Dins dels processos de recuperació de metalls de dissolucions diluïdes s'ha realitzat un estudi del procés d'extracció d'or i de zinc mitjançant resines amberlite XAD-2 impregnades amb sulfur de triisobutil fosfina (TIBPS) i àcid di-(2-etilhexil) fosfòric (DEHPA) respectivament.S'ha realitzat un estudi de l'equilibri de l'adsorció d'espècies metàl·liques d'aquests metalls amb les resines indicades anteriorment. Amb la metodologia emprada per a la determinació dels punts d'equilibri dels experiments en batch i en columna, s'ha vist que una única isoterma no podia descriure el fenomen global d'equilibri i que en funció de la metodologia emprada s'obtenien isotermes diferents.Es va introduir una nova variable per poder explicar el fenomen observat, i per tant, amb aquesta nova variable l'equació de la isoterma es converteix amb l'equació d'una supèrfície que s'ha definit com a Superfície d'Equilibri.S'han determinat les equacions de les Suprfícies d'Equilibri dels sistemes d'adsorció estudiats (Au(III) TIBPS/XAD-2 i Zn(II) DEHPA/XAD-2) observan una bona coincidència de tots els punts d'equilibri obtinguts sobre la superfície, així com, un bon ajust de totes les isotermes obtingudes en funció de les diferents metodologies emprades sobre les respectives superfícies d'equilibri. Aquest nou concepte generalitza el concepte d'isoterma d'un procés d'adsorció.Fimalment, s'ha plantejat un model matemàtic d'adsorció per a determinar el coeficient efectiu de difusió (De) i el coeficient de transferància de matèria (kf) per ambdós sistemes d'adsorció estudiats mitjançant l'aplicació del model de difusió de sòlid homogeni (HSDM), utilitzant com a condició de contorn en el model la isoterma de Langmuir obtinguda mitjançant els experiments en columna de llit fix i emprant també l'equació obtinguda mitjançant el nou concepte de Superfície d'Equilibri.Els resultats obtinguts són molt satisfactoris, per tant, es pot concloure que la Superfície d'Equilibri és una bona eina per a descriure l'equilibri en els processos d'adsorció d'or i zinc amb les resines amberlite XAD-2 impregnades amb TIBPS i DEHPA respectivament. / The study of the extraction process of gold and zinc with Amberlite XAD-2 resins impregnated with tri-isobutylphosphine sulfide(TIBPS) and di-(2-ethylhexyl) phosphoric acid (DEHPA), respectively, has been studied.The equilibria governing the metallic ions adsorption by the studied systems have been established. Taking into account the methodology used to get the equilibria points corresponding to batch and column experiments performed, it was noticed that a unique isotherm could not describe the global equilibrium and that different isotherms were obtained in function of the experimental methodology carried out.It was introduced a new variable for explaining the phenomenon observed. By doing this, the isotherm became a surface that it was called equilibrium isotherm.The equations corresponding the Equilibrium Surfaces of the adsorption systems studied (Au(III) / TIBPS-XAD-2 and Zn(II) / DEHPA-XAD-2) were determined. The equilibria points obtained by batch and column experiments as well as obtained isotherms were very well placed on the surface. Thus, this new concept generalises the concept of isotherm in an adsorption process. Finally, the homogeneous solid diffusion model (HSDM) was applied for performing an adsorption mathematical model for determining the effective diffusion coefficient (De) and the mass transfer coefficient (kf) of both studied systems. The obtained results were very successful, so, it can be concluded that the Equilibrium Surface is a very good tool for describing the equilibria of the studied adsorption processes.

Στην εργασία αυτή μελετήθηκε η ρόφηση και η εκρόφηση του παρασιτοκτόνου ατραζίνη (atrazine) σε πρότυπες εδαφικές ουσίες καθώς και σε ένα τυπικό δείγμα εδάφους, τόσο σε αντιδραστήρες διαλείποντος έργου (batch) όσο και σε πληρωμένες κλίνες (bed). Ως πρότυπες ουσίες επιλέχθηκαν η πυριτία (silica-gel, SiO2), η αλούμινα (γ-alumina, Al2O3), το ανθρακικό ασβέστιο (calcite, CaCO3) και το χουμικό οξύ (humic acid). Η ατραζίνη ροφείται σημαντικά στο χουμικό οξύ στην πυριτία και στο έδαφος, όμως βρέθηκε ότι έχει πολύ μεγαλύτερη συγγένεια για το χουμικό οξύ σε σύγκριση με την πυριτία. Η ατραζίνη δεν έδειξε να ροφείται στη γ-αλούμινα και το CaCO3, ανεξαρτήτως από τις πειραματικές συνθήκες που χρησιμοποιήθηκαν. Σε όλες τις περιπτώσεις, η κινητική μελέτη έδειξε δύο διακριτά στάδια: ένα πρώτο γρήγορο στάδιο ρόφησης της ατραζίνης, διαδεχόμενο από ένα δεύτερο πιο αργό στάδιο. Η κινητική της ρόφησης υπακούει ικανοποιητικά στο μοντέλο Elovich. Στα χρονικά πλαίσια που μελετήθηκε η ρόφηση και η εκρόφηση, η διεργασία είναι αντιστρεπτή και η ατραζίνη εκροφείται ποσοτικά. Οι ισόθερμοι ρόφησης της ατραζίνης λήφθηκαν σε διαφορετικές τιμές ιοντικής ισχύος, pH και θερμοκρασίας και υπακούουν στο μοντέλο Freundlich. Σε όλες τις περιπτώσεις που μελετήθηκαν, η αύξηση της ιοντικής ισχύος του διαλύματος προκάλεσε αύξηση της ροφημένης ποσότητας της ατραζίνης. Η ρόφηση της ατραζίνης μειώνεται καθώς το pH του διαλύματος αυξάνεται. Όσον αφορά στην πυριτία, η ρόφηση της ατραζίνης φαίνεται ότι γίνεται κυρίως μέσω δεσμών υδρογόνου με τις υδροξυλομάδες της επιφάνειας. Όσον αφορά στο χουμικό οξύ, το σημαντικότερο ρόλο στη ρόφηση παίζει η διάχυση της ατραζίνης προς το εσωτερικό του στερεού όπου η ρόφηση επιτυγχάνεται κυρίως μέσω υδρόφοβων αλληλεπιδράσεων. Η προσρόφηση της ατραζίνης στην πυριτία αυξάνεται σημαντικά καθώς αυξάνεται η θερμοκρασία του διαλύματος, μια τάση που δεν παρατηρείται κατά τη ρόφηση της ατραζίνης στο χουμικό οξύ. Η θερμοδυναμική ανάλυση έδειξε ότι η ρόφηση στα μοντέλα εδάφους είναι φυσική αφού παρατηρήθηκαν τιμές της ενθαλπίας ρόφησης στην περιοχή των 10 kJ mol-1. Οι λαμβανόμενες ισόθερμοι ρόφησης από τα πειράματα σε πληρωμένες κλίνες ήταν σε καλή συμφωνία με αυτές που λήφθηκαν από τα πειράματα στους αντιδραστήρες διαλείποντος έργου. Η παρουσία χουμικού οξέος στις κλίνες προκαλεί με το χρόνο δραστική μείωση της διαπερατότητας. / Adsorption and desorption of the herbicide atrazine was investigated on the principal inorganic constituents of soil, as well as on a typical Greek soil sample. The studies were conducted both in batch, stirred reactors and in packed beds. Silica-gel (SiO2), γ-alumina (Al2O3) and calcite (CaCO3), were selected as model inorganic substances. Humic acid was selected as a model substance representative of the organic part of soil. Significant adsorption of atrazine was measured on the humic acid, silica and on the soil suspensions in electrolyte solutions. Atrazine exhibited higher affinity for humic acid rather than for silica. Atrazine did not adsorb on γ-alumina and on CaCO3 regardless the experimental conditions (pH range or total solid available for adsorption). In all cases, kinetic results have shown two distinct features: a first, fast sorption step, followed by a second, slow step. The kinetics data of atrazine uptake on both substrates yielded satisfactory fit to the Elovich model. Atrazine was found to be completely desorbed from both the humic acid and the silica substrates. Adsorption isotherms for atrazine were obtained at different values of ionic strength, pH and temperature. The adsorption data gave the best fit to the Freundlich model. In all cases investigated, the amount of adsorbed atrazine increased upon increasing the ionic strength of the solution. The adsorption of atrazine decreased with increasing solution pH. The adsorption of atrazine on silica was primarily dominated by the formation of hydrogen bonds with the surface hydroxyl groups. In the case of humic acid, the diffusion of atrazine to the interior of the solid seemed to play the most significant role. Inside the organic substance particles, sorption took place mainly through hydrophobic interactions. The sorption of atrazine on silica surface increased considerably with increasing temperature, a trend not found in the case of humic acid. The thermodynamic analysis yielded adsorption energy values of the order of 10 kJ mol-1 suggesting physical adsorption. The isotherms obtained from the packed bed experiments were in a good agreement with those obtained from batch experiments. Finally, humic acid grains, mixed with silica in packed beds, were found to change morphology upon hydration which resulted to swelling. The humic substances clogged a large portion of the pores of the packed beds, decreasing drastically their permeability.

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Orientador: Newton Luiz Dias Filho / Resumo: No presente trabalho, a 3-cloropropil sílica gel (SG) foi preparada e organofuncionalizada com dois grupos funcionais, 2-aminotiazol (SATZ) e 5-amino-1,3,4-tiadiazol-2-tiol (SATT). Com o objetivo de produzir novos materiais através da modificação química da superfície da sílica gel, com aplicabilidade na remoção de íons metálicos em meio etanólico, tendo a possibilidade de serem aplicados na remoção de metais pesados em combustível etanol e aguardente. Esses novos materiais também podem ser trabalhados como novos eletrodos quimicamente modificados na detecção de nitrito encontrado na urina e em águas naturais. Esses materiais foram caracterizados por técnicas de espectroscopia na Região do Infravermelho (FTIR), ressonância magnética nuclear (RMN) e microscopia eletrônica de varredura (MEV). Posteriormente foram realizados estudos de adsorção de íons metálicos (Cu+2, Cd+2 e Zn+2) para o SATZ e SATT em solvente etanólico (99%). Para testar a capacidade de adsorção de íons metálicos, determinou-se a cinática de adsorção para todos íons Cu+2, Cd+2 e Zn+2 (40 minutos), determinou-se a capacidade de adsorção (Nf) através de isotermas com diferentes concentrações molares dos íons metálicos. Ambos os adsorventes tiveram uma capacidade máxima de adsorção maior para os íons Zn2+ do que para os íons Cd2+ e Cu2+, de acordo com a seguinte ordem: Zn2+>Cd2+>Cu2+. Em uma segunda etapa do trabalho após a adsorção dos íons cúpricos (Cu2+) pelo SATT, reagiu-se o SATT com hexacianoferrato (III) ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In the present work, 3-chloropropyl silica gel (SG) was prepared and organofunctionalized with two functional groups, 2-aminothiazole (SATZ) and 5-amino-1,3,4-thiadiazole-2-thiol (SATT). With the objective of producing new materials through the chemical modification of the silica gel surface, with applicability in the removal of metallic ions in ethanolic medium, having the possibility of being applied in the removal of heavy metals in fuel ethanol and brandy. These new materials can also be worked as new chemically modified electrodes in the detection of nitrite found in urine and in natural waters. These materials were characterized by Infrared Region Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR) and Scanning Electron Microscopy (SEM) techniques. Subsequently, adsorption studies of metal ions (Cu + 2, Cd + 2 and Zn + 2) were performed for SATZ and SATT in ethanolic solvent (99%). The adsorption kinetics were determined for all metal ions Cu + 2, Cd + 2 and Zn + 2 (40 minutes), the adsorption capacity (Nf) was determined through isotherms with different molar concentrations of the metal ions. Both adsorbents had a maximum adsorption capacity it was higher for Zn2 + ions than for Cd2 + and Cu2 + ions, according to the following order: Zn2 +> Cd2 + > Cu2+ . In a second step of the work after the copper ions (Cu2+) adsorption by SATT, the SATT was reacted with potassium hexacyanoferrate (III), thus forming the CuSATTH complex. The graphite paste electrode chemically mod... (Complete abstract click electronic access below) / Mestre

Orientador: Vânia Regina Nicoletti Telis / Banca: Caciano Pelayo Zapata Noreña / Banca: Joel Fernando Nicoleti / Banca: José Francisco Lopes Filho / Banca: José Antônio Gomes Vieira / Resumo: Os objetivos deste trabalho foram analisar a influência do tipo e da quantidade de aditivos, além de diferentes métodos de secagem da polpa de maracujá em pó, nas isotermas, propriedades termodinâmicas de sorção e nos atributos de qualidade do produto obtido. No capítulo 1 descreve-se o efeito de diferentes aditivos - maltodextrina DE 10 e goma arábica - sobre as isotermas de sorção nas temperaturas de 20, 30, 40 e 50 ºC de polpa de maracujá em pó obtida por secagem a vácuo. O modelo de GAB se ajustou aos dados de sorção. As isotermas apresentaram comportamento da curva do tipo II, na classificação de Brunauer. Observou-se que a adição de maltodextrina DE 10 e de goma arábica à polpa de maracujá desidratada reduziu a umidade de equilíbrio em relação à umidade da polpa pura e não houve diferença considerável entre as umidades de equilíbrio das amostras da polpa com 18% de goma arábica e polpa com 18% ou 55% de maltodextrina. O aumento da concentração da maltodextrina não teve influência sobre os valores de umidade de equilíbrio. O calor isostérico de sorção da polpa em pó aumentou com o decréscimo da umidade, ao mesmo tempo em que apresentou menores valores para a polpa em pó com aditivos do que os observados para a polpa pura. Através da teoria da compensação isocinética, pode-se concluir que o processo de sorção de água pela polpa de maracujá em pó é um processo espontâneo e controlado pela entalpia para todas as amostras testadas. No capítulo 2 foi analisada a influência de três métodos de secagem: em estufa a vácuo (60 ºC), spray drying (140 ºC) e liofilização sobre as isotermas da polpa de maracujá em pó com 55% de maltodextrina DE 10. O pó produzido em spray dryer apresentou maior capacidade de sorção em relação aos pós desidratados em estufa a vácuo e em liofilizador. No capítulo 3 foi avaliada a influência... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objectives of this work were to analyze the influence of type and quantity of additives, in addition to different drying methods, on the production of powdered passion fruit pulp, on its water sorption isotherms and on its themodynamical properties, as well as evaluating the quality attributes of the obtained product. Chapter 1 describes the effect of different additives - maltodextrin DE 10 and Arabic gum - on the sorption isotherms at temperatures of 20, 30, 40 e 50 ºC of passion fruit pulp powder obtained by vacuum drying. The sorption data were well adjusted by GAB model. The isotherms presented behavior of type II curves according to the Brunauer classification. The addition of maltodextrin DE 10 and Arabic gum to the passion fruit pulp powder decreased the equilibrium water content when compared to the pure powdered pulp and no considerable differences between the equilibrium moisture content of samples with 18% of arabic gum and with 18% or 55% of maltodextrin were observed. The increase in maltodextrin concentration did not affect the equilibrium water contents. The isosteric heat of sorption of the powdered pulp increased with decreasing water content, at the same time that lower values were obtained to powdered pulp with additives than to pure powdered pulp. Through the isokinetic compensation theory it could be concluded that the water sorption process by the powdered passion fruit pulp is an enthalpy controlled, spontaneous process for all tested samples. In chapter II, the influence of three drying methods: vacuum drying (60 ºC), spray drying (140 ºC) and freeze drying over the powdered passion fruit pulp isotherms with 55% of maltodextrin DE 10, was analyzed. The passion fruit pulp powder produced by spray drying presented higher sorption ability than vacuum dried and freeze dried pulp. In chapter 3, the influence of different concentrations and different dextrose... (Complete abstract click electronic access below) / Doutor

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-08-03T17:08:27Z No. of bitstreams: 1 ANA PAULA PRETTE - TESE PPGEA 2012..pdf: 24680734 bytes, checksum: 1ae74f0a6e5641ff2a39682b249a0e6b (MD5) / Made available in DSpace on 2018-08-03T17:08:27Z (GMT). No. of bitstreams: 1 ANA PAULA PRETTE - TESE PPGEA 2012..pdf: 24680734 bytes, checksum: 1ae74f0a6e5641ff2a39682b249a0e6b (MD5) Previous issue date: 2012-10 / A relação entre o conteúdo de umidade e a atividade de água proporciona informações úteis para o armazenamento e processamento de alimentos. Objetivou-se a aplicação do processo de secagem para polpa e resíduos de jaca (Artocarpus heterophyllus Lam.), visando seu possível aproveitamento na indústria. Na pesquisa foram determinadas isotermas de dessorção para a polpa, casca, mesocarpo, eixo central e sementes de jaca a 40, 50, 60 e 70 °C, na faixa de conteúdo de umidade entre 0,001 e 0,278 kg-kg"1 e atividades de água entre 0,02 a 0,753. O modelo teórico de GAB e os modelos empíricos de Oswin, Halsey, Henderson e Iglesias-Chirife foram empregados para a modelagem. Foi proposta a primeira derivada da solução analítica da equação de Clausius-Clapeyron para calcular o calor isostérico de sorção e a entropia diferencial para os resíduos e polpa de jaca, através dos modelos de GAB e Oswin quando o efeito da temperatura em equilíbrio higroscópico foi considerado. Secagem de casca, polpa e sementes de jaca foram realizadas em um secador de leito fixo, nas velocidades do ar de 0,7; 1,4 e 1,8 nrs"1 e temperaturas de 40, 50, 60 e 70 °C. Os modelos de Peleg, Page, Henderson-Pabis e difusivo foram empregados na modelagem das curvas de secagem. Observou-se período de taxa decrescente nos experimentos. Com as informações obtidas na secagem, foram formulados produtos alimentícios a base de polpa e resíduos de jaca, os quais foram caracterizados via química, nutricional, sensorial e microbiológica. / The objective of this paper is the drying process implementation for pulp and jackfruit waste items {Artocarpus heterophyllus Lam.) for a possible application in the industry.The relationship between moisture content and water activity provides useful information for processing and storage of jackfruit wastes. The desorption isotherms for pulp, peel, mesocarp, central axis and seeds of jackfruit were determined at four different temperatures (40, 50, 60 and 70 °C) over wide ranges of moisture content (0,001-0,278 kg-kg"' and water activity (0,02-0,753). The theoretical model of GAB and the empirical models of Oswin, Halsey, Henderson and Iglesias-Chirife were used to modeling the desorption isotherms. The analytical solution of the Clausius-Clapeyron equation was proposed to compute the isosteric heat of sorption and the differential entropy, for peel, mesocarp and pulp of jackfruit, by means of the GAB and Oswin models when the effect of temperature on hygroscopic equilibrium was considered. Drying kinetics for peel, pulp and seeds of jackfruit in convective hot air forced equipment were determined, at three air velocities (0,7; 1,4 and 1.8 nvs"1) and four temperatures (40, 50, 60 and 70 °C).In the graphical analysis, a falling rate period was found for all experimental curves. Finally, with the information obtained in the drying process, products were formulated with the pulp and others jackfruit items, which were characterized via chemical, nutritional, sensory and microbiological.

Na atualidade estudos direcionados para a avaliação do risco químico e do impacto ambiental produzidos por compostos químicos de uso intensivo, como agrotóxicos, petroquímicos e fármacos, vêm ganhando importância por elucidarem as implicações ao meio ambiente e à saúde pública decorrentes deste uso pela sociedade moderna de forma a estabelecer parâmetros restritivos para suas aplicações, evitando-se danos posteriores. Este Estudo compreendeu as observações de sorção e de interação do antibiótico de uso animal e agrícola oxitetraciclina (OTC) com solos brasileiros e ácidos húmicos (AH) extraídos de solos, tendo-se como objetivos gerais comprovar a sorção aos solos e aos AH e verificar a influência da matéria orgânica (MO) e do pH sobre a sorção, definindo quais os mecanismos moleculares de interação envolvidos, cabendo destacar que as tetraciclinas são uma das principais classes de antibióticos utilizadas na pecuária brasileira, tanto para tratamento de enfermidades quanto como Antibióticos Promotores de Crescimento (APC), além de serem freqüentemente aplicados na agricultura para controle de fungos e bactérias. Utilizou-se a Cromatografia Líquida de Alta Eficiência (CLAE) para a coleta de dados quantitativos que permitiram a construção de isotermas de sorção solo-OTC em pH 4,8 e AH-OTC em três valores de pH (3,1, 4,8 e 8,3) para a comprovação da sorção e da influência do conteúdo de MO no primeiro caso, e na sorção aos AH, para o segundo caso. Os solos foram caracterizados conforme procedimento padrão da EMBRAPA, enquanto que os AH foram caracterizados segundo procedimentos recomendados pela literatura por meio das técnicas instrumentais de Análise Elementar, Absorção na Região do Infravermelho Médio, Ressonância Magnética Nuclear e Ressonância Paramagnética Eletrônica. Foram utilizadas as técnicas espectroscópicas de Absorção na Região do Infravermelho (Próximo e Médio) e Absorção e Fluorescência na Região do UV-Visível, para a avaliação dos possíveis mecanismos de interação envolvidos, como ligação de hidrogênio, interação hidrofóbica e transferência de elétrons. A isoterma de Freundlich apresentou-se como um modelo matemático adequado para a verificação da sorção solos-OTC e AH-OTC, a partir da aplicação de um método cromatográfico adequado, comprovando a sorção para os dois casos, bem como o efeito do conteúdo de MO dos solos e do pH do meio sobre a capacidade e a intensidade da sorção, a qual foi quantificada como de capacidade de sorção inferior em comparação a dados obtidos em clima temperado e de alta capacidade de sorção quando comparada à legislação ambiental brasileira. Foi observado que a OTC interagiu com os AH em uma larga faixa de valores de pH, indo de 3,1 a 8,3. Contudo, o meio no qual foi possível observar de uma forma mais acentuada a interação entre AH e OTC foi o meio básico (pH 8,2), sendo notado a existência de mecanismos de interação associados e dependentes do pH do meio, como: ligação de hidrogênio, interação hidrofóbica e transferência de prótons. / At present further studies on the risk assessment of chemical and environmental impact produced by chemical-intensive, such as pesticides, petrochemicals and pharmaceuticals, have gained importance for elucidating the implications for the environment and public health arising from this use by modern society to establish restrictive parameters for their applications, avoiding further damage. This Study comprised observations of sorption and interaction of antibiotic for animal and agriculture use oxytetracycline (OTC) with brazilian soils and humic acids (HA) extracted from soil, having as objectives to prove the general sorption to soils and the AH and the influence of organic matter (OM) and pH on the sorption, which define the molecular mechanisms of interaction involved, highlighting that tetracyclines are a major classes of antibiotics used in the brazilian cattle industry, both for treatment of diseases such as antibiotic growth promoters (AGP), and frequently also applied in agriculture to control fungi and bacteria. The High Performance Liquid Chromatography (HPLC) was used to collect quantitative data that allowed the construction of sorption isotherms soils-OTC in pH 4.8 and AH-OTC in three pH values (3.1, 4, 8 and 8.3) for proof of sorption and the influence of OM content in the first case, and sorption to AH, for the second case. The soils were characterized as standard procedure of EMBRAPA, while AH were characterized according to procedures recommended by the literature by means of instrumental techniques for Elemental Analysis, Absorption in the Region of the Middle Infrared, Nuclear Magnetic Resonance and Electron Paramagnetic Resonance. The Spectroscopic Absorption in the Infrared Region (Middle) and Fluorescence and Absorption in the Region and the UV-Visible were used for the evaluation of interaction mechanisms involved, such as hydrogen bonding, hydrophobic interactions and electron transfer. The Freundlich isotherm was presented as a mathematical model suitable for the verification of soils-OTC sorption and AH-OTC sorption from the application of a chromatographic method that is suitable, proving the sorption for the two cases as well as the effect of OM content of soils and the pH on the capacity and sorption intensity, which was quantified as the lower sorption capacity in comparison with data from temperate and high sorption capacity when compared to Brazilian environmental legislation. It was observed that the OTC interacted with the HA in a wide range of pH values, ranging from 3.1 to 8.3. However, the way in which it was possible to observe a more pronounced interaction between HA and OTC was the basic medium (pH 8.2), and noted the existence of mechanisms of interaction associated and dependent on pH, such as: link hydrogen, hydrophobic interaction and proton transfer.

Submitted by LILIAN FACHIN LEONARDO BETIOL null (lilianfacleo@hotmail.com) on 2016-12-04T18:12:23Z No. of bitstreams: 1 Tese - Formatada (1) Corrigida.pdf: 1975637 bytes, checksum: a2ca74a2f726452b217e860e0c11c866 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-12-06T13:52:01Z (GMT) No. of bitstreams: 1 betiol_lfl_me_sjrp.pdf: 1975637 bytes, checksum: a2ca74a2f726452b217e860e0c11c866 (MD5) / Made available in DSpace on 2016-12-06T13:52:01Z (GMT). No. of bitstreams: 1 betiol_lfl_me_sjrp.pdf: 1975637 bytes, checksum: a2ca74a2f726452b217e860e0c11c866 (MD5) Previous issue date: 2016-11-21 / As isotermas de sorção tornaram-se importantes para prever o comportamento da cinética de secagem e as condições de armazenamento de resíduos da indústria alimentícia. O conhecimento de tal propriedade é útil para projetar equipamentos ou operações para fins de armazenamento ou processamento. O bagaço quando é apenas descartado, representa um desperdício de matéria prima, de compostos orgânicos com categoria bioquímica definida (proteínas, açúcares, ceras, graxas, resinas), que poderia ser aproveitada. Dentro deste contexto, a presente pesquisa teve como objetivo caracterizar quimicamente o bagaço de mandioca e fazer a determinação experimental das isotermas de sorção destes resíduos da indústria de fécula, além de calcular a entalpia e entropia, temperatura media harmônica e calor isostérico de adsorção. Para isso, o teor de umidade de equilíbrio nas isotermas de sorção, de bagaço de mandioca, foi determinado utilizando o método gravimétrico estático nas temperaturas de 20 a 80 °C. Modelos teóricos e empíricos foram usados para representar os valores experimentais das isotermas de sorção, sendo que o modelo de GAB foi o que apresentou os melhores ajustes. Utilizando o modelo de GAB foi possível determinar o calor isostérico de adsorção como função do teor de umidade. A teoria da compensação foi confirmada pela relação linear entre entalpia e entropia. Maiores valores de temperatura isocinética do que a temperatura harmônica reforçam a teoria da compensação e sugeriram que a adsorção de água pelo bagaço de mandioca é considerado um processo conduzido pela entalpia. / The sorption isotherms become important to predict the drying kinetics behavior and waste storage conditions of the food industry. The knowledge of such property is useful for designing equipment or operations for storage or processing. The bagasse is only when discarded, is a waste of raw materials, organic compounds with defined biochemical category (proteins, sugars, waxes, greases, resins), which could be harnessed. Within this context, this study aimed to chemically characterize the Cassava Bagasse and make the experimental determination of the sorption isotherms of these starch industry waste and calculates the enthalpy and entropy, harmonic average temperature and isosteric heat of adsorption. For this, the equilibrium moisture content in the sorption isotherms of cassava bagasse was determined using the gravimetric static method in temperatures 20-80 ° C. Theoretical and empirical models were used to represent the experimental values of sorption isotherms, and the GAB model was the one that presented the best fit. Using the GAB model was possible to determine the isosteric heat of adsorption and moisture content of the function. The theory of compensation was confirmed by the linear relationship between enthalpy and entropy. Isokinetic higher temperature values than the harmonic temperature reinforce the theory of compensation and suggested that the adsorption of water by mancioca bagasse and considered one of enthalpy driven process.

Os materiais reativos orgânicos, como turfas e compostos, apresentam um considerável potencial efetivo de utilização na remediação de áreas contaminadas por metais potencialmente tóxicos, haja vista sua elevada capacidade de adsorção, comumente associada a altos teores de matéria orgânica. O emprego do composto orgânico se torna vantajoso por ser uma possibilidade de destinação final correta dos resíduos sólidos urbanos compostáveis, conforme as políticas públicas, podendo agregar valor econômico e ambiental ao resíduo. Nessa perspectiva, na seleção dos materiais reativos mais viáveis para serem empregados na retenção de metais é imprescindível sua caracterização (geológica e geotécnica) e o estudo de sua real capacidade adsortiva, através de ensaios de adsorção. Assim, o objetivo desta pesquisa foi a caracterização geológica e geotécnica de uma turfa (proveniente da bacia hidrográfica do rio Mogi Guaçu, município de Cravinhos) e de quatro compostos (compostos total, indiano, estático e alambrado, advindos de composteiras localizadas na Universidade de São Paulo - São Carlos), bem como ensaios de adsorção (equilíbrio em lote) com chumbo (Pb), zinco (Zn) e cádmio (Cd). Para tanto foram realizados os seguintes ensaios de caracterização: granulometria, massa específica dos sólidos, densidade, teor de umidade, parâmetros físico-químicos (potencial hidrogeniônico (pH), &Delta;pH, potencial de oxi-redução (Eh) e condutividade elétrica (CE), ponto de efeito salino nulo (PESN), matéria orgânica (MO), teor de cinzas (Cz), capacidade de troca catiônica (CTC), capacidade de retenção de água (CRA), composição elementar (C, H e N), carbono orgânico, Difratometria de Raios-X (DRX), Fluorescência de Raios-X (FRX), Microscopia Eletrônica de Varredura/Espectroscopia de Energia Dispersiva por Raios-X (MEV/EDS) e Análise Térmica Diferencial (ATD). A partir do conhecimento minucioso dos parâmetros físicos e químicos dos materiais foi possível proceder o ensaio de equilíbrio em lote com soluções monoelementares de Pb, Zn e Cd com oito concentrações distintas e inferiores a 220 mg L-1 e razão material reativo/solução de 1/50 (conforme definido em etapa preliminar). Quanto aos resultados de caracterização, turfa e compostos apresentaram características promissoras para a adsorção. A turfa revelou um pH moderadamente ácido (5,1), um &Delta;pH negativo (-1,0) atestando para a presença majoritária de cargas negativas na superfície das partículas, o que foi confirmado pelo PESN (3,6) < pH (5,1), um considerável teor de MO (520,43 mg kg-1) e uma CTC elevada (91,00 cmolc kg-1). Já os compostos exibiram valores de pH ligeiramente ácidos a ligeiramente básicos (6,4 a 7,7), &Delta;pH negativo (-0,4 a -1,0), MO promissora (193,92 a 418,70 mg kg-1) e CTC variável (29,00 a 75,00 cmolc kg-1). Em termos gerais, os compostos total e indiano apresentaram características mais favoráveis para a retenção metálica o que foi confirmado por etapa preliminar do ensaio de adsorção. Como o composto indiano sobressaiu levemente na imobilização de Cd e Zn e por ele apresentar maior controle no processo de compostagem ele foi o escolhido para a realização do ensaio de equilíbrio em lote com variadas concentrações de Pb, Zn e Cd, assim como a turfa. Os resultados finais de adsorção atestaram que a turfa e o composto indiano apresentaram a mesma ordem de afinidade metálica: Pb > Cd > Zn, sendo que o composto revelou uma tendência superior de adsorção. A turfa revelou uma porcentagem de remoção metálica (A%) superior a 90% para concentrações de Pb de até 137 mg L-1, enquanto o composto adsorveu mais de 98% do Pb em todas as concentrações estudadas (26 a 214 mg L-1), não atingindo o estado de saturação. Dessa forma, turfa e compostos, caracterizados por um baixo custo e uma significativa disponibilidade, podem ser enquadrados como potenciais materiais reativos orgânicos para a imobilização de cátions metálicos, principalmente Pb2+ e Cd2+. / Organic reactive materials, such as peat and compounds, have a considerable potential for use in the remediation of contaminated areas by potentially toxic metals, due to their high adsorption capacity, commonly associated with high organic matter content. The use of organic compound becomes advantageous because it is a possibility of final destination for the compostable municipal solid waste, according to the public policies, being able to add economic and environmental value to the waste. In this perspective, the selection of the most viable reactive materials to be used in the retention of metals is needful, its characterization (geological and geotechnical) and the study of its real adsorptive capacity through adsorption tests are essential. Thus, the objective of this research was to characterize the geological and geotechnical characteristics of a peat (from Mogi Guaçu\'s basin in the city Cravinhos) and four compounds (total, indian, static and wired, from composters located at the University of São Paulo), besides batch tests with lead (Pb), zinc (Zn) and cadmium (Cd). To achieve the objectives, the following tests were done: particle size analysis, solids specific mass\' determination, density, moisture content, physico-chemical parameters (potential hydrogenion - pH, &Delta;pH, oxy-reduction potential - Eh and electrical conductivity - EC), point of zero salt effect (PZSE), organic matter (OM), ash content, cation exchange capacity (CEC), water retention capacity (WRC), elemental composition (C, H and N), organic carbon, X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Scanning Electron Microscopy/X-Ray Dispersive Energy Spectroscopy (SEM/DES) and Differential Thermal Analysis (DTA). From the detailed knowledge of the physical and chemical parameters of the materials was possible to perform the batch equilibrium test with monoelemental solutions of Pb, Zn and Cd with different concentrations below 220 mg L-1 and reactive material/solution ratio of 1/50 (as defined in the preliminary stage). Regarding the characterization results, peat and compounds presented promising characteristics for adsorption. The peat showed moderately acidic pH (5.1), negative &Delta;pH (-1.0) attesting to a majority presence of negative charges on the surface of the particles, which was confirmed by the PZSE (3.6) < pH (5.1), a considerably high OM content (520.43 mg kg-1) and a high CEC (91.00 cmolc kg-1). The compounds exhibited from slightly acidic to slightly basic pH values (6.4 to 7.7), negative &Delta;pH (-0.4 to -1.0), promising OM (193.92 to 418.70 mg kg-1) and variable CEC (29.00 to 75.00 cmolc kg-1). In general, terms, the total and indian compounds presented more favorable characteristics for metal retention, what was confirmed by the preliminary step of the adsorption test. As the Indian compound had a small enhancement on the immobilization of Cd and Zn and due, it showed greater control in the composition process, it was chosen for a batch equilibrium test with varying concentrations of Pb, Zn and Cd, as well as a peat. The final adsorption results showed that the peat and the indian compound had the same order of metal affinity: Pb > Cd > Zn, whereby the compound showed a higher adsorption tendency. The peat showed a metal removal percentage (A%) higher than 90% for Pb concentrations up to 137 mg L-1, while the compound adsorbed more than 98% at all concentrations studied (26 to 214 mg L-1) not reaching the saturation state. Thus, peat and organic compounds, characterized by a low cost and a significant availability, can be classified as potential organic low-cost reactive materials for metal cations immobilization, mainly Pb2+ and Cd2+.

La méthode microgravimétrique statique a permis d’observer que la pulpe de l’aiélé est plus hygroscopique que l’amande de karité à 25°C. A l’inverse, on fait l’observation contraire entre 35 et 55°C. Le modèle d’Oswin décrit le mieux les données de sorption des deux produits sur toute la gamme d’activité de l’eau. Les isothermes de l’amande de karité et de la pulpe de l’aiélé présentent le phénomène d’hystérésis entre 25 et 55°C. La conservation de ces oléagineux doit s’effectuer dans une atmosphère d’humidité relative comprise entre 40 et 60% afin d’obtenir des teneurs en eau recommandées. Un modèle adapté de prédiction des isothermes de sorption de ces oléagineux en deçà de 25°C et au delà de 55°C a été obtenu. L’extraction de la matière grasse au CO2 supercritique donne des rendements inférieurs à ceux obtenus de l’extraction à l’hexane. L’indice d’acide des matières grasses extraites au CO2 est supérieur à celui des lipides extraits à l’hexane. Ces indices, pour les lipides extraits des produits stockés à 18°C, sont les plus élevés. Quelque soient le mode de stockage et le solvant d’extraction, l’indice d’iode baisse avec le stockage. Le CO2 présente une sélectivité vis-à-vis de l’acide linolénique. Les lipides extraits au CO2 présentent les taux d’acides gras libres les plus élevés. Il ressort des résultats que le stockage -33°C est le meilleur. Toutefois, il ne doit pas dépasser 5 mois. L’extraction des lipides au CO2 supercritique doit utiliser les fruits frais ou stockés à -33°C. Les produits stockés à 18°C sont les plus durs et la dureté est corrélée négativement à la teneur en eau, mais positivement à l’indice d’acide des matières grasses extraites / The static microgravimetric method permitted to observe that the Canarium pulp was more hygroscopic at 25°C than the sheanut kernels. On the other hand, sheanut kernel was more hygrocopic in the temperature range 35°C-55°C. The Oswin model best described the sorption data of the two products in the whole water activity range. Hysteresis was observed in the entire temperature range 25-55°C for sheanut kernel and Canarium pulp. It is suggested that these products should be stored in an environment with a relative humidity of 40-60%, in order to attain the recommended moisture content for storage. A model was adapted to predict the sorption isotherms of shea and Canarium below 25°C and above 55°C. The oil yields obtained with supercritical CO2 were lower than those obtained with hexane. The acid values of butter and oil extracted with carbon dioxide were greater than those of lipids extracted using hexane. The acid values of samples stored at 18°C were the largest. The iodine value of the oils decreased with an increase of the storage period, irrespective of the storage temperature and the solvent used for extraction. The extraction with CO2 did not extract linolenic acid. The proportion of free fatty acids increased when carbon dioxide was used for extraction. From the foregoing, it is suggested that storage at -33°C for up to 5 months presents the best means of preserving these products. Only fresh or fruits stored at -33°C should be used for the extraction of lipids using carbon dioxide. The products stored at 18°C were the most hard and the hardness was correlated negatively to the water content, but positively to the acid value of fatty material extracted