in this study, a multi-criteria decision analysis was performed to prioritize research on surface modifications of reverse osmosis membranes. It was found that surface modifications have been mainly focused on reducing membrane fouling and to a much lower extent on removal of disinfection byproducts and their precursors. The RO membrane modification alternatives for fouling reduction and N-Nitrosodimethylamine (NDMA) removal were ranked based on multiple criteria using the Analytical Hierarchy Process (AHP) and the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). This multi-criteria decision analysis process resulted in the identification of the top five promising modifications to reduce fouling and improve NDMA rejection. Grafting and coating the RO membranes with complex polymeric salts were the highest ranked modification approaches to reduce fouling. Heat-treatment of RO membranes achieved the highest NDMA rejection (98%); however, this technique was the second highest ranked modification approach for NDMA removal because it scored lower for other evaluation criteria.

This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.

The purpose of this work is to develop and evaluate electroding methods for a reverse osmosis (RO) membrane that results in an in situ sensor able to detect RO membrane protein fouling. Four electroding techniques were explored: i) gold exchange-reduction, ii) encapsulated carbon grease, iii) "direct assembly process" (DAP), and iv) platinized polymer graft. The novel platinized polymer graft method involves chemically modifying the RO membrane surface to facilitate platinization based on the hypothesis that deposition of foulant on the platinized surface will affect platinum/foulant/solution interfacial regions, thus sensor impedance. Platinized polymer graft sensors were shown to be sensitive to protein fouling. Electrodes were characterized by their electrical properties, SEM and XPS. Assembled sensors were evaluated for sensitivity to electrolyte concentration and protein fouling. Micrographs showed coating layers and pre-soak solution influence gold exchange-reduction electrode formation. High surface resistance makes gold exchange-reduction an unsuitable method. Concentration sensitivity experiments showed carbon grease and DAP electroding methods produce unusable sensors. Carbon grease sensors have time-dependent impedance response due to electrolyte diffusion within the micro-porous polysulfone support. DAP electroded sensors proved quite fragile upon hydration; their impedance response is transient and lacks predictable trends with changes in concentration. A parametric study of the platinized polymer graft method shows amount of grafted monomer correlates to grafting time, and deposited platinum is a function of exchange-reduction repetitions and amount of grafted monomer. Platinized polymer graft sensors were fouled in both dead-end and cross-flow RO systems, and their impedance trends, while varying between sensors, indicate protein-fouling sensitivity. / Master of Science

This research covers simulation of Cyclic Steam Stimulation (CSS) Thermal Enhanced Oil Recovery (TEOR) and potential benefits for use of produced water in agriculture and food security, using a case study of oil fields in South Sudan. Oil production in many oil fields in South Sudan is declining, has high water cut, and low recovery factor. It is costly to manage the produced water. At the same time, agriculture in South Sudan is almost entirely rainfed, and this affects food security. Produced water can be managed by using it for TEOR and agriculture to solve water management issues, enhance oil production, reduces competition over water resources, and improve food security. Field A is a deep reservoir in South Sudan with oil gravity between 25 and 31 API. There are limited and mixed results from applications of TEOR methods in deep reservoirs. As such history matching and sensitivity analysis, and CSSS TEOR simulations were performed to examine most uncertain reservoir properties and the compatibility of Field A properties with CSS TEOR method. The results of simulation show that aquifer volume (AQV) and productivity index (PI) are the most uncertain property that affect reservoir pressure; cumulative oil, gas, and water production; water cut; and gas oil ratio. CSS TEOR simulation was not successfully due to the high API gravity suggesting that Field A is not a good candidate for CSS TEOR. The produced water is sufficient to irrigate large areas of farms and watering thousands of livestock. However, analysis results from untreated water; water treated by demulsifer-defoamer and bioremediation shows high total dissolved solids (TDS) and sodium absorption ratio (SAR) values. Therefore, reverse osmosis (RO) membrane technology was applied to treat the produced water. RO rejected more than 90% of elements in the produced water with exception of elements B, Cu, Pb, and Ca. Consequently, water from RO does not meet food and agriculture organization (FAO) standards for all uses in agriculture. ANOVA showed that there was no significant difference in TDS reductions between the different applied treatment technologies. Therefore, caution is needed when using statistical analysis to verify operationalization of RO technology which rejected more than 90% of the elements in the produced water. / Doctor of Philosophy / This research discusses how to increase oil production by injecting steam in the reservoir and leaving it to soak before the next injection and start of oil production, along with potential benefits for use of produced water in agriculture and food security, all using a case study of oil fields in South Sudan. In many oil fields in South Sudan the volume of oil produced is decreasing while that of water is increasing rapidly, so that now nearly 90% of the total fluids produced is water. Management of produced water can be very costly. Despite the large quantities of produced water, agriculture in South Sudan still depends on rain water, and this dependency on rain water can affect crop production and food security, and also cause conflict amongst nomads and farmers over water resources during the dry season. These problems can be mitigated by using produced water to increase oil production and then be applied for agricultural uses. The first study simulated steam injection in the reservoir in Oil Field A. The results showed that process of injection did not work well due to the properties of the oil in that formation, and therefore other methods may be needed to increase oil production in Field A. In the second study, water which is produced together with oil (produced water) was analyzed to check its quality. This analysis determined that the water has very high concentration of total dissolved solids. Treatment methods that have been applied in the oil fields for treating produced water do not currently make the water clean enough to be use for agriculture use. Therefore, reverse osmosis membrane technology was applied to reduce the concentration of the elements in the water. Reverse osmosis treatment technology is capable of removing 90 % concentration of most elements in the produced water, but some potentially harmful elements, such as boron, remained. As a result, the water treated by reverse osmosis can only be used for livestock watering unless additional treatment methods are adopted to reduce boron concentrations to acceptable level.

This thesis deals with an agricultural wastewater treatment (liquid digestate) by membrane technology. There is a fundamental description of characteristics of membrane technology with regard to application of agricultural wastewater treatment in this thesis. Experimental device for treatment of liquid digestate is designed and it consists of three steps – microfiltration, ultrafiltration and reverse osmosis. The first step consists of four filters with different pore sizes (80, 25, 10 and 5 µm). The second step is ultrafiltration and the third and key step is reverse osmosis. In the final step monovalent ions such as NH4+ are separated. Reverse osmosis consists of two stage system which results in higher recovery. Three experiments were carried out in order to verify the efficiency of separation dissolved solids.