A contaminação do solo com resíduos tóxicos tornou-se um dos maiores problemas ambientais. Na maioria das vezes, as condições do local incluem a contaminação da água subterrânea. Neste contexto, os metais pesados têm sido motivo de preocupação, destacando-se o cromo hexavalente como poluente de elevada toxicidade e mobilidade. Quando um problema de contaminação no solo é identificado, ações de remediação devem ser aplicadas. Dentre as tecnologias existentes, uma das mais promissoras é o uso de barreiras reativas permeáveis. A barreira é construída com materiais reativos de forma a interceptar a pluma contaminada, atenuando a concentração do contaminante a níveis aceitáveis ou controláveis. É possível converter resíduos agrícolas em carvões ativados, material adsorvente resultante de processo pirolítico. Esses carvões podem apresentar desempenhos diferenciados em aplicações específicas. A presente tese tem como objetivo geral avaliar a aplicação de carvões ativados, oriundos da pirólise de casca de arroz, em barreiras reativas permeáveis. Os objetivos específicos consistem em estudar o desenvolvimento de carvões quimicamente ativados e investigar, por meio de ensaios de laboratório, sua aplicação na remoção de cromo hexavalente de meios aquosos e de meios porosos saturados. Para a preparação dos carvões ativados, foi desenvolvida uma unidade pirolítica rápida a vácuo com características escaláveis e com ênfase no controle e registro das variáveis do processo. Foram preparados carvões por ativação química com K2CO3 e KOH e determinadas suas características físico-químicas, texturais e análise morfológica por microscopia eletrônica de varredura. Ensaios de batelada e um ensaio de coluna com soluções de cromo foram realizados para avaliação da atenuação do contaminante. Os carvões ativados apresentaram baixa densidade aparente, similares valores de pH e de condutividade elétrica e elevado conteúdo de cinzas quando comparados com carvões de outras biomassas. A ativação química com reagentes alcalinos, associada às condições pirolíticas, resultou em superfícies menos ácidas, característica favorável para adsorção de Cr(VI). Resultaram em adsorventes mesoporosos, característica necessária para a adsorção de íons de elevado peso molecular; exibiram baixas áreas superficiais e similaridade morfológica entre si com a predominância da estrutura de sílica. Embora os carvões tenham apresentado baixas áreas superficiais, a adsorção teve a predominância da influência do diâmetro médio dos poros, seguido da área de mesoporos e da carga superficial negativa, indicando o potencial de aplicação dos carvões na remoção de Cr(VI). O ensaio de coluna possibilitou demonstrar o emprego do carvão ativado de casca de arroz em barreiras reativas, indicando suas limitações em pHs próximo à neutralidade e candidatando-o a situações de tratamento em série ou seqüenciais. Os trabalhos realizados estabeleceram base segura para o desenvolvimento de equipamento adequado para a pirólise e domínio do processo de manufatura do carvão ativado. A análise conjunta dos resultados sugere que as condições do processo pirolítico a vácuo adotado, juntamente com a ativação química com baixas concentrações de reagente ativantes, configuram uma rota atrativa para a elaboração de material poroso a partir de casca de arroz, com potencial aplicação na remoção de Cr(VI) em barreiras reativas permeáveis. / Soil contamination with toxic waste has become one of the biggest environmental problems. Site conditions often include groundwater contamination. In this context, heavy metals have been a matter of concern with chromium hexavalent recognized as pollutant of high toxicity and mobility. When a problem of soil contamination is identified, remediation tasks must be applied. Amongst the new technologies, the use of permeable reactive barriers is one of the most promising. This barrier is constructed with reactive materials in order to intercept the contaminated plume, attenuating the contaminant concentration to acceptable or controllable levels. It is possible to convert agricultural waste into activated carbon, an adsorbent material resulting from the pyrolytic process. This carbon can perform differently face to environmental applications. The present thesis has as a major objective to evaluate the application of activated carbons, derived from rice husk pyrolysis, in permeable reactive barriers, with emphasis on the remediation of contaminated soil with heavy metals. The specific objectives consist of studying the development of activated carbon from chemical activation and also investigating, through laboratory tests, its application in chromium removal from watery and saturated porous media. With the purpose of preparing activated carbons, a fast pyrolytic unit of rice husk was developed, with characteristics that can be scaled up and with emphasis on the control and register of process variables. Chemical activated carbons using K2CO3 and KOH have been prepared in different activation conditions and determined their physico-chemical and textural parameters. The morphological analysis was performed by scanning electron microscopy. Batch tests and a column test with solutions of chromium were performed to evaluate the attenuation of the contaminant. The activated carbons showed a low apparent density, similar values of pH and electrical conductivity and high ash content compared to carbons from other biomass. The chemical activation with alkaline reagents, associated with pyrolytic conditions, resulted in less acidic surface, characteristic favorable for Cr(VI) adsorption. The adsorbent manufactured results in mesoporous carbons, a characteristic necessary for the adsorption of ions of high molecular weight, exhibited low surface areas and morphological similarities between them, with the predominance of the structure of silica. Despite the carbons have shown low surfaces areas, the adsorption showed the predominant influence of the average pore diameter, followed by the mesopores area and surface negative charge, indicating the potential application of these carbons in Cr(VI) removal. The column test has demonstrated the use of activated carbon from rice husk in reactive barriers, showing its limitations in pHs close to neutrality and pointing it to cases of serial or sequential processing. The work carried out established safe basis for the development of suitable equipment for the pyrolysis and for the domain of the manufacturing process of activated carbon. The analysis of the results suggests that the conditions of the adopted vacuum pyrolytic process, jointly with the chemical activation with low concentrations of activate reagent, constitute an attractive route for the preparation of porous material from rice husk, with potential application in removing Cr (VI) in permeable reactive barriers.

abstract: N-nitrosodimethylamine (NDMA) is a probable human carcinogen and drinking water disinfection by-product. NDMA forms as the product of reactions between chloramines and precursor compounds in water. This dissertation aims to provide insight into the removal of NDMA precursors, their nature, and a method to aid in their identification. Watershed-derived precursors accounted for more of and greater variability to NDMA formation upon chloramination than polymer-derived precursors in environmental samples. Coagulation polymers are quaternary amines, which have low NDMA yield but high use rates. Watershed-derived precursors were removed up to 90% by sorption to activated carbon, but activated carbon exhibited much less (<10%) sorption of polymer-derived precursors. Combined with literature NDMA molar yields of model anthropogenic compounds, where anthropogenic chemicals in some cases have NDMA yields >90% and biological compounds always have yields <2%, trace, organic, amine containing, anthropogenic chemicals were implicated as the most likely source of NDMA precursors in the watershed. Although activated carbon removes these precursors well, identification of individual compounds may result in more cost effective mitigation strategies. Therefore, I developed a method to isolate NDMA precursors from other organic matter into methanol to facilitate their identification. Optimization of the method resulted in a median recovery of NDMA precursors of 82% from 10 surface waters and one wastewater. The method produces 1,000X concentrated NDMA precursors and, in collaboration with the University of Colorado Center for Environmental Mass Spectrometry, time of flight mass spectrometry (TOF-MS) was performed on multiple treated wastewater and raw drinking water isolates. During TOF-MS, tertiary amines can cleave to form a neutral loss and an R group ion that is dependent on the original structure and I wrote a software program to “trawl” exported TOF-MS spectra for the diagnostic neutral loss resulting from fragmentation of tertiary amines. Methadone was identified as one new NDMA precursor that occurs at concentrations that form physiologically relevant levels of NDMA in surface water and wastewater. The approach used here to identify NDMA precursors is adaptable to other unknown disinfection by-product precursors given that a functional group is known that can 1)control sorption and 2)produce a predictable diagnostic fragment. / Dissertation/Thesis / Doctoral Dissertation Civil and Environmental Engineering 2015

abstract: Activated Carbon has been used for decades to remove organics from water at large scale in municipal water treatment as well as at small scale in Point of Use (POU) and Point of Entry (POE) water treatment. This study focused on Granular Activated Carbon (GAC) and also activated Carbon Block (CB) were studied. This thesis has three related elements for organics control in drinking water. First, coagulation chemistry for Alum and Aluminum Chlorohydrate (ACH) was optimized for significant organics removal to address membrane fouling issue at a local municipal water treatment plant in Arizona. Second, Rapid Small Scale Column Tests were conducted for removal of Perfluorinated compounds (PFC), PFC were present in groundwater at a local site in Arizona at trace levels with combined concentration of Perfluorooctaneoic Acid (PFOA) and Perfloorooctanesulfonic Acid (PFOS) up to 245 ng/L. Groundwater from the concerned site is used as drinking water source by a private utility. PFC Removal was evaluated for different GAC, influent concentrations and particle sizes. Third, a new testing protocol (Mini Carbon Block (MCB)) for bench scale study of POU water treatment device, specifically carbon block filter was developed and evaluated. The new bench scale decreased the hydraulic requirements by 60 times approximately, which increases the feasibility to test POU at a lab scale. It was evaluated for a common POU organic contaminant: Chloroform, and other model contaminants. 10 mg/L of ACH and 30 mg/L of Alum with pH adjustment were determined as optimal coagulant doses. Bituminous coal based GAC was almost three times better than coconut shell based GAC for removing PFC. Multiple tests with MCB suggested no short circuiting and consistent performance for methylene blue though chloroform removal tests underestimated full scale carbon block performance but all these tests creates a good theoretical and practical fundament for this new approach and provides directions for future researchers. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2017

abstract: Granular activated carbon (GAC) is effectively used to remove natural organic matter (NOM) and to assist in the removal of disinfection byproducts (DBPs) and their precursors. However, operation of GAC is cost- and labor-intensive due to frequent media replacement. Optimizing the use of GAC is necessary to ensure treatment efficiency while reducing costs. This dissertation presents four strategies to reduce improve GAC usage while reducing formation of DBPs. The first part of this work adopts Rapid Small Scale Tests (RSSCTs) to evaluate removal of molecular weight fractions of NOM, characterized using size exclusion chromatography (SECDOC). Total trihalomethanes (TTHM), haloacetic acids (HAA5) and haloacetonitriles (HAN) formation were quantified after treatment with GAC. Low MW NOM was removed preferentially in the early bed volumes, up until exhaustion of available adsorption sites. DBP formation potential lowered with DOC removal. Chlorination prior to GAC is investigated in the second part of this work as a strategy to increase removal of NOM and DBP precursors. Results showed lower TTHM formation in the effluent of the GAC treatment when pre-chlorination was adopted, meaning this strategy could help optimize and extend the bed life if GAC filters. The third part of this work investigates in-situ GAC regeneration as an alternative to recover adsorption capacity of field-spent GAC that could potentially offer new modes of operation for water treatment facilities while savng costs with reactivation of spent GAC in an external facility. Field-spent GACs were treated with different oxidant solutions and recovery in adsorption capacity was evaluated for NOM and for two micro pollutants. Recovery of GAC adsorption capacity was not satisfactory for most of conditions evaluated. This indicates that in-situ GAC regeneration could be more effective when the adsorbates are present at high concentrations. Lastly, this work investigates the impact of low molecular weight polyDADMAC on N-nitrosodimethylamine (NDMA) formation. Water treatment facilities rely on polyDADMAC as a coagulant aid to comply with NOM removal and turbidity requirements. Since polymer-derived NDMA precursors are not removed by GAC, it is essential to optimize the use and synthesis of polyDADMAC to reduce NDMA precursors during water treatment. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2017

abstract: Specific inorganic and organic pollutants in water (As(V), Cr(VI), THMs, and hardness) cause health concerns or aesthetic problems. The goal of this dissertation is to demonstrate novel approaches to improve the performance of point of use and municipal activated carbon processes to provide safe and reliable water to the public at distributed centralized locations. Template Assisted Crystallization system would adjust saturation index (SI) value of TAC treated water to zero when SI value of influent water was in the range at 0.08~0.3. However, the reduction in SI when SI values were higher (e.g. 0.7~1.3) was similar to the reduction at lower SI values which could be due to limitations in kinetics or mass transfer with the template on TAC media. Pre-chlorination prior to municipal-scale granular activated carbon (GAC) treatment was evaluated to control THM formation in distribution systems. Pre-chlorination decreased UVA, shift the dissolved organic carbon (DOC) molecular weight distribution and pre-formed trihalomethanes (THM). GAC treatment of pre-chlorinated water achieved lower THM formation in distribution systems. To add functionality in POU systems to remove As(V) and Cr(VI), activated carbon was nano-tized to fabricate nano-enabled carbon block (CB) by (1) impregnating iron or titanium metal oxides chemically or (2) attaching titanium based P25 through electrostatic attraction force. Nanoparticle loadings of 5 to 10 wt % with respect to activated carbon enables reduction of As(V) or Cr(VI) from levels of common occurrence to below regulatory levels across carbon block designs. Minimal impacts on As(V) and Cr(VI) sorption were observed up to a nanoparticle pre-treatment temperature of 200 C, which is the temperature for CB production. Through controlling pH at 4.5 during mixing of nanoparticles with pH IEP=6 and activated carbon with pH IEP=3, electrostatic attachment of nanoparticles to activated carbon could be achieved prior to fabricating carbon block. A mini carbon block test device was designed, fabricated, and validated to mimic performances of full-scale carbon block using less volumes of test water. As(V) removal tests showed Fe impregnated CB achieved the highest As(V) removal while P25 attached CB had the lowest among three nanoparticles loaded CBs. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

Made available in DSpace on 2014-10-09T12:49:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:29Z (GMT). No. of bitstreams: 1 09827.pdf: 4140612 bytes, checksum: 01f7cbe137d515506b3c08b7bf14bb3e (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2015-05-08T14:59:48Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2106593 bytes, checksum: ab15bacf25992ba8bafb4cdeb1c81ec6 (MD5) Previous issue date: 2012-09-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Activated carbon, AC, is a pure state carbon with large porosity, which adsorbs molecules or ions from a fluid medium. In general, it is obtained from the controlled burning of agricultural or industrial by-products. When produced in conventional furnaces, the operating temperatures may rise up to 900°C, resulting in yields inferior to 20 %. The low yield is a consequence of the precursor's large thermal degradation caused by the heat wave front which moves slowly from the surface to its core. Therefore, there is a significant formation of meso and macropores, which lead to a final value of density, &#961;, below of 0.5 g.cm-3. On the other hand, thermal degradation caused by microwaves is less aggressive. The heating process occurs from the core of the precursor to its exterior. As a consequence the activated carbons are denser, have a more selective microporosity, and are more suitable to gas storage. This paper reports the preparation and the results of the qualitative analysis of physically and chemically activated carbons, from coconut shell, using an adapted microwave oven. This adapted microwave allows the settling down of temperature programs' ramp and heating rates. The BET surface area of activated carbons prepared in the microwave oven surpassed 1200 m2.g-1, the apparent density situated at around 0.5 g.cm-3, and the yields remained above 40 %. Comparisons between the electricity consumption of the electrical conventional kiln and of the micro-wave oven in producing a certain quantity of an activated carbon with a BET surface area over 800 m2/g, showed that the use of the microwave oven had allowed, each time, a reduction of about 3,2 kW.h, which represents an average of electricity saving of 85.5 %. / Carvão ativado, CA, é uma forma de carbono puro de grande porosidade, que adsorve moléculas ou íons de um meio fluido. É obtido a partir da queima controlada de precursores, geralmente, subprodutos de baixo custo, oriundos da agricultura, ou da indústria. Quando produzido em fornos convencionais, as temperaturas de trabalho podem ser superiores a 900 °C, reduzindo a menos de 20 % a massa de carvão produzida com relação à do precursor (rendimento). Isto se dá em virtude da grande degradação ocasionada pela frente de calor destes fornos, que lentamente se desloca da superfície ao núcleo da massa do precursor. Em consequência, via de regra, a massa específica final, &#961;, registra valores abaixo de 0,5 g.cm-3. No caso das micro-ondas a degradação térmica da matéria se dá, de forma menos agressiva, do interior do precursor para o exterior, proporcionando carvões ativados mais densos, com microporosidade mais seletiva, e, logo, mais adequada ao armazenamento de gás. O presente trabalho relata a obtenção de carvões ativados, por via física e química, a partir do endocarpo do coco da baía, em um forno micro-ondas adaptado, onde é possível se programar rampas de temperaturas e razões de aquecimento. Avalia-se o consumo de energia elétrica do forno micro-ondas adaptado em relação ao do forno elétrico convencional. A área superficial de BET dos carvões química e fisicamente preparados foi superior a 1200 m2.g-1, a massa específica manteve-se próximo a 0,5 g.cm-3, e os rendimentos ficaram acima de 40 %. Ao se comparar o consumo de energia elétrica para produzir, tanto no forno convencional como no micro-ondas, uma determinada quantidade de carvão ativado, com área de BET superior a 800 m2/g, verificou-se que a redução gerada pelo micro-ondas foi de aproximadamente 3,2 kW.h, representando um percentual de economia de energia de 85,5 %.

Made available in DSpace on 2015-05-14T12:09:23Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1888869 bytes, checksum: dbaae38c1299dd8ef37444fdd79d603a (MD5) Previous issue date: 2013-03-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Sugar-alcohol industries are characterized by high water demand, and generate proportional volumes of waste to be disposed. Within the ethanol production process, stillage emerges as an effluent, that is, 15 liters of stillage for every liter of ethanol produced, which is characterized as a high effluent polluting stream: about one hundred times higher than domestic sewage. Its potential pollution is due to the richness in organic content, low pH, high corrosivity and high values of chemical oxygen demand (COD). This work aims to characterizing stillage "in natura" and the use of various coagulants for its treatment, such as FeCl3, Al2SO4 and CaO, in order to treat stillage preliminarily. After the coagulation / flocculation processes, evaluated as a function of the coagulants concentration, the treatment with activated carbon produced from sugar cane bagasse were carried out. The porous structure of carbons and the adsorption of N2 (g). The efficiency of the treatments were quantified in terms of the removal of COD, BOD5, TOC, total solids, color and turbidity. The experimental results showed that the coagulation / flocculation processes, with the coagulant s concentration of 10 g/l, removes a significant amount of organic load, color and turbidity. The subsequent procedure with the activated carbon treatment completes the purification of stillage satisfactorily, that reached average removal rates above 90% for COD, and up to 99% for color and turbidity. / As indústrias sucroalcooleiras se caracterizam por grande demanda de água e geram volumes proporcionais de resíduos a serem descartados. No processo produtivo do etanol, a vinhaça surge como um efluente, ou seja, para cada litro de etanol produzido são gerados 15 litros de vinhaça, sendo caracterizada como um efluente de elevado poder poluente, cerca de cem vezes maior que o do esgoto doméstico. Seu potencial poluidor decorre da sua riqueza em matéria orgânica, baixo pH, elevada corrosividade e altos valores de Demanda Química de Oxigênio (DQO). Este trabalho teve como objetivo caracterizar a vinhaça in natura e avaliar a utilização de diversos coagulantes como FeCl3, Al2SO4 e CaO, com o intuito de tratar preliminarmente a vinhaça. Após o processo de coagulação/ floculação, analisado em função da concentração dos coagulantes, foi realizado o tratamento com carvão ativado produzido a partir do bagaço de cana, sendo determinada a estrutura porosa do carvão e adsorção de N2(g). A eficiência do tratamento foi quantificado em termos de remoção de DQO, DBO5, sólidos totais, cor e turbidez. Os resultados experimentais mostraram que o processo de coagulação/ floculação com concentração de coagulante de 10 g.L-1 removeu uma quantidade significativa de carga orgânica, cor e turbidez. A etapa subsequente com o tratamento do carvão ativado completou satisfatoriamente a purificação da vinhaça, gerando eficiência de remoção superior a 90% para a DQO e 99% para cor e turbidez.

Made available in DSpace on 2015-05-14T12:09:39Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2705810 bytes, checksum: eb7528a28bf11f243846ad12d09da42b (MD5) Previous issue date: 2014-03-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study investigated the treatment of an industrial textile effluent by combined physicochemical processes, coagulation/flocculation - activated carbon. Trials in Jar-Test using the same time for mixing and sedimentation, have improved organic matter and pollutants removal efficiency from the effluent for the coagulants (Al2(SO4)3 e FeCl3) employed. The treatment characterization for optimum concentration found was measured through the determination of SST, DBO, DQO, COT, nitrate, turbidity and surfactants content. For the parameters investigated, the percent removal in accordance with the best optimization trial were 85.6%, 88.9% and 96.2% for DQO, DBO and turbidity, respectively, using the coagulant FeCl3. For the adsorptive treatment of the pre-treated textile effluent, activated carbons were produced the endocarp of coconut (Coccus Nucifera), with chemical activated using Al2(SO4)3 and physical one using water vapor (steam). The ratio of activator:precursor effect on the activation were analyzed, as well as the carbonization temperature, retention time and type of activation on the textural properties of the activated carbons produced. The activated carbons were characterized by N2 adsorption to determine: SBET, SM, VP, VM, VMS and D. The CAQ232FQ carbon showed higher microporosity and SBET (1009 m2.g-1), and it was used in adsorption experiments. The CAQ232FQ carbon was also characterized by: MEV, Boehm, FTIR, TG, DTA, pH, pHPCZ and apparent density. Adsorption experiments with CAQ232FQ carbon were made for pre-treated textile effluent and synthetic sewage. The pH was not adjusted during the adsorption and the temperature was maintained at 26 ºC. The isotherms obtained for both effluents are better adapted to Freundlich model, however, adsorption processes for the pre-treated industrial effluent follows the kinetic model of pseudo-second order, differently to the synthetic industrial effluent which follows model of pseudo-first order. As a concluding remark, adsorption tests with CAQ232FQ carbon have proved to be effective for color removal, considering that the adsorption rate of the dye was higher than 97% in both effluents and the reduction rate of the analyzed parameters was higher than 99% for the industrial textile effluent. / O trabalho investigou o tratamento de um efluente têxtil industrial por processos físico-químicos combinados, coagulação/floculação carvão ativado. Ensaios em ―jar-test‖, utilizando o mesmo tempos de mistura e sedimentação, aperfeiçoaram e verificaram a eficiência de remoção de poluentes do efluente em relação aos coagulantes (Al2(SO4)3 e FeCl3) empregados, a caracterização do tratamento para a concentração ótima encontrada foi por meio das análises de SST, DBO, DQO, COT, nitrato, surfactantes e turbidez. Para os parâmetros investigados, o percentual de remoção de acordo com o melhor ensaio de otimização foram de 85,6%, 88,9% e 96,2% para DQO, DBO e turbidez, respectivamente, utilizando o coagulante FeCl3. Para o tratamento adsortivo do efluente têxtil pré-tratado foi produzindo carvões a partir do endocarpo de coco da baia (Coccus Nucifera) ativados quimicamente com Al2(SO4)3 e fisicamente com vapor d água. Analisou-se o efeito da proporção ativante/precursor, temperatura de carbonização, tempo de retenção e tipo de ativação sobre as propriedades texturais dos carvões produzidos. Os carvões foram caracterizados por adsorção de N2 para determinar: SBET, SM, VP, VM, VMS e D. O carvão CAQ232FQ apresentou maior microporosidade e SBET (1009 m2.g-1), sendo utilizado nos experimentos de adsorção. O carvão CAQ232FQ foi caracterizado também por: MEV, Boehm, FTIR, TG, DTA, pH, pHPCZ, e dens. aparente. Ensaios de adsorção com o carvão CAQ232FQ foram feitos para o efluente têxtil pré-tratado e para o efluente sintético. O pH não foi ajustado durante a adsorção e a temperatura foi mantida em 26oC. As isotermas obtidas para ambos os efluentes se ajustam melhor ao modelo de Freundlich, no entanto o processo de adsorção para o efluente industrial pré-tratado segue o modelo cinético de pseudo-segunda ordem, diferentemente do efluente industrial sintético que segue modelo de pseudo-primeira ordem. Em suma os ensaios de adsorção com o carvão CAQ232FQ se mostraram eficientes visto que a taxa de adsorção do corante foi superior a 97% para ambos os efluentes e a taxa de amenização dos parâmetros analisados foi superior a 99% para o efluente têxtil industrial.

Submitted by Mayara Sakamoto Lopes (mayarasakamoto@hotmail.com) on 2017-10-26T16:08:16Z No. of bitstreams: 1 Dissertação_Mayara Sakamoto Lopes.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-10-31T17:53:45Z (GMT) No. of bitstreams: 1 lopes_ms_me_bauru.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) / Made available in DSpace on 2017-10-31T17:53:45Z (GMT). No. of bitstreams: 1 lopes_ms_me_bauru.pdf: 6344472 bytes, checksum: 53e6e860cec7380199632c6eda1ee064 (MD5) Previous issue date: 2017-10-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As indústrias têxteis caracterizam-se pelos elevados volumes de água consumida e de efluente lançado, o qual, por possuir coloração intensa, reduz a penetração da luz solar nos corpos hídricos receptores e afeta a fotossíntese. Nesse trabalho, avaliou-se a adsorção do corante Azul Reativo 19 (RA19) por carvão ativado comercial (CAP), CAP tratado por ozônio (CAP – O3), lama vermelha (LV) e LV tratada por ozônio (LV – O3). Os adsorventes foram caracterizados quanto ao pH, condutividade elétrica, número de iodo, índice de azul de metileno, granulometria, composição química, mineralogia e micromorfologia. Investigou-se a influência do pH e da temperatura no processo de adsorção. Além disso, analisou-se a cinética da adsorção de RA19 a diferentes concentrações iniciais (300, 500, 1000, 2000 e 3000 mg/L), por meio dos modelos de pseudo primeira ordem, pseudo segunda ordem, difusão intrapartículas e Elovich; e avaliou-se a capacidade de adsorção dos quatro adsorventes, por isotermas de Langmuir e Freundlich. Os resultados indicaram que o tratamento por ozônio não altera significativamente a composição química do CAP e da LV, mas possivelmente reduz o volume de mesoporos do CAP. A eficiência de remoção do RA19 por CAP independe do pH inicial da solução, mas por LV, é favorecida em pH mais baixo (igual a 3). Observou-se que 120 minutos são suficientes para atingir o equilíbrio da reação; e que o aumento da concentração inicial de corante reduz a eficiência de remoção, mas aumenta a capacidade de adsorção. Os dados experimentais ajustaram-se aos modelos de pseudo segunda ordem e de Elovich, indicando que o processo é controlado por quimissorção. Para todos os adsorventes, a adsorção do RA19 é multicamada em superfícies heterogêneas, visto que os dados se ajustaram à isoterma de Freundlich. Os resultados termodinâmicos sugeriram que existe afinidade entre o RA19 e os adsorventes, sendo que a reação ocorre espontaneamente; além disso, a adsorção por CAP e por CAP – O3 é endotérmica, e a adsorção por LV e por LV – O3 é exotérmica. A maior (216,4 mg/g) e a menor (138,7 mg/g) capacidade de adsorção foram obtidas pelo CAP e pelo CAP – O3, respectivamente. Concluiu-se que a ação do ozônio desfavoreceu a adsorção do RA19, em termos de fração residual, quantidade de corante adsorvido, velocidade de reação, e capacidade máxima de adsorção. / Textile industries are characterized by high water consumption and by large effluent release, which is strongly colored and therefore reduces sunlight penetration into water and affects photosynthesis. This study evaluated the adsorption of Reactive Blue 19 (RB19) by commercial activated carbon (PAC), PAC treated by ozone (PAC – O3), red mud (RM) and RM treated by ozone (RM – O3). The adsorbents were characterized by pH, electric conductivity, iodine number, Methylene Blue index, granulometry, chemical and mineralogical composition and micromorphology. Influence of pH and temperature was investigated. Additionally, the RB19 adsorption kinetics was evaluated at different initial concentrations (300, 500, 1000, 2000 and 3000 mg/L) with the pseudo first order, pseudo second order, intraparticle diffusion and Elovich models; and the adsorptive capacity of the adsorbents was investigated by Langmuir and Freundlich isotherms. The results showed that ozone treatment does not significantly change the chemical composition of PAC and RM, but it possibly reduces PAC’s mesopore volume. The initial pH does not influence the efficiency of RB19 removal by PAC, but it influences the removal by RM, being higher at lower pH (equal to 3). The adsorption reached an equilibrium state at about 120 minutes from the beginning of the experiments; and it was observed that increasing initial dye concentration, removal efficiency was reduced, while adsorption capacity was improved. The experimental data fitted well to the pseudo second order and Elovich kinetics models, which indicate that the process is controlled by chemisorption. The RB19 removal obeys the Freundlich isotherm model, showing multilayer adsorption on heterogeneous surface. The thermodynamic studies indicated that RB19 has affinity to the adsorbents, and the reaction occurs spontaneously; furthermore, the adsorption by PAC and PAC – O3 is endothermic, while the adsorption by RM and RM – O3 is exothermic. The highest (216.4 mg/g) and the lowest (138.7 mg/g) adsorption capacity were obtained by PAC and PAC – O3, respectively. It was concluded that ozone negatively affects RB19 adsorption, in terms of residual fraction, amount of dye adsorbed, reaction rate and maximum adsorption capacity.