Dissertations / Theses on the topic 'Flocculation chemicals'

This paper is about the studies carried out to analyze the feasibility of using an innovative treatment system in the primary treatment process for municipal waste water. Furthermore, experiments are conducted to analyze the optimal parameters for utilizing the treated waters for irrigation purposes and for biogas production from the recovered sludge. The work is carried on the incoming municipal wastewater from Hammarby locality with around 30,000 inhabitants. Chemicals used in this process are, a metal salt namely polymerized aluminum chloride (PAX XL36) and two flocculation chemicals namely, a high molecular weight polymer (HM) (SNF Nordfloc C-192) and a low molecular weight polymer (LM) (Purfix 120). The choice of these chemicals was based on the recommendations made by previous studies on flocculation chemicals. These chemicals aid in flock formation and the DAF unit which provides compressed air, aids in flock flotation. The study is focused on optimizing parameters which implies minimal usage of chemicals and aimed to attain maximum sludge production with best possible treated water quality. All the experiments have been carried out on a pilot scale unit, designed with required specifications and with the foresight to scale up into a large scale unit based on the results. These are obtained by performing a series of analysis specifically formulated for this study. In laboratory experiments were carried out to analyze COD (chemical oxygen demand), Ammonium, Nitrate, Total nitrogen and phosphorus using Dr. Lange cuvettes. As the prime focus is on reuse of the treated water for irrigation purpose and biogas production, all the parameters are modulated in accordance with the standard water quality prescriptions for the water to be used for irrigation. In accordance with the climatic conditions of the region, various parameters are modulated in such a way that in summers the outcome water quality is emphasized and maximization of sludge/organic matter is emphasized during winter season.

The purpose of this research was to characterise the physical properties of microalgae, as a function of growth and suspension conditions, to enable exploitation of these characteristics for improved separation whilst allowing for water recycle.

On a papermaking machine, fines and colloids are retained in a paper sheet. The most important particle interactions are among particles having a high weight fraction and a short characteristic interaction time. Most of these interactions follow Langmuir kinetics, in which the flocculation efficiency is one of the important parameters. To enhance retention, many retention aids are available, one of which is neutral polyethylene oxide (PEO) used in combination of a phenolic cofactor (CF).
In this work, a new model was derived in which all possible interactions were considered and assumed to follow Langmuir kinetics. Since fines are the main component in the headbox of mechanical grade furnishes, fines homo- and heteroflocculation with a PEO/CF retention aid were investigated in a circulating flow loop, and found to follow Langmuir kinetics. The small amount of fines deposited on the fibers was attributed to the large detachment rate in turbulent shear. The apparent difference in the deposition time and the half time of flocculation was attributed to difference in efficiency. Fines homoflocculation showed that fines are flocculated (without a retention aid) to various extents depending on shear, and that aggregates of flocs will form when a retention aid is added.
The PEO/CF flocculation efficiency was found to be a function of various parameters, i.e., aging of PEO solution, stirring intensity and time of stirring during dissolution, concentration at storage, shearing and dilution prior to injection. Optimum conditions were found for most parameters, and a critical shear intensity was determined. This PEO behavior was attributed to the extent of entanglements of PEO coils, which can be characterized prior to its addition to the flocculation vessel by a newly developed method. In this method, the pressure drop of a PEO solution passing through a capillary constriction was measured and correlated with its flocculation efficiency. Using the derived correlation, the flocculation efficiency can be estimated, and the relevant parameters can be controlled. Moreover, the salt effect on a PEO/CF system in a pulp was investigated. Salt was found to react with a CF causing a decrease in the flocculation efficiency. The effect of this reaction can be eliminated if PEO is added directly after CF addition.

The retention of process colloids in the paper web is essential for papermaking process efficiency and product quality. Fines (fibre fragments) and fillers strongly affect the optical, surface and mechanical properties of paper. A very efficient flocculation aid system to deposit fine material (colloids) on fibres (collectors) consists of a polymer used in conjunction with anionic microparticles. The objective of this thesis is to elucidate the mechanism of fines retention with poly(electrolyte)-montmorillonite flocculant systems. Two main subjects are addressed. Firstly, polymer transfer between colloidal particles and collectors was characterised and modelled, and the influence on the papermaking process was evaluated. Secondly, the role of anionic microparticles in a dual flocculation aid was investigated. The influence on the flocculation kinetics and the adsorption behaviour of dissolved and colloidal compounds were studied.
The hetero-flocculation of wood fibres and fines induced by polymer and microparticles was analysed in a stirred tank reactor. The deposition of fines on fibres in the presence of polymer is transient. This is attributed to polymer transfer between surfaces upon particle detachment, which leads to the formation of an electro-steric barrier. The resulting polymer layers have limited bridging abilities. A mathematical model describing the simultaneous particle deposition and polymer transfer was developed and validated. The kinetics is determined by three rate constants: a deposition rate constant (k1), a detachment rate constant (k2) and a polymer transfer coefficient (beta). The influence of shear, salt concentration and polymer chemistry on the kinetics was quantified.
Microparticles act as bridging agents between adsorbed polymer layers. They provide a stronger bond than single polymer layers. Bond strengthening occurs irrespective of the bridging ability of the adsorbed layers towards cellulosic surfaces. The mechanism is explained in terms of charge densities and polymer layer conformations. The de-layering of montmorillonite is crucial for its efficiency.
Finally, the efficiency of montmorillonites as white water scavengers was quantified using model wood colloids and polymers. Dissolved and colloidal substances adsorb on montmorillonites following a low-affinity Langmuir isotherm. Dissolved polymers form molecular monolayers, while colloids adsorb as particles. Montmorillonite was found an efficient scavenger for colloidal material.
Montmorillonite used in conjunction with a poly(electrolyte) has three effects in improving fines retention. It augments the bond strength as a bridging agent between adsorbed polymer layers, it allows the retention of colloids coated with inactive polymer layers and finally it scavenges the dissolved and colloidal substances, which would otherwise decrease the poly(electrolyte) efficiency.

Adding polyethylene oxide (PEO) at the wet end of a paper machine, can result in an increase in retention of the fine particles. The results obtained with PEO and the cofactors (SNS, MPR, and CAR), are discussed in terms of the association-induced polymer bridging mechanism.
Dynamic Light Scattering (DLS) of polymer solutions revealed that each of the three cofactors are forming complexes with PEO. CAR radically increased the apparent diameter of the PEO chains, and MPR seems to decrease it. In latex suspensions, the SNS was found very efficient in the sequence latex-polymer-cofactor (LPC), increasing the PEO hydrodynamic layer thickness (HLT).
Flocculation experiments with the help of a Photometric Dispersion Analyser (PDA), with PEO only (no cofactor) suggested that the fines are composed of more than one component. SNS was found to make all the fines alike by adsorbing on them. Adding the PEO after SNS gave homoflocculation. As a result, the specific surface of fines, calculated by PEO adsorption was found to be 0.223 m$ sp2$/g.
The association-induced polymer bridging mechanism can happen in three different manners depending if the cofactor and the polymer are adsorbing onto fines. When neither of PEO nor cofactor adsorb onto the collector, the PEO/cofactor association-complexes bridge the particles (van de Ven and Alince (1996)). When the cofactor (e.g. SNS) and the polymer adsorb onto the fines, in the sequence fines-cofactor-polymer (FCP), with a chemical ratio cofactor/PEO of 3/1, adsorption of the PEO chains onto cofactor-coated fines is likely to occur at the beginning followed by the flocculation of the fines. In the sequences fines-polymer-cofactor (FPC), when the polymer adsorbs onto the fines and the cofactor adsorbs (e.g. SNS) or not (e.g. MPR), a reenforcement of the bondstrength was noticed. (Abstract shortened by UMI.)

Premature yeast flocculation (PYF) is a sporadic problem encountered during industrial brewing fermentations. Current hypothesis states that factors, thought to arise from fungal infection of the barley in the field and/or the malt in the maltings cause yeast to flocculate prematurely and/or heavily before the depletion of the sugars in the wort. This results in poorly attenuated worts, with higher residual extract and lower ABV, flavor abnormalities (i.e. diacetyl, SO2), lower carbonation levels, disruption of process cycle times and potential issues with the re-use of the yeast in subsequent fermentations. Consequently, PYF generates significant financial and logistical problems both to the brewer and the maltster. In the current study a small-scale fermentation assay was developed and optimized to predict the PYF potential of malts, as well as to investigate the importance of yeast strain in the incidence and severity of the phenomenon. Furthermore, the impacts of the PYF factor(s) (i.e. arabinoxylans, antimicrobial peptides) on yeast fermentation performance and metabolite uptake were also studied, whilst the Biolog detection system was investigated as a potential rapid tool which to detect PYF. The results obtained suggested that our in-house assay can be successfully used to predict the PYF potential of malts 69 or 40 h post-pitching depending upon the yeast strain used. Whilst ale yeasts were not found susceptible to PYF, lager yeasts exhibited different degrees of susceptibility even to the same PYF factor(s). More specifically, the more flocculent lager yeast SMA was found to be more susceptible than the medium flocculent lager yeast W34/70. However, interestingly, the fermentation performance of a PYF+ wort could be significantly improved by using a non-flocculent and relatively insensitive to PYF lager yeast. It was also shown that worts with lower amount of glucose and maltose could be responsible for poor fermentation profiles and/or heavy PYF as well as elevated residual sugars and lower fermentability. The observation that linoleic acid (6 mg.l-1) exacerbated PYF (P = 0.047) and made its detection more rapid was found to be contrary to the “titration hypothesis” (Axcell et al., 2000) which hypothesized that the addition of fatty acids might “titrate” out antimicrobial peptides so that they can no longer bind to the yeast cells. High gravity fermentations with worts inducing PYF did not have a significant effect (P > 0.05) on yeast physiological characteristics or fermentation performance suggesting that the PYF+ sample used in this study was inducing PYF though the ‘bridging’ polysaccharide mechanism rather than through the antimicrobial peptides. The Biolog system can be used for the metabolic characterization of different flocculence lager yeasts incubated in different fermentation media, whilst wort composition had a significant effect in redox reduction reactions.

The Ceratium species occurring in the Vaal River since 2000, was identified as Ceratium hirundinella (O.F. Müller) Dujardin as proposed by Van Ginkel et al (2001). Ceratium hirundinella is known to cause problems in drinking water purification and has been penetrating into the final drinking water of Rand Water since 2006. Ceratium hirundinella is associated with many other water purification problems such as disrupting of the coagulation and flocculation processes, blocking of sand filters and algal penetration into the drinking water. Ceratium hirundinella also produce fishy taste and odorous compounds and causes discolouration of the water. The aims of this study were to determine the main environmental factors which are associated with the bloom formation of C. hirundinella in the source water and to investigate the influence of C. hirundinella on the production of potable water. In order to optimise treatment processes and resolve problems associated with high C. hirundinella concentrations during the production of potable water, jar testing and chlorine exposure experiments were performed. Multivariate statistical analyses were performed to determine the main environmental variables behind C. hirundinella blooms. Ten years data (2000 - 2009) from the sampling point C–VRB5T in the Vaal River, (5 km upstream from the Barrage weir) were used for this investigation, because C. hirundinella occurred there frequently during the ten year period. In this study, it was found that C. hirundinella was favoured by high pH, Chemical Oxygen Demand (COD), orthophoshapte (PO4), and silica concentrations, as well as low turbidity and low dissolved inorganic nitrogen (DIN) concentrations. No correlation was found between C. hirundinella and temperature, suggesting that this alga does not occur during periods of extreme warm or extreme cold conditions, but most probably during autumn and spring. The results of the multivariate statistical analysis performed with historical data from Vaalkop dam, indicate that the dinoflagellate C. hirundinella seems to be favoured by low temperature and turbidity, and high DIN, Fe, Methyl–orange alkalinity, Cd, PO4, Conductivity, pH, hardness and SO4 concentrations. In order to optimise treatment processes such as coagulation, flocculation and sedimentation, jar testing experiments were performed to investigate different coagulant chemicals namely: cationic poly–electrolyte only, cationic poly–electrolyte in combination with slaked lime (CaO) and CaO in combination with activated silica. Water from four different sampling localities were chosen to perform the different jar testing experiments: 1) sampling point M–FOREBAY (in the Forebay, connecting the canal to the Zuikerbosch Purification plant) near Vereeniging due to its proximity to the Zuikerbosch treatment plant, 2) M–CANAL_VD (upstream from the inflow of the recovered water from Panfontein) to determine the influence of (if any) the recovered water from Panfontein on Forebay source water, 3) source water from Vaalkop Dam (M–RAW_VAALKOP) and 4) source water from Rietvlei Dam (water from both Vaalkop and Rietvlei Dams contained high concentrations of C. hirundinella at that time of sampling) to determine which coagulant chemical is the most effective in removing high concentrations of C. hirundinella cells during the production of drinking water. The jar testing experiments with Vaalkop Dam and Rietvlei Dam source water (rich with C. hirundinella) indicated that using cationic poly–electrolyte alone did not remove high concentrations of C. hirundinella efficiently. However, when CaO (in combination with cationic poly–electrolyte or activated silica) were dosed to Vaalkop Dam source water a significant decrease of C. hirundinella concentration was observed. This indicates that the C. hirundinella cells were “shocked or stressed” when exposed to the high pH of the CaO, rendering it immobile and thereby enhancing the coagulation and flocculation process. However, when 10 mg/L CaO in combination with poly–electrolyte was dosed to Rietvlei Dam source water the turbidity and chlorophyll–665 results indicated that this coagulant chemical procedure was ineffective in removing algal material from the source water. The jar testing experiments using the cationic poly–electrolyte alone or cationic poly–electrolyte in combination with CaO on M–FOREBAY and M–CANAL_VD source water, showed a decrease in turbidity, chlorophyll–665 concentration, and total algal biomass, with an increase of coagulant chemical. When CaO in combination with activated silica was dosed, the inherent turbidity of the lime increased the turbidity of the Vaalkop Dam, M–FOREBAY and M–CANAL_VD source water to such an extent that it affected coagulation negatively, resulting in high turbidity values in the supernatant. Regardless of the turbidity values, the chlorophyll–665 concentration and total algal biomass (C. hirundinella specifically in Vaalkop Dam source water) decreased significantly when CaO was dosed in combination with activated silica. Therefore it was concluded that a cationic poly–electrolyte alone is a good coagulant chemical for the removal of turbidity, but when high algal biomass occur in the source water it is essential to add CaO to “stress” or “shock” the algae for the effective removal thereof. However, when CaO in combination with activated silica was dosed to Rietvlei Dam source water a decrease in turbidity and chlorophyll–665 concentration was found with an increasing coagulant chemical concentration. These results confirm the fact that coagulant chemicals may perform differently during different periods of the year when water chemistry changes and that certain coagulant chemicals may never be suitable to use for certain source waters. For the effective removal of algae during water purification, it is recommended that cationic poly–electrolyte in combination with CaO are used as coagulant chemical at the Zuikerbosch Water Purification Plant. Turbidity is not a good indication of algal removal efficiency during jar testing experiments. If problems with high algal concentrations in the source water are experienced it is advisable to also determine the chlorophyll–665 concentrations of the supernatant water during the regular jar testing experiments, since it will give a better indication of algal removal. Chlorine exposure experiments were performed on water from Vaalkop Dam (M–RAW_VAALKOP) and Rietvlei Dam source water, to determine the possibility of implementing pre– or intermediate chlorination with the aim to render the cells immobile for more effective coagulation. The chlorine exposure experiments with Vaalkop Dam and Rietvlei Dam source water showed similar results. The chlorine concentration to be dosed as part of pre– or intermediate chlorination will differ for each type of source water as the chemical and biological composition of each water body are unique. When the effect of chlorine on the freshwater dinoflagellate C. hirundinella was investigated, it was found that the effective chlorine concentration where 50 % of Ceratium cells were rendered immobile (EC50) was approximately 1.16 mg/L for Vaalkop Dam source water. For the source water sampled from Rietvlei Dam, it was found that the EC50 was at approximately 0.87 mg/L. Results of analyses to determine the organic compounds in the water after chlorination revealed that an increase in chlorine concentration resulted in increase in total organic carbon concentration (TOC), as well as a slight increase in MIB and trihalomethanes (CHCl3). Pre– or intermediate chlorination seem to be an effective treatment option for the dinoflagellate C. hirundinella to be rendered immobile and thereby assisting in its coagulation process. The use of pre– or intermediate chlorination to effectively treat source waters containing high concentrations of C. hirundinella is a viable option to consider. However, the organic compounds in the water should be monitored and the EC50 value for each source water composition should be determined carefully as to restrict cell lysis and subsequent release of organic compounds into the water.
Thesis (M.Sc. (Environmental Science))--North-West University, Potchefstroom Campus, 2012.

Thesis submitted in fulfillment of the requirements for the degree Master of Technology: Chemical Engineering In the Faculty of Engineering At the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY 2013
A number of foods, pharmaceutical and industrial products are formulated as emulsions. The immiscibility of oil and water makes emulsions thermodynamically unstable, thus requiring emulsifiers. Natural and synthetic substances have been used as emulsifiers with preference for the former for safety, cost and availability purposes. Bambara groundnut (BGN) is an important source of nutrient in many African communities. Similar to soybean, flaxseed, and other leguminous products, the important blend of high protein and carbohydrate composition of BGN makes it a potential candidate as an emulsifier where, it can serve additional nutritional role in such emulsions. No literature evidence exists to support any earlier study on the potential emulsifying property of BGN. It is therefore of interest to investigate the potential of BGN flour (BGNF) and starch (BGNS) in stabilizing oil-in-water emulsions. The current study aimed to investigate the emulsifying properties of Bambara groundnut flour and starch. A batch of BGN was milled to produce the BGNF. BGNS was extracted from the BGNF. Emulsions were prepared using a wide range of flour-oil-water and starch-oil-water composition as generated through computational modelling. Emulsions were physically observed for stability, and then subjected to various stability studies using the Turbiscan® (which gives kinetic information on the process leading to phase separation; and allows for the detection of two kinds of destabilisation phenomena (particle migration): creaming and sedimentation) and optical microscope (which helps to detect particle size variation or aggregation in order to measure coalescence and/or flocculation). The most stable emulsions (one BGNF-stabilized and the other BGNS-stabilzed) were determined and subjected to same stability studies in the presence of varying physicochemical and physic-mechanical environmental conditions: effects of homogenization speed (9,000 – 21,000 rpm), pH (2 - 10), the presence of salt (2 – 10% w/v NaCl) and vinegar (2 – 10% v/v). Results were expressed in terms of relative stability (using creaming/sedimentation rate) and absolute oil droplet growth (coalescence and flocculation). The emulsifier-oil compositions (emulsifier and water make 100 mL gelatinized mixture before the addition of oil) that gave the most stable emulsions were 9 g BGNF-39 g oil and 5 g BGNS-30 g oil. The two emulsions had only 15% and 30% growth in oil droplet diameter respectively by day 5, compared to over 3000% in the unstable ones. The emulsions were generally observed physically to be stable till day 5 with minimal creaming. Emulsions prepared with BGNS were physically observed to have increasing viscosity with time. There was microbial growth on the emulsions after 3 days. This might have been encouraged because of the rich nutritional composition of BGN. The stability of the emulsions increased significantly (p < 0.05) with the speed of homogenization (up to 15, 000 rpm beyond which the difference in stability was not significant). Compared to control (pH 7), emulsion stability decreased significantly (p < 0.05) with decreasing (up to 16% instability by Day-5 at pH 2) and increasing pH (10% instability at pH 10) with corresponding increase in droplet size. Emulsion stability increased significantly (p < 0.05) with increasing NaCl concentration (35% instability at 2% NaCl compared to 18% instability at 10% NaCl). Stability however decreased sharply with increasing concentration of vinegar (55% instability at 10% vinegar compared to 19% instability at 2% vinegar). The BGNF-stabilized emulsions were more stable (ordinarily and in the presence of the additives) than the BGNS-stabilized ones. Instability values in the BGNS emulsions, in most cases, double those for BGNF. Emulsions were successfully stabilized with BGNF and BGNS. The emulsions were optimal when prepared at a homogenization speed of 15,000 rpm and at neutral pH. The higher the concentration of salt, the more stable the emulsions. Increasing concentration of vinegar however, destabilized the emulsions.

Flocculants are commonly used in industrial settings where solid-liquid separations are desired including industrial and municipal wastewater management and potable water production facilities. Conventional flocculants include inorganic metal salts and synthetic organic polymers. The cost, availability, and harmful effects of the non-biodegradable nature of these flocculants have led to the widespread study of natural flocculants. Current natural flocculants being studied include polysaccharides cultivated from microbial extracellular matrix products and plant based materials. In this study, the mucilage of Opuntia ficus-indica cactus was evaluated as a natural flocculant for sediments and bacteria. The O. ficus-indica cactus is also known as the nopal or prickly pear and is commonly used as a food source in Mexico and Latin America. Using simple extraction techniques non-gelling (NE) and gelling (GE) mucilage extracts were isolated from fresh cactus pads. Column tests were used to evaluate the flocculation and removal of suspended sediment and bacteria caused by mucilage addition. Throughout this work the mucilage's ability as a flocculant was evaluated by varying mucilage type and concentration, suspended contaminant type and concentration, and cation type and concentration. Many of the results are explained in terms of the morphology and chemical composition of the GE and NE mucilage extracts. The extracts consist primarily of polysaccharides and differences in physical structure between mucilage types were seen using atomic force microscopy and transition electron microscopy. A variety of suspended particles were used to evaluate the mucilage as a flocculant including kaolin, acid-washed kaolin, and bacteria. The bacteria employed in this study include Bacillus cereus, Escherichia coli HB101 K12, and fully attenuated Bacillus anthracis Sterne strain. The addition of monovalent (Na+ and K+), divalent (Ca2+ and Mg2+), and trivalent (Al3+ and Fe3+) cations was studied alone and in combination with mucilage. In cation studies Ca2+ had the most profound effect on flocculation efficiency; therefore its efficacy was further explored. Mucilage was most effective with dosages between 5 and 50 mg/L for the contaminants studied. Using these optimal concentrations, 20 to 200 L of water could be treated with only 1 g of mucilage powder. Based on the extraction method used in this work, 1 g of mucilage can be obtained from a cactus pad weighing approximately 250 g (wet weight). Mucilage remained an effective flocculant over a wide range of suspended contaminant concentrations showing that mucilage is a versatile flocculant that can be tailored for a variety of applications. Overall, this work shows that the O. ficus-indica cactus is an effective flocculant for suspended sediments and bacteria. The cactus' low cost, abundance, and current use in many areas make it an attractive alternative to traditionally used flocculants. Additionally, this work builds upon existing knowledge pertaining to natural flocculants and could offer insight into their general behaviors for water treatment applications.

Este presente trabalho teve como objetivo a investigação do desempenho de um biopolímero experimental à base de cálcio, desenvolvido e fornecido por uma empresa americana, na coagulação, floculação e sedimentação da vinhaça bruta como tratamento físico-químico na remoção de carga orgânica e na concentração de compostos fertilizantes no lodo. O estudo do tratamento da vinhaça por meio da aplicação deste biopolímero possibilitaria, hipoteticamente, uma redução significativa da carga orgânica como tratamento inicial da vinhaça, além de concentrar os nutrientes presentes na vinhaça no lodo gerado para uso fertilizante. Foram realizados ensaios com coagulantes convencionais (sulfato ferroso, cloreto férrico e óxido de cálcio) para efeito de comparação entre estes e o biopolímero. Os ensaios de coagulação, floculação e sedimentação foram realizados em escala de laboratório com uso do equipamento Jar Test. Os ensaios foram divididos em três etapas. Na primeira etapa foram realizados ensaios aplicando-se determinadas dosagens de biopolímero e variando-se os tempos de coagulação, velocidades de rotação, além de realizar ou não a mistura lenta após a etapa de coagulação, a fim de verificar se estes parâmetros poderiam otimizar o processo de tratamento com o aplicação do biopolímero. Para segunda etapa do procedimento experimental foram realizados ensaios com os outros coagulantes: óxido de cálcio, sulfato férrico e cloreto férrico. Os ensaios com o cloreto férrico e o sulfato férrico foram realizados nas seguintes condições: velocidade de mistura rápida de 200 rpm por um período de tempo de 30 segundos e velocidade de mistura lenta de 80 rpm por um período de 20 minutos. Já os ensaios com óxido de cálcio foram realizados com apenas velocidade de mistura rápida de 200 rpm variando os períodos de tempo em 1, 5 e 10 minutos. O tempo de sedimentação para separação dos flocos formados foi de 2 horas para todas as etapas. O tratamento com biopolímero experimental apresentou resultados de remoção de matéria orgânica abaixo dos valores esperados, que era na faixa de 60% a 80%. Os resultados limitaram-se a valores de 10% a 35% de remoção de DQO. Porém, a remoção de turbidez atingiu valores elevados, próximos a 90%. Para os compostos relacionados à fertilização NPK (nitrogênio, fósforo e potássio), o tratamento com biopolímero experimental obteve as melhores eficiências de remoção de fósforo (48,3%) e de NTK (17,2%) em relação aos demais coagulantes, porém não apresentou remoção de potássio. Não houve diferença significativa na eficiência de remoção de DQO quando se alteram as condições operacionais de velocidade de agitação. Já o aumento no tempo de agitação diminui a eficiência de remoção de DQO.
This work aimed to investigate the performance of an experimental biopolymer calcium-based, developed and supplied by an American company, on gross vinasse coagulation, flocculation and sedimentation as a physical chemical treatment on organic load removal and on fertilizer compounds concentration in sludge. The study of the vinasse treatment through the application of this biopolymer would allow, hypothetically a significant reduction of the organic load as vinasse initial treatment, besides concentrating the vinasse found nutrients in the sludge created for fertilizer use. Assays were performed with conventional coagulants (ferrous sulfate, ferric chloride and calcium oxide) for comparison between them and the biopolymer. Tests of coagulation, flocculation and sedimentation were carried out in laboratory scale using Jar Test equipment. The experiments were divided in three stages. In the first stage assays were performed applying certain dosages of biopolymer and varying the clotting time, rotational speeds in addition to performing or not performing the slow mixture after the clotting stage in order to check if these parameters could optimize the treatment process with the biopolymer application. For the second stage of the experimental procedure tests were developed with other coagulants: calcium oxide, ferric sulphate and ferric chloride. Tests with ferric chloride and ferric sulphate were performed under the following conditions: fast mixing speed of 200 rpm for a period of 30 seconds and slow mixing speed of 80 rpm for a period of 20 minutes. Considering the assays with calcium oxide, they were carried out using only rapid mixing speed of 200 rpm by varying the time periods at 1, 5 and 10 minutes. The sedimentation time to the formed flakes separation was two hours for all stages. Treatment with experimental biopolymer presented results of removal of organic matter below the expected values, which was in the range 60% to80%. The results limited to values of 10% to 35% of COD clearance. However, the removal of turbidity reached high values near 90%. For compounds related to NPK (nitrogen, phosphorus and potassium) fertilization, the treatment with experimental biopolymer obtained the best efficiency of phosphorus removal (48,3) and TKN removal (17.2%) in comparison with the other coagulants, but showed no removal of potassium. There was no significant difference in COD removal efficiency when the operating conditions of agitation speed are changed. Regarding to the increase in the agitation time, it reduces the efficiency of COD removal.

Lixiviados de aterros sanitários apresentam altas concentrações de nitrogênio amoniacal e matéria orgânica, além de outros poluentes, que não permitem seu descarte no meio ambiente, sem um prévio tratamento. Lixiviados de aterros sanitários mais antigos, com matéria orgânica mais estabilizada, apresentam grande potencial poluidor, principalmente devido à presença de substâncias recalcitrantes que, usualmente, não são removidas através de tratamento biológico, necessitando, portanto, da aplicação de um pós-tratamento. A presente pesquisa objetivou aplicar o tratamento físico-químico a dois efluentes de sistemas biológicos de tratamento. O primeiro sistema era constituído de um reator de lodo ativado operado em bateladas seqüenciais (70 Litros) cujo efluente era submetido à processo de coagulaçãofloculação usando sais de ferro e alumínio, para remoção da matéria orgânica recalcitrante. Operou-se, em paralelo, uma lagoa aerada, em escala de bancada, dimensionada para remoção da matéria orgânica biodegradável cujo efluente era submetido a processo de precipitação química para remoção de amônia, através da formação do mineral estruvita (MgNH4PO4.6H2O). Os resultados obtidos demonstraram que o cloreto férrico (FeCl3) foi o coagulante mais apropriado sob o ponto de vista econômico, embora, dosagens elevadas (1.160 mg FeCl3/L), frente a 2.465 mg Al2(SO4)3.6H2O/L tenham sido requeridas para o alcance de remoções da matéria orgânica recalcitrante. Com a aplicação de FeCl3 o pH ótimo de coagulação foi próximo de 4,0 e para o Al2(SO4)3; por volta de 5,0. Ao longo dos testes, avaliouse a influência das condições de mistura sobre os fenômenos físico-químicos. Os resultados demonstram que, para o despejo estudado, o gradiente de velocidades e o tempo de mistura não exercem influência sobre os fenômenos de coagulaçãofloculação. Quanto à precipitação química da amônia na forma do mineral estruvita, as melhores remoções (~ 90%) foram alcançadas quando o limite de solubilidade do mineral estruvita foi excedido, para tanto se faz necessária aplicar uma razão molar igual a 1,5:1:1,4 entre os íons envolvidos (Mg+2:NH4 +:PO4 -3). Entretanto, o efluente final desse sistema apresentou uma concentração residual de fósforo solúvel superior a 12 mg P-PO4 -3/L, o que o torna pouco recomendável para fins práticos.
Landfill leachates present high ammonia and organic matter concentrations, besides other pollutants, which do not allow its discharge to the environment without a previous treatment. Older landfill leachates, with more stabilized organic matter, present great pollutant potential, mainly due to the presence of recalcitrant substances that not often are removed by biological treatment and need the application of a post-treatment. The present research aimed to apply the physicochemical treatment for two biological wastewater treatment plant effluents. The first one was constituted by an activated sludge (sequence batch reactor - 70 liters), which effluent was submitted to a coagulation-flocculation process, using iron and aluminum salts, for recalcitrant organic matter removal. A lab scale aerated lagoon was operated in parallel. The lagoon was dimensioned for biodegradable organic matter removal, which effluent was submitted to a chemical precipitation process for ammonia removal (formation of the mineral struvite (MgNH4PO4.6H2O).The results showed that the ferric chloride (FeCl3) was the more appropriated coagulant considering the economic point of view, however high dosages (1,160 mg FeCl3/L) comparing with 2.465 mg Al2(SO4)3.6H2O/L had been required to achieve recalcitrant organic matter removal. Applying FeCl3, the optimum pH was of the order of 4.0 and for Al2(SO4)3, approximately 5.0. During the tests, the influence of the mixture conditions on the physicochemical phenomena was evaluated. The results demonstrated that the velocities gradient and the mixture time do not influenced the coagulation-flocculation phenomena. Regarding to the chemical precipitation of ammonia in struvite form, the better removals (~ 90%) were achieved when the solubility limit of the mineral was exceeded. Due to this fact, it was necessary to apply a molar rate of 1.5:1:1.4 between the ions (Mg+2:NH4 +:PO4 -3). Nevertheless, the final effluent of this system presented a residual soluble phosphorus concentration higher than 12 mg P-PO4 -3/L, hence it is not recommended for practical purposes.

Microalgae are considered as a potential feedstock for many promising applications. Some active substances in microalgae have plant biostimulation effects potentially useful in agriculture. However, to produce such a microalgal biomass, specific microalgae cultivation and post-treatment processes must be designed to preserve active substances. A particular focus is provided on cultivation (tubular photobioreactor) and different plausible post-treatment scenarios for microalgae separation (flocculation and centrifugation) and preservation (sterilization and drying). For each step, yield and energy consumption are modeled using data taken from literature or lab and pilot scale experiments. Industrial equipment for scale-up process is also studied by comparing existing systems. These models enable to make an economic evaluation of the whole process and to study its profitability for each scenario. The breakeven price is calculated as a function of the production rate. Several parameters are suggested to improve system efficiency and profitability at the end of this study. However, a better microalgae characterization and more experiments on potential post-treatment systems are required to improve the accuracy of the model.

A proposta deste trabalho foi utilizar quatro diferentes coagulantes - sulfato de alumínio, cloreto férrico, hidroxicloreto de aluminio e sulfato ferrico; construir os diagramas de coagulação; e assimilar as regiões de maior ou menor eficiência da remoção de turbidez ou da cor. Para permitir uma avaliação de custos na utilização dos coagulantes, observo-se nos diagramas as regiões onde os valores de turbidez remanescente são aproximadamente iguais para diferentes coagulantes. Com essa consideração, foi stabelecida a relação entre consumo e custo dos produtos quimícos utilizados. Os coagulantes que apresentaram particularidades para as águas estudadas foram: o cloreto ferrico que mostrou melhor desempenho para valores de ph baixos; o sulfato ferrico que mostrou-se mais economico; e o hidroxicloreto de aluminio que atua numa grande faixa de ph. Na conclusão dos estudos, verifica-se que cada água a ser tratada deve ser analisada através de diagramas de coagulação, visando a otimização dos parâmetros de ph versus dosagem e buscando o melhor coagulante pelo menor custo.
The purpose of this study was to use four different coagulants - aluminum sulphate, iron chloride, polyaluminum hidroxichloride and ferric sulphate; to build the coagulation diagrams; and to mark the regions of higher or lower efficiency in the removal of turbidity or color. To allow a cost appraisal in the use of the coagulants, the region where the values of remaining turbidity, which are approximately the same for different coagulants, was examined in the diagrams. This being taken into consideration, the relation between consumption and cost of the chemical products was established. The coagulants that presented certain peculiarities for the studied waters were: iron chloride, that showed better performance for low pH values; the ferric sulphate, that showed itself as more economical; and the polyaluminum hidroxichloride, that functions in a large interval of pH. In the conclusion of the study, it was observed that each type of water to be treated must be analyzed through coagulation diagrams, aiming at the optimization of pH parameters versus dosages and looking for the best coagulant with lower cost.

Landfill leachate contains a variety of contaminants and is created when rainwater percolates the landfill. For landfill management the leachate is the main issue that can cause problems to the environment. At the landfill of Fläskebo, Renova AB treats the leachate in a local treatment plant. The treatment consists of a chemical treatment step with chemical precipitation, flocculation, sedimentation and filtration, and a final step with a carbon and peat filter. Renova has to ensure that the condition of the leachate reaches the regulation set for the landfill before it is released to the recipient. This regulation has not yet been established and a final suggestion will be given to the county administrative board in spring 2006.

In this master thesis the chemical treatment of Fläskebo is optimized. A comparison between the control program and the regulation was made to estimate the contamination of the leachate. Also the effectiveness of the two steps is evaluated. For optimization, the leachate was first tested in a laboratory with different coagulants and flocculants.

The purpose was to increase the precipitation of particles and metals; arsenic, cadmium, chromium, mercury, lead, copper, nickel and zinc through sweep floc coagulation and hydroxide precipitation. After the laboratory tests the precipitation was tested in the treatment plant with higher pH and coagulant. Also the process control for sodium hydroxide was examined.

The leachate had a small content of organic matter and nutrients, but had a large content of halogenated substances (AOX) and the heavy metals nickel and copper. High concentrations of contaminants were reduced better than low concentrations in the two treatment steps. The carbon and peat filter material also caused an increase of the arsenic content in the leachate after filtration. From the laboratory work the results showed a better reduction of metals with iron-chloride, PlusJÄRN and the anjonic polyacrylamid, Fennopol A. Because of the high content of chloride the iron- sulphate, PurFect was chosen for further tests. The optimal pH for the heavy metals arsenic, zinc, copper and nickel was between pH 9 and 9, 5. The precipitation in the treatment plant showed better results with sodium hydroxide and a higher pH, pH 9 in the flocculation basin. An increase of the coagulant PurFect from 202 mg/l to 225 mg/l meant only a higher chemical cost. The process control of sodium hydroxide showed an oscillating and unstable control performance, which may lead to a higher consumption of chemicals.

Lakvatten har varierande föroreningsgrad och karaktär och bildas då regnvatten perkolerar igenom en deponi. För en deponiverksamhet är lakvattnet den huvudsakliga påverkan på den omgivande miljön. Vid en av Renova ABs deponier, Fläskebo, utanför Göteborg sker reningen av vattnet i den lokala reningsanläggningen. Reningen består av kemisk fällning, flockning, sedimentering och filtrering samt ett kol- och torvfilter. För att få släppa ut lakvattnet har Renova just nu ett prövotidsvillkor på lakvattnets kvalité och till våren 2006 skall förslag på slutgiltiga utsläppsvillkor lämnas till Länsstyrelsen.

I detta examensarbete har den kemiska reningen av lakvattnet från Fläskebo optimerats utifrån lakvattnets karaktär. Lakvattnets föroreningsgrad bedömdes efter en jämförelse av analysresultatet inom kontrollprogrammet och riktvärdena i prövotidsvillkoret. Dessutom utvärderades effektiviteten i varje enskilt reningssteg, den kemiska reningen och kol- och torvfiltret. För optimering av den kemiska reningen testades lakvattnet först på lab med olika fällnings- och flockningsmedel. Uppgiften var att öka partikelfällningen och reducera metallerna arsenik, kadmium, krom, kvicksilver, bly, koppar, nickel och zink i lakvattnet genom svepkoagulering och hydroxidfällning.

Utifrån resultaten på lab testades sedan fällningen i full skala, pH höjdes i flockningsbassängen och så även dosen fällningsmedel till vattnet. En inledande undersökning av regleringen av lutdosering gjordes med några stegsvarsexperiment.

Lakvatten innehöll låga halter av organiskt material och närsalterna kväve och fosfor, medan de halogena ämnena (AOX) och tungmetallerna nickel och koppar var höga. De båda reningsstegen, kemisk rening och kol- och torvfiltret var generellt bra på att rena föroreningar i höga koncentrationer men var sämre vid låga. Kol- och torvfiltret ökade koncentrationen i vattnet av arsenik genom materialets interna läckage. I fällningsförsöken gav järnkloriden, PlusJÄRN och den anjoniska polyakrylamiden, Fennopol A bäst resultat i att avskilja metaller. Järnsulfaten PurFect gav näst bäst resultat och valdes istället för järnkloriden för vidare försök då kloridhalten i lakvattnet redan var högt. Optimalt pH för arsenik, zink, koppar och nickel var inom pHintervallet 9 och 9,5. Fällningen i full skala ute i verket visade ett bättre resultat vid tillsatt lut och ett högre pH (pH 9) i flockningsbassängen. Däremot betydde en höjning av fällningskemikalien från 202 mg/l PurFect till 225 mg/l enbart en ökad kemikaliekostnad och en överdosering. Det visade sig dessutom att lutregleringen var svängig och på gränsen till instabil. Regulatorn bör därför ses över så att risken för ökad kemikaliekonsumption och kostnader minskar.

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O tratamento de esgoto pode ser insuficiente para a completa eliminação de vírus entéricos, tais como adenovírus humanos (HAdV) e rotavírus do grupo A (RVA). Portanto, o retorno do lodo e do efluente tratado ao ambiente pode representar riscos à saúde pública. Este estudo foi conduzido para otimizar um protocolo de floculação orgânica para recuperação viral a partir de lodo de esgoto e efluente tratado, bem como realizar um monitoramento de HAdV e RVA na estação de tratamento de esgoto (ETE) de Juiz de Fora, MG. Nos estudos de otimização, foram propostas adaptações no protocolo de floculação com leite desnatado para lodo e efluente tratado, com modificações no tempo de agitação da amostra, na concentração final de leite desnatado e/ou na etapa de centrifugação. No estudo de monitoramento, esgoto bruto (P1), esgoto primário (P2), lodo (P3) e efluente tratado (P4) foram coletados bimensalmente em 2014 (durante as épocas seca e chuvosa), totalizando 96 amostras (simples e compostas). As cargas virais foram determinadas por PCR quantitativo e o bacteriófago PP7 foi usado como controle interno. Amostras de HAdV e RVA foram submetidas ao sequenciamento e a viabilidade das partículas de HAdV foi avaliada em amostras de P4. Os parâmetros físico-químicos e a contagem de coliformes termotolerantes (CT) foram determinados em cada ponto. Nos estudos de otimização, foram selecionadas duas condições que apresentaram as maiores taxas de recuperação viral no lodo (menor tempo de agitação e maior concentração de leite desnatado) e no efluente tratado (sem primeira etapa de centrifugação e com maior concentração de leite desnatado). Ambas provaram ser ferramentas úteis para pesquisa viral em amostras de campo, inclusive para a pesquisa de vírus gigantes. No monitoramento, o HAdV foi detectado em 85,4% (82/96) dos concentrados, com cargas virais variando de 3,27 x 102 a 2,42 x 106 cópias do genoma por mililitro (cg/mL), ao longo do ano. A presença de RVA foi observada em 52,1% (50/96) dos concentrados (1,38 x 103 a 3,65 x 105 cg/mL), com maior detecção na época seca. A carga viral não foi influenciada pelo tipo de amostra, sendo detectada tanto em amostras simples, quanto em amostras compostas. Todas as amostras de HAdV sequenciadas pertenciam à espécie F tipo 41 e as amostras de RVA pertenciam ao genótipo I1. O tratamento de esgoto reduziu a quantidade de matéria orgânica e sólidos, bem como a contagem de CT e as cargas virais. No entanto, a presença de HAdV e RVA foi observada mesmo após o tratamento, inclusive em amostras de efluente tratado consideradas adequadas pelas legislações atuais, com detecção de partículas infecciosas de HAdV. Foram observadas correlações positivas entre a carga viral e a demanda bioquímica de oxigênio, os sólidos sedimentáveis e sólidos suspensos totais. Os dois protocolos otimizados neste estudo podem ser facilmente adequados para uso em laboratório de rotina, podendo impulsionar o monitoramento viral nos subprodutos gerados na ETE. A carga viral detectada na ETE salienta a disseminação ambiental de RVA e HAdV e aponta o potencial do HAdV como um marcador viral de contaminação em ambientes aquáticos.
Sewage treatment may be insufficient for the complete elimination of enteric viruses such as human adenoviruses (HAdV) and group A rotaviruses (RVA). Thus, the return of sewage sludge and treated effluent to the environment poses concerns potential for public health. This study was conducted to optimize an organic flocculation procedure for viral recovery from sludge and treated effluent, and carry out a surveillance of HAdV and RVA in a wastewater treatment plant (WWTP) at Juiz de Fora, MG. In optimization studies, conditions were proposed for sludge and treated effluent with changes in the stirring time, in the final concentration of skimmed-milk and/or in the centrifugation step. In surveillance study, raw sewage (P1), primary sewage (P2), sludge (P3) and treated effluent (P4) were collected bimonthly in 2014 (during the dry and the rainy season), totaling 96 samples (simple and composite). Quantitative PCR determined viral loads and PP7 bacteriophage was used as internal control. HAdV and RVA strains were selected for sequencing, and the HAdV viability was evaluated in P4 samples. Physicochemical parameters and thermotolerant coliforms (TC) counting were determined at each point. After the optimization studies, two conditions were selected: the ones that showed the highest viral recovery rates in sludge (lower stirring time and higher concentration of skimmed-milk) and treated effluent (without the first centrifugation step and with a higher concentration of skimmed-milk). These conditions proved to be a useful tool for viral search in the field samples, including for the research of giant virus. In surveillance study, HAdV was detected in 85.4% (82/96) of the concentrated, with viral loads ranging from 3.27 x 102 to 2.42 x 106 genome copies per milliliter (gc/mL), throughout the year. RVA presence was observed in 52.1% (50/96) of the samples (1.38 x 103 to 3.65 x 105 gc/mL) with detection greater in the dry season. Viral load was not influenced by the type of sample being detected both in single samples, as in composite samples. All the sequenced HAdV strains belonged to species F type 41, and RVA strains belonged to genotype I1. Sewage treatment reduced the content of organic matter and solids, as well as the TC counts and the viral loads. However, the presence of HAdV and RVA was observed after treatment, even in samples considered adequate by current laws with detection of infectious HAdV particles. Positive correlations were observed between viral load and biochemical oxygen demand, sedimented solids and total suspended solids. Two optimized protocols in this study are easily suitable for routine laboratory use and can boost viral monitoring in by-products generated in the WWTP. Viral load detected in WWTP stress the environmental dissemination of HAdV and RVA and addressed the potential of HAdV as a virological marker of contamination in aquatic environments.

Des émulsions particulièrement stables peuvent être formulées à l'aide de particules colloïdales (émulsions dites de Pickering). L'objectif de cette étude est d'accéder à la compréhension des mécanismes de stabilisation des interfaces, ainsi que du lien entre propriétés interfaciales et propriétés macroscopiques des émulsions. Dans ce cadre, la stratégie adoptée repose sur l'utilisation de particules colloïdales dont les caractéristiques peuvent être variées continûment à la fois en amont par la chimie de synthèse (variation de la mouillabilité, de la déformabilité) et in situ par un stimulus (pH, sel, température...). De plus, les émulsions stabilisées par de telles particules deviennent, elles aussi, sensibles aux stimuli et la déstabilisation des émulsions peut être déclenchée à la demande. Les mécanismes d'adsorption, les interactions entre particules aux interfaces et les propriétés résultantes des émulsions sont étudiés. L'établissement de concepts généraux régissant la stabilisation/déstabilisation des émulsions permet d'en contrôler, via la formulation ou le procédé (température, cisaillement), les propriétés d'usage. Enfin les émulsions stabilisées par des particules colloïdales peuvent être utilisées en tant que précurseurs dans la formulation de matériaux plus complexes : ceci est illustré par l'élaboration de capsules à libération thermostimulée.

Asphaltene precipitation, flocculation, and deposition in the reservoir and producing wells cause serious damages to the production equipment and possible failure to develop the reservoirs. From the field production prospective, predicting asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore may avoid high expenditures associated with the reservoir remediation, well intervention techniques, and field production interruption. Since asphaltene precipitation, flocculation, and deposition strongly depend on the pressure, temperature, and composition variations (e.g. phase instability due to CO2 injection), it is important to have a model that can track the asphaltene behavior during the entire production system from the injection well to the production well, which is absent in the literature. Due to economic concerns for asphaltene related problems, companies spend a lot of money to design their own asphaltene inhibition and remediation procedures. However, due to the complexity and the lack of knowledge on the asphaltene problems, these asphaltene inhibition and remediation programs are not always successful. Near-wellbore asphaltene inhibition and remediation techniques can be divided into two categories: changing operating conditions, and chemical treatment of the reservoir. Although, the field applications of these procedures are discussed in the literature, a dynamic model that can handle asphaltene inhibition and remediation in the reservoir is missing. In this dissertation, a comprehensive non-isothermal compositional reservoir simulator with the capability of modeling near-wellbore asphaltene inhibition and remediation is developed to address the effect of asphaltene deposition on the reservoir performance. This simulator has many additional features compared to the available asphaltene reservoir simulators. We are able to model asphaltene behavior during primary, secondary, and EOR stages. A new approach is presented to model asphaltene precipitation and flocculation. Adsorption, entrainment, and pore-throat plugging are considered as the main mechanisms of the asphaltene deposition. Moreover, we consider porosity, absolute permeability, and oil viscosity reductions due to asphaltene. It is well known that the asphaltene deposition on the rock surface changes the wettability of the rock towards oil-wet condition. Although many experiments in the literature have been conducted to understand the physics underlying wettability alteration due to asphaltene deposition, a comprehensive mathematical model describing this phenomenon is absent. Based on the available experimental data, a wettability alteration model due to asphaltene deposition is proposed and implemented into the simulator. Furthermore, the reservoir simulator is coupled to a wellbore simulator to model asphaltene deposition in the entire production system, from the injection well to the production well. The coupled reservoir/wellbore model can be used to track asphaltene deposition, to diagnose the potential of asphaltene problems in the wellbore and reservoir, and to find the optimum operating conditions of the well that minimizes asphaltene problems. In addition, the simulator is capable of modeling near-wellbore asphaltene remediation using chemical treatment. Based on the mechanisms of the asphaltene-dispersant interactions, a dynamic modeling approach for the near-wellbore asphaltene chemical treatments is proposed and implemented in the simulator. Using the dynamic asphaltene remediation model, we can optimize the asphaltene treatment plan to reduce asphaltene related problems in a field. The results of our simulations show that asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore are dynamic processes. Many parameters, such as oil velocity, wettability alteration, pressure, temperature, and composition variations influence the trend of these processes. In the simulation test cases, we observe that asphaltene precipitation, flocculation, and deposition can occur in primary production, secondary production, or EOR stages. In addition, our results show that the wettability alteration has the major effect on the performance of the reservoir, comparing to the permeability reduction. During CO2 flooding, asphaltene precipitation occurs mostly at the front, and asphaltene deposition is at its maximum close to the reservoir boundaries where the front velocity is at its minimum. In addition, the results of the coupled reservoir/wellbore simulator show that the behavior of asphaltene in the wellbore and reservoir are fully coupled with each other. Therefore, a standalone reservoir or wellbore simulator is not able to predict the asphaltene behavior properly in the entire system. Finally, we show that the efficiency of an asphaltene chemical treatment plan depends on the type of dispersant, amount of dispersant, soaking time, number of treatment jobs, and the time period between two treatment jobs.
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