Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.

The esterification of lactic acid with ethanol over Lewatit S 100, strong cation ion exchange resin catalyst, was studied in counter current vapor-liquid contactor type differential reactor by feeding ethanol and lactic acid solution as vapor and liquid phases, respectively. The ethanol vapor phase was diluted by dry air and the water removal was achieved by the mass transfer of water from liquid to vapor phase. Effect of ethanol to lactic acid feed molar ratio and vapor flow rate on fractional conversion and water removal efficiency were tested at 40-70&deg / C of column temperature range. It was observed that Lewatit S 100 was adequate catalyst for esterification of lactic acid with ethanol. Increase in ethanol to lactic acid feed molar ratio enhanced both lactic acid conversion and water removal by upper product stream. However, lactic acid conversion was suppressed by the increase of inlet vapor flow rate because of the decrease in ethanol concentration in gas phase which affected both esterification reaction rate and mass transfer rate. The reaction temperature is the other important parameter that affects the mass transfer of ethanol from vapor to liquid phase. Although reaction rate and equilibrium conversion values were promoted by temperature, the lower solubility of ethanol in liquid phase limited the fractional conversion while promoted the water mass transfer from liquid to vapor phase. The optimized vapor phase velocity and temperature can yield higher conversions than the equilibrium conversion at the same temperature and initial composition. Therefore, low pressure organic acids such as lactic acid can be successfully esterified by using counter current V-L contactor type reactors and by using integrated reaction and separation units.

The synthesis of ion-exchange resin which can be used in various separation and chemical purposes, such as diffusion dialysis, electro dialysis, electrolysis and fuel cells has of considerable interest. For all these applications, the interactions of the ionic groups and the resulted morphologies are critical for establishing the unique properties. Considerable researches have been continued to understand the microstructure of these materials. The aim of this study is to synthesize polypropylene (PP) based ion exchange resins and to investigate their ion-exchange properties. In the first part of this study polypropylene was functionalized by grafting maleic anhydride onto the polypropylene and the product was characterized by ATR. The effect of maleic anhydride introduced to the grafting medium and the effect of the radical initiator on the maleic anhydride content of the MA-g-PP samples were investigated. In the second part, neutralization of the MA-g-PP samples with Na+, K+, Mg2+ and Ca2+ ions and peroxide cross-linking of neutralized MA-g-PP samples were performed. Characterization of the neutralized MA-g-PP samples were performed by ATR and SEM-EDX. In the last part of the study, ion exchange properties of MA-g-PP resins towards Cu2+, Co2+, Cd2+, Pb2+ and Fe3+ ions at different pHs were investigated by batch equilibrium method. Rate of metal uptake, concentration effect on the metal uptake and regeneration of the MA-g-PP samples were also examined.

iv The recovery of lactic acid from its dilute aqueous solutions is a major problem. The ester of lactic acid, namely, methyl lactate has a wide range of applications. The esterification of an aqueous solution of lactic acid with methanol is a reversible reaction. As excess of amount water is present in the reaction mixture, the conversion is greatly restricted by the chemical reaction equilibrium limitations. In this study the esterification kinetics of lactic acid with methanol both in the absence and presence of an ion exchange resin as a heterogeneous acid catalyst was investigated with isothermal batch experiments between 40 - 70 0 C and at atmospheric pressure. Self-polymerization of lactic acid was enlightened by considering the hydrolysis reaction of lactoyllactic acid at the reaction temperatures and at various initial concentrations. Both homogeneous and heterogeneous reaction rate constants were evaluated. Methyl lactate process development was also investigated. The process was based on the recovery of 10% lactic acid by reaction with methanol in a absorption column using ion-exchange resin Lewatit SPC-112 H+. The effect of various parameters including lactic acid concentration or reactant molar ratio, lactic acid feed flow rate, methanol and inert carrier rate on reactor performance were studied. The reaction of methyl lactate formation over the ion exchange resin catalyst was observed to be slower than the mass transfer rate whereas mass transfer of methanol in gas phase was the limiting step for methanol transfer to the liquid mixture. Mass transfer of water from liquid phase to the gas phase was controlled by the mass transfer resistance of liquid phase. Thus, it can be concluded that the counter-current gas-liquid reactors with acidic solid catalysts can be used as simultaneous reaction and separation equipment.

Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.

Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.

Orientador: Antonio Jose de Almeida Meirelles / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-04T02:50:19Z (GMT). No. of bitstreams: 1 Cren_ErikaCristina_M.pdf: 1127595 bytes, checksum: 7415435cfaea6997d1e6216cfc7a873c (MD5) Previous issue date: 2005 / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

The ability of natural zeolite and synthetic ion-exchange resin for ammonia removal from aqueous solution was studied through batch experiments. The results showed that both zeolite and ion-exchange resin were effective (up to 87% of removal) in eliminating ammonia from aqueous solution. Factorial design and response surface methodology were applied to evaluate and optimize the effects of pH, dose, contact time, temperature and initial ammonia concentration. Low pH condition was preferred with the optimum pH found to be 6 for both zeolite and ion-exchange resin. High dose generated high removal rate and low exchange capacity. Results of factorial design and response surface methodology showed that temperature was not a significant parameter. The model prediction was in good agreement with observed data (R2 = 0.969 for zeolite and R2 = 0.957 for resin, respectively). For zeolite, the optimum Qe was 22.90 mg/g achieved at pH=7 and initial ammonia concentration of 3000 mg/L. For ion-exchange resin, Qe of 28.78 mg/g was achieved at pH=6 and initial TAN concentration of 3000 mg/L. The reaction kinetics for both of them followed the Pseudo-second order kinetic model (R2=0.998 and R2=0.999, respectively). Equilibrium data were fitted to Langmuir and Freundlich isotherm models with Freundlich model providing a slightly better predication for zeolite (R2=0.992) and Langmuir providing more accurate prediction for ion-exchange resin (R2=0.996). The ion-exchange resin can be completely regenerated by 2N H2SO4.

abstract: In this study, the stereolithography (SLA) 3D printing method is used to manufacture honeycomb-shaped flat sorbents that can capture CO2 from the air. The 3D-printed sorbents were synthesized using polyvinyl alcohol (PVA), propylene glycol, photopolymer resin, and an ion exchange resin (IER). The one-factor-at-a-time (OFAT) design-of-experiment approach was employed to determine the best combination ratio of materials to achieve high moisture swing and a good turnout of printed sorbents. The maximum load limit of the liquid photopolymer resin to enable printability of sorbents was found to be 44%. A series of moisture swing experiments was conducted to investigate the adsorption and desorption performance of the 3D-printed sorbents and compare them with the performance of IER samples prepared by a conventional approach. Results from these experiments conducted indicate that the printed sorbents showed less CO2 adsorptive characteristics compared to the conventional IER sample. It is proposed for future research that a liquid photopolymer resin made up of an IER be synthesized in order to improve the CO2-capturing ability of manufactured sorbents. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2020

A análise química de solo fornece suporte para o manejo de sua fertilidade, por meio de extratores que visam determinar o grau de suficiência ou deficiência de nutrientes no solo. As metodologias que avaliam a disponibilidade de fósforo (P) certamente são as que apresentam as maiores controvérsias devido, principalmente, à complexidade do comportamento do nutriente no solo. No Brasil, os métodos mais utilizados para avaliar a disponibilidade de P em solos agricultáveis são Mehlich e resina de troca iônica. O método que emprega tiras de papel de filtro impregnadas com óxido de ferro (Papel-Pi) possui princípio semelhante ao da resina, no entanto é pouco utilizado no Brasil. Devido à deficiência generalizada de nutrientes nos solos brasileiros o gesso agrícola constitui-se um insumo adequado para minimizar condições adversas. Porém, foram relatados problemas na avaliação da disponibilidade de P em solos com elevados teores de gesso (gipsíferos) devido à reação deste com o íon bicarbonato (HCO3 -), presente na solução Olsen ou na resina de troca iônica, formando carbonato de cálcio que precipita e/ou adsorve o P disponível. Nestas situações os teores de P tendem a ser subestimados. Em solos ácidos, onde o gesso é amplamente utilizado, não há relatos sobre este problema. Assim, objetivou-se com o presente trabalho estudar a interferência do gesso na disponibilidade de P em solos ácidos, sendo conduzidos quatro experimentos. Em três experimentos de incubação aplicaram-se tratamentos com doses variando de 0 até 75 g kg-1 de fosfogesso, gipsita ou gesso puro, além de doses de P na forma de superfosfato triplo (SFT) ou fosfato natural reativo (FNR). Foram utilizadas amostras de cinco solos com características químicas e físicas variadas. Foi conduzido um experimento com doses de fosfogesso em casa de vegetação cultivando-se milho. Avaliaram-se os teores de P nas amostras de solo pelos métodos da resina de troca iônica (saturada com NaHCO3), Mehlich e Papel-Pi, e no experimento de casa de vegetação, estes teores foram correlacionados com a produção de massa seca e com o P acumulado pelo milho. Em todas as situações estudadas o gesso interferiu na avaliação dos teores de P-resina, fato não observado para os teores de PMehlich e P-Papel-Pi. Confirmou-se a hipótese de que métodos que empregam HCO3 - podem subestimar os teores de P devido à interferência do gesso, naturalmente dos solos ou adicionado com a finalidade de corrigi-los. Houve boa correlação entre os teores de P-Papel-Pi e P-Mehlich, exceto quando utilizou-se FNR, pois a solução Mehlich superestimou estes valores devido à sua ação ácida. De forma geral, não houve boa correlação entre os teores de P no solo e a produção de massa seca e o P acumulado pelo milho, devido ao desenvolvimento irregular das plantas em função das maiores doses de fosfogesso. Portanto, confirmou-se que os problemas da interação do bicarbonato com o gesso, relatados até então para solos gipsíferos ou calcareos, podem ocorrer também em solos ácidos com aplicação de gesso. No entanto, notou-se claramente que a quantidade de gesso necessária para causar esta interferência supera as doses normalmente aplicadas. / The soil chemical analysis provides technical support for soil fertility management through methodologies aiming to evaluate the level of sufficiency or deficiency of nutrients. The methods used to evaluate the phosphorus (P) bioavailability are certainly the most controversial which is due, mainly, to the complex interactions of this nutrient in the soil. In Brazil, the most common methodologies to evaluate soil P bioavailability in agricultural soils are the Mehlich and the ion exchange resin. The method that uses filter paper strips impregnated with iron oxide (Pi paper) is very similar in principle to the ion exchange resin, but has not been adequately studied in Brazil. Due to general soil fertility problems, gypsum has been applied acting as a soil subsurface ameliorant and also to decrease high soil sodium contents. Although, problems have been detected when evaluating P bioavailability in soils with high contents of gypsum due to the reaction of bicarbonate (HCO3 -), contained in the Olsen solution or in the ion exchange resin, because of the precipitation of calcium carbonate. In these situations the levels of P tend to be underestimated. In acid soils, where gypsum is widely applied, there is no investigation and reports on this problem, which was the objective of this study. Four experiments were carried out. In three incubation experiments different combinations were tested of P rates varying from 0 to 75 g kg-1 of phosphogypsuym, gipsite or reagent grade gypsum and the P sources triple superphosphates and Arad phosphate rock (APR). Five soil samples with different chemical and physical properties were used. Also, a greenhouse experiment was carried out with two short corn crops submitted to rates of gypsum applied to the soil. The soil samples were analyzed by three different methodologies, i.e., the ion exchange resin with NaHCO3 -, Mehlich and Pi paper, and in the greenhouse experiment the soil contents by these different procedures were correlated with dry-matter yield and P uptake by the corn plants. In all situations the presence of gypsum did interfere in the P bioavailability by the resin method, with a clear trend to decrease the P contents. The hypothesis that methods that utilize the HCO3 - can underestimate the amounts of soil P due to the presence of gypsum, natural or added to soils, was once again confirmed. An adequate correlation was found between the amounts of P evaluated by the Pi Paper and the Mehlich procedure, except when the APR was used, once the Mehlich tended to overestimate the values due to its acidic condition. In general, there was no adequate relation between the soil P and corn dry-matter yield or P uptake, which was probably due to irregular development of plants in treatments where high rates of gypsum was applied. It was shown that the interaction of HCO3 - with gypsum, before only reported for soils high in gypsum, can also occur in acid soils but it was noticed that the amount of gypsum to cause the interference is generally higher than the rates normally used at field conditions.