Orientador: Everson Alves Miranda / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T06:45:13Z (GMT). No. of bitstreams: 1 Oliveira_Sheilade_M.pdf: 1089976 bytes, checksum: 416dea7e320edfbe15467ca471df7a72 (MD5) Previous issue date: 2013 / Resumo: As indústrias cítricas geram grandes quantidades de efluentes líquidos. Estes efluentes são potencialmente poluidores para descarte em corpos d'água e necessitam de tratamento adequado. A maioria das plantas de tratamento de efluentes cítricos utiliza processos biológicos, devido a custos operacionais mais baixos quando comparado aos processos físico-químicos. Porém, estas plantas têm apresentado problemas de eficiência de remoção da carga orgânica e inibição da atividade biológica, em função das características tóxicas do efluente cítrico, devido à presença residual do d-limoneno, um monoterpeno extraído da casca da laranja. O d-limoneno, quando separado e purificado, tem ampla aplicação industrial, na área cosmética como fragrância e na área alimentícia como agente antimicrobiano e também pode ser bioconvertido em produtos como ácidos e alcoóis perílicos e carvona que podem ser utilizados na terapia do câncer. Os objetivos deste estudo foram selecionar e identificar microrganismos capazes de degradar o d-limoneno em altas concentrações (até 5%), simulando condições similares aos efluentes cítricos e avaliar o comportamento de consórcio destes microrganismos. Também foi avaliada a qualificação dos produtos obtidos da bioconversão do d-limoneno. Os microrganismos foram isolados a partir do lodo ativado de uma estação de tratamento de esgotos. Uma pré-seleção, de 56 linhagens de bactérias foi realizada, durante as 3 etapas de enriquecimento com o d-limoneno, através da técnica de esgotamento em superfície. Foram selecionadas 10 linhagens, que apresentaram maior crescimento visual, que foram caracterizados através da morfologia, coloração diferencial (Gram) e análise filogenética. A biodegradação do d-limoneno foi avaliada pela remoção de DQO em meios de cultivos diferentes variando as concentrações de d-limoneno (1%, 3% e 5%) sob condição agitada e estática na temperatura de 30°C. A bioconversão dos produtos foi qualificada por cromatografia gasosa. Foram isoladas bactérias Gram-positivas, do gênero Bacillus resistentes à concentração de 5% de d-limoneno sem fonte complementar de carbono. A remoção de DQO foi de 77% e terpineol, alcoóis ciclodecanol e octanediol foram qualificados como produtos bioconvertidos / Abstract: The citrus' industries generate large quantities of wastewater. These effluents are potentially polluting to disposal in water bodies and require treatment. Most sewage treatment plants citrus use biological process due to lower operating costs compared to physical-chemical processes. However these plants have presented problems in the efficiency removal of organic charge and inhibition of the biological activity due to citric toxic characteristics because of the presence of residual d-limonene, a monoterpene extracted from orange peel. The d-limonene, when it is separated and purified, has large industrial application, on field cosmetics as fragrances and foods fields as antimicrobial agent. Besides, the d-limonene can be bioconverted in perillic acids and perillyl alcohol, ?-terpineol and carvone that can be used in cancer therapy. The achievement of this study was select and isolate microorganism able to degradation high containing limonene (since 5%), simulating the same condition of wastewater characterizes of citric plants and evaluated the consortium microorganism behavior. In addition, the products of biotransformation d-limonene were qualified. Microorganisms were isolated from activated sludge of sewage treatment plant. A pre-selection, with 56 strains, was undertaken, during the 3 stage of enrichment with d-limonene, using depletion technique to isolate microorganisms. Ten strains were selected that showed the greater visual growth. They were characterized through of morphology, Gram and phylogenetic analysis. The d-limonene biodegradation was determinate by reduction COD in different cultivation media, varying the concentration of d-limonene (5 %, 3 % and 1 %) in agitated and stationary condition at temperature 30°C. The bioconversion of product obtained was confirmed by gas chromatography. Gram-positive bacteria were isolated of the Bacillus genus, bacteria resist to 5% of limonene-containing without complementary source of carbon. The removal of COD was 77% and terpineol, cyclodecanol and octadienol was evaluated as products bioconverted / Mestrado / Desenvolvimento de Processos Biotecnologicos / Mestra em Engenharia Química

The biological treatment of metalworking fluids (MWFs) is a cost effective alternative to conventional waste disposal processes. While research has proven that this process is capable of treating large volumes of wastes with high organic concentrations, there are uncertainties about the mechanisms by which the treatment occurs, and there are limitations that must be overcome. There is a need to understand the importance of the mechanisms by which carbon (and hence COD) is removed from the wastewater. This will allow for waste practitioners to make better decisions for optimizing the process, and for disposing of waste (i.e sludge) that is generated. The biological treatment process is also susceptible to biocides present within formulations. These compounds either need to be removed before the treatment process, or the bioreactors need to be made more resistant to them to ensure that their presence does not hinder the reactor functioning. This study aims to answer the uncertainties about the carbon removal mechanisms involved in the treatment of oil-containing MWFs. In the first experimental chapter, it is shown that the predominant mechanism of carbon removal is oil/water separation induced by emulsifier degradation, and hence the bioprocess treatment rate is significantly affected by the biodegradability of surfactants and by the presence of cations found naturally in the water that used to prepare the emulsions. The study then provides insights into the potential that coagulation and coalescence has for removing inhibitory components commonly found in MWFs. Coagulation and coalescence is shown to effectively remove biocides with low aqueous solubility (iodopropynyl butylcarbamate) and those that partition themselves into the oil phase (o-phenyl phenate and its sodium salt). Finally, to improve the resistance of reactors to inhibitory compounds, factors influencing the development of fixed-film reactors are investigated. A micro-cosmic system is used to study the both physico-chemical effects and nutritional factors on the development of biofilm reactors. It is shown that biofilm yields can be controlled through pH adjustment, and that these yields are maximized with phosphate stimulation and ammonium limitation. It is then shown that fixed-film reactors are able to treat metalworking fluids even under conditions deemed to be inhibitory. In summary, this project provides insights into further understanding and enhancing the biological treatment of MWFs.

PFCs are used in a wide variety of industrial and commercial applications for more than 50 years. Among variation of PFCs, Perfluorooctane sulfonate (PFOS) (CF3(CF2)7SO3-) and perfluorooctanoic acid (PFOA) (CF3(CF2)6COO-) are the most dominant PFCs. In May 2009, PFOS, its salts and perfluorooctane sulfonyl fluoride (PFOSF) are designated as new Persistent Organic Compounds (POPs) which are resistant, bio-accumulating, and having potential of causing adverse effects to humans and environment (IISD, 2009). However, products containing PFCs are still being manufactured and used, which could be the main reason why they are still observed in the environment and biota (Berger et al., 2004; Saito et al., 2003; Sinclair et al., 2004). The study is focused on the PFCs contamination in water and industrial wastewater around the Central and Eastern Thailand, where is one of the major industrialized areas in the country. The samplings were conducted in major rivers, Chao Phraya, Bangpakong and Tachin River. PFCs were contaminated in all rivers. The average total PFCs were 15.10 ng/L, 18.29 ng/L and 7.40 ng/L in Chao Phraya, Bangpakong and Tachin River, respectively. PFOS and PFOA were the predominant PFCs in all samples. The total of 118.6 g/d PFOS and 323.6 g/d PFOA were released from the three rivers to the Gulf of Thailand. The survey was also conducted in small rivers, reservoirs, and coastal water around Eastern Thailand, where many industrial zones (IZ) are located. The geometric mean (GM) concentration of each PFC was ranged from 2.3 to 107.7 ng/L in small rivers, 2.2 to 212.2 ng/L in reservoirs, and 0.8 to 41.1 ng/L in coastal water samples. The higher PFCs contaminations were detected in the surface water around the industrial zones, where might be the sources of these compounds. Field surveys were also conducted in ten industrial zones (IZ1 – IZ10) to identify the occurrences of PFCs from in industries. The recovery rates of PFCs in the samples indicated that the matrix interference or enhancement was an important problem in PFCs analysis. The elevated concentrations were detected in electronics, textile, chemicals and glass making industries. Total PFCs concentrations in the influent of WWTP were ranged from 39.6 to 3, 344.1 ng/L. Ten industrial zones released 188.41 g/d of PFCs. All of the treatment processes inside industrial zones were biological processes, which were reported that they were not effective to remove PFCs. The influence of industrial discharges was affected not only the rivers and reservoirs but also in the coastal water. The PFCs in rivers and reservoirs were discharged to the Gulf of Thailand, which is the important food source for Thai people and exports. Due to the problems in industrial wastewater analysis, several optimizing options were applied in PFCs analytical method especially in Solid Phase Extraction (SPE) procedure. The combination of PresepC-Agri and Oasis®HLB was the better option for analyzing PFCs in water samples. The optimum flow rate for loading the samples was 5 mL/min. Methanol (2 mL) plus Acetronitrile (2 mL) was the effective way to elute PFCs from the cartridges. The specific solvent percentages to elute each PFCs were identified for both water and industrial wastewater samples. The matrix removal methods by using Envi-Carb and Ultrafilter were effective for different types of industrial wastewater samples. PFCs were detected in surface waters, which are the sources of tap and drinking water for the people in Central and Eastern Thailand. The surveys were conducted in Bangkok city. Samples were collected from water treatment plants (WTPs), tap water, and drinking water. PFCs were detected in all tap water and drinking water samples. PFOS and PFOA concentrations in raw water of WTP were found 4.29 ng/L and 16.54 ng/L, respectively. The average PFOS and PFOA concentrations in tap water were detected 0.17 and 3.58 ng/L, respectively. The tap water results also showed that PFOS and PFOA concentrations were not similarly detected in all area in the city. PFOA were detected higher in the western area, while PFOS concentration was quite similar in all areas. Overall, it can be concluded that the current treatment processes were not completely remove PFCs. Nevertheless, PFCs in particulate phase were effectively removed by the primary sedimentation and rapid sand filtration. Elevated PFCs were found in the industrial zones (IZ2 and IZ5). To understand the distribution and fate of PFCs during industrial wastewater process, PFCs mass flows were studied. Higher PFCs in adsorbed phase were detected only in activated sludge and some influent samples. In IZ2, PFOA loading in the dissolved phase increased after activated sludge process by 5%. There was no degradation of PFOA inside the polishing pond. The highest loading to the treatment plant was PFOS with the loading of 2, 382 mg/d and 1, 529 mg/d in dissolved and adsorbed phase, respectively. Unlike PFCAs that showed no removal in the treatment process, PFOS were decreased during the treatment processes with 36% in the activated sludge process and 36% in the polishing pond. The predominant in this IZ5 was PFOS. The increasing of PFOS was also found in this treatment plant dissimilar to IZ2. PFOS was increasing by 45% in dissolved phase and 47% in adsorbed phase. All of PFCs in this industrial zone were detected higher in the effluent, indicated that PFCs’ precursors should be the major effects of this contamination. / Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14930号 / 工博第3157号 / 新制||工||1473(附属図書館) / 27368 / UT51-2009-M844 / 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 藤井 滋穂 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15659号 / 工博第3317号 / 新制||工||1501(附属図書館) / 28196 / 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 藤井 滋穂 / 学位規則第4条第1項該当

Industrial operations produce a notable amount of wastewaters with high concentration of chemical oxygen demand (COD), mostly consisting of organic carbon compounds. The treatment performance of electrochemical methods for organic removal and the effects of process parameters are the subject of this research. Three research tasks were performed. The first task was the removal of organic pollutants from three different industrial wastewaters using two different electrochemical methods; combined electrocoagulation + electrooxidation (EC+EO) and b) electrochemical peroxidation (ECP). Using only EC process was found to be significantly successful in removing suspended and colloidal pollutants and could remove more than 90% COD and 80% of TOC. The study showed that combined EC+EO process had better removal capability compared to ECP when operated under similar process conditions. The second task was to study the effect of the process parameters; pH, H2O2 dosage, current density, and operation time; and to optimize and estimate the best treatment conditions for the methods using Box-Behnken Design (BBD). For sugar beet wastewater, the results showed that EO could remove 75% of organics at optimum conditions of pH 5.3; current density of 48.5 mA/cm2; and operation time of 393 min. The canola oil refinery wastewater achieved more than 90% pollutant removal when the conditions were optimized at pH 5.8 – 6 with applied current density of 9.2 mA cm-2¬ run for nearly 300 min. The rate of degradation of the wastewater derived organic pollutants followed a first order kinetics for all the wastewaters investigated and the models were validated for goodness of fit with high R2. The final task was to compare treatment efficiency between the electrochemical processes. Based on the energy consumed and the performance efficiency to remove COD, sCOD, TOC and DOC in the three different wastewaters studied, EC+EO process was found suitable for the treatment of canola and sunflower oil wastewater. On the other hand, from the model prediction and the experiments conducted, EO resulted in better removal capability compared to ECP. Also, the consumption of energy by ECP was comparatively higher than EO process while taking longer time of operation for significant removal. / North Dakota Water Resources Research Institute; North Dakota Agricultural Experimental Station; Frank Bain Agricultural Scholarship

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20692号 / 工博第4389号 / 新制||工||1682(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 高岡 昌輝, 教授 藤井 滋穂 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Aevitas is an industrial wastewater treatment plant that receives about 300 m3/day of mixture of wastewater from different industries. The chemical oxygen demand of higher 600 ppm and the variety of the chemical constitution of industrial wastewater are two significant problems on Aevitas. Therefore, there is a strong need for developing advanced analytical techniques that can identify the specific compounds that are the source of COD. During 10 months, about 75 industrial samples were characterized using a battery of tests including GC/MS, COD, TOC, and pH to identify the chemicals that are main source of COD in the industrial wastewaters. Results showed that the COD of 87% of 75 provided samples from Aevitas plant was higher than 600. At the first step of process design, activated carbon was used to eliminate the identified organic chemicals from the wastewaters. The maximum and minimum of COD removal (depends on the chemical composition) of the wastewaters were obtained as 94 and 24%, respectively. Moreover, the amount of COD and TOC that can be adsorbed on the surface of 1 gram of the activated carbon were 25 and 7 mg, respectively. Although activated carbon is capable to reduce the COD, its capacity of adsorption is limited. To overcome this problem an alternative process, membrane filtration was applied for COD removal. Two types of crossflow NF (NF270, NF90, NFX, NFW, NFS, TS80, XN45, and SXN2_L) and RO (BW60 and TW30) membranes in two modules of the spiral wound and flat sheet were used. The filtration results of 11 different industrial wastewaters showed that NF90, TS80, NFX, and NFS were effective in COD removal. However, in terms of output flux NFX and NFS flat sheet were better than others were. Similar to the activated carbon process, the COD removal in filtration process was between 30 and 90%. The obtained results can be used to scale up the membrane filtration process at Aevitas. / Thesis / Master of Chemical Engineering (MChE) / Aevitas is an industrial wastewater treatment plant, which is situated at the City of Brantford. Every day, this plant receives about 15 trucks of the mixture of wastewaters from many different industries. The input wastewater into the plant should be treated and meet the environmental standard so that it can be discharged into a municipal wastewater plant. Currently, the maximum allowable chemical oxygen demand (COD) for discharging the treated wastewater from Aevitas to the municipal wastewater treatment plant is 600 ppm. Despite the fact, the current system in Aevitas is not efficient to meet this criterion. Thus, we strive to design efficient processes to overcome the problem. To this end, 75 samples were collected from Aevitas to observe the kind of chemicals that are the source of COD and then, two processes including activated carbon adsorption and membrane filtration were used for further reduction of COD. Although activated carbon can reduce the COD, the limited adsorption capacity was a major concern for its long-term application, especially if the COD of influent wastewater is higher than 2000 ppm. Membrane filtration was used as an alternative for activated carbon and the results showed that membrane could reduce the COD below 600 in 48% of the cases.

Wastewaters that are produced by industrial processes are more challenging to treat than municipal wastewaters, primarily due to two reasons. Firstly, industrial wastewaters contain high concentrations of several different contaminants (e.g. metals, nutrients and organics etc.), which can be challenging for a single process to treat. Secondly, the compositional properties of the wastewaters can vary significantly as it is dependent on several upstream processes. Commercial membrane technologies have shown significant adoption in desalination and municipal wastewater treatment applications. Their favourable selectivity and tunable properties have garnered interest from both academia and industry to push these technologies into industrial wastewater treatment. Despite showing promising contaminant removal results, current studies have shown that fouling due to high contaminant loadings, and variable treatment efficacies due to feed property variations, limit the adoption of commercial membranes into these applications. Current research addresses these challenges through the new material development or surface modifications, however, there is a need to approach these challenges at a process level by integrating existing membrane technology into adaptive processes. This thesis aims to advance the adoption of commercial membrane technology into ‘tough-to-treat’ industrial wastewater applications. Firstly, the effects of high contaminant concentrations and variable feed properties on membrane treatment is studied by using advanced techniques, such as gas chromatography – mass spectrometry, to resolve the composition of feed and permeate streams from membrane processes treating real wastewaters. It was determined that fast and efficient screening tools are required to optimize and adapt membrane processes to respond to this variability. This thesis then introduces high-throughput and miniaturized screening platform that combines analytical centrifugation with filter plate technology to rapidly optimize two-stage coagulation-filtration processes with an extremely low material and time requirement. / Thesis / Doctor of Philosophy (PhD) / Wastewaters sourced from industrial processes are considered ‘tough-to-treat’ due to high contaminant concentrations and time-varying compositional properties. Recent advancements in membrane technologies have demonstrate great promise in treating industrial wastewaters, however, these membranes often need to be integrated with other treatment technologies to overcome challenges with treating these wastewaters. This thesis aims to push the adoption of integrated membrane processes for treating high-strength industrial wastewaters. By utilizing advanced analytical techniques to investigate the effects of high contaminant loadings and variable feed properties on membrane processes, it was determined that screening tools are needed to rapidly design and optimize membrane process that are tailored to the properties of the wastewater. This thesis introduces a high-throughput and miniaturized screening platform that combines analytical centrifugation and filter-plate technology to holistically screen two-stage coagulation-filtration processes with little time and material requirements.

The treatability of a high strength industrial wastewater, 9,000 mg/L as chemical oxygen demand (COD), by three sequencing batch reactor (SBRs) systems operated under alternating redox environments: anaerobic/aerobic (ANA), anoxic/aerobic (ANX), and aerobic was investigated. A synthetic wastewater was modeled after a wastewater from an existing chemical processing facility. The largest component, hydroxypivaldehyde, was unavailable for the use in this research and was substituted by pivalic acid, both of which have a tertiary carbon. No significant degradation occurred in the anaerobic phase of operation; however, 55-65% of the COD was removed during anoxic operation. Simultaneous removal of pivalic acid and acetic acid was seen in both the anoxic and aerobic reaction phases. The anoxic/aerobic SBR provided the best overall treatability of the synthetic wastewater based on: effluent quality, sludge characteristics and settling properties. The results suggested that anoxic/aerobic treatment schemes are a viable treatment alternative for industrial wastewaters containing high concentrations of organic acids, including acids with tertiary carbons. The treatability of the three alternating redox environments on the Industry's wastewater was also investigated. Again, no significant degradation of the industrial wastewater occurred during the anaerobic reaction phase. During the anoxic reaction phase, 15-20% of the COD was removed from the industrial wastewater in contrast to the high removals seen with the synthetic wastewater. The aerobic SBR provided the best COD removal for the industrial wastewater. The performance differences between the synthetic and industrial wastewaters stress the importance of treatability studies on the actual industrial wastewater. Biological treatment of the synthetic and Industry wastewaters was unable to achieve the effluent goal of 100 mg/L as COD. Sand filtration followed by granular activated carbon adsorption treatment of the effluent from the synthetic wastewater-fed ANA SBR provided the COD removal necessary to achieve the effluent goal. / Master of Science