Chitin, chitosan recovered from fly crabs shells have been investigated by the elemental analysis, potentiometric titraton and FT–IR spectrometry methods. The molecular weght of chitosan was determined by measuring their viscosity. The adsorption kinetics of reactive dye and equilibrium conditions has been investigated. The adsorption of reactive dye on chitin and chitosan proceeds according to pseudo – second – order kinetic equation. Adsorption investigations under equilibrium conditions showed that. Theses results were fitted by both Langmuir and Freudlich models.

This study was to prepare nanoscale MgO using the homogeneous precipitation process and to investigate its destructive adsorption with dye wastewater of reactive black-5 and reactive blue-19. In addition, UV-vis Spectrophotometer, Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and Gas Chromatograph/Mass Spectrometer (GC/MS) were used to analyze the intermediates resulting from destructive adsorption. Based on the results obtained, the destructive adsorption mechanisms for the treatment of dye wasterwater by nanoscale MgO were proposed in this study. In this work, the optimal operating conditions for nanoscale MgO synthesis were determined to be the following: (1) a chemical reaction time of 7 hr, (2) reaction temperature of 125¢J, (3) molar ratio of 9 for urea/MgCl2¡D6H2O, (4) water addition of 250 mL, (5) mixing intensity of 90 strokes per min, (6) calcination at 450¢J for 4 hr, (7) reflux time of 24 hr, (8) freeze-drying method, (9) two stage calcinations. Using these operating conditions one is able to prepare 2-D nanoscale MgO of hexagonal platelets with a thickness of 20-30 nm and BET surface area of 120-125 m2/g. The adsorption model of nanoscale MgO for RB-5 and RB-19 was fitted to the Langmuir equation and their adsorption capacity were 196.08 mg/g and 163.93 mg/g, respectively. Both of them were fitted to the pseudo-second-order kinetic model equation. The optimal operating conditions of nanoscale MgO for destructive adsorption of both dyes were determined to be the following: (1) an initial dye concentration of 1000 mg/L, (2) a nanoscale MgO dose of 15 g/L, (3) a vigorous mixing of 30 min, (4) no need of system pH adjustment. Under such conditions, chemical oxygen demand (COD) and American Dye Manufacturers Institute (ADMI) of RB-5 and RB-19 were lower than the textile effluent standards. According to the UV-vis spectrophotometer scanning results, the color removal of nanoscale MgO for RB-5 and RB-19 was good. At the same time, the absorbance of their second maximal peaks was decreased and some peaks were observed. Therefore, it proved that the model dyes were destroyed. Experimental results have shown that nanoscale MgO has a better performance of destructive adsorption on RB-5 than that of RB-19. This might be ascribed to the following reasons: (1) a greater molecular weight, (2) a longer molecule structure, (3) more sulfate ethyl sulfone groups for RB-5, and (4) a hard to be destroyed structure of anthraquinone for RB-19. The destructive adsorption of dye wastewater by nanoscale MgO presumably took place mainly on the surface active sites of nanoscale MgO, including anion/cation vacancies, superoxide anion, edge, corner, isolated OH, lattice bound OH and assiocited-OH groups. According to the results of MALDI-TOF/MS and GC/MS analysis, the relevant reaction mechanism for RB-5 could be divided into three stages: (1) adsorption and water-soluble groups exfoliation stage, (2) chromophor decomposition and decolorization stage, and (3) further degradation stage for light-color intermediates. On the other hand, the relevant reaction mechanism for RB-19 might involve only the adsorption and auxochrome exfoliation stage and chromophor decomposition and decolorization stage.

No / A new technique using ozone loaded on adsorbents for industrial waste-water treatment has been investigated. This is a three-step process: ozone adsorption on a fixed bed column; water treatment on the bed loaded with ozone; and finally drying/ regeneration of the wet bed. Silica gel of mean particle size of 1.5 mm has been tested for ozone loading capacities followed by water treatment, both at ambient temperature. The mechanisms of the mass transfer process during ozone loading and water treatment have been established. The drying of the adsorbent using vacuum and dry air is feasible, but it is a time-consuming operation. A design procedure is described for the whole system.

This work was concerned with the determination of mass transfer and kinetic parameters of ozone reactions with four organic compounds from different families, namely reactive dye RO16, triclocarban, naphthalene and methanol. In order to understand the mechanisms of ozone reactions with the organic pollutants, a radical scavenger (t-butanol) was used and the pH was varied from 2 to 9. Ozone solubility (CAL*) is an important parameter that affects both mass transfer rates and chemical reaction kinetics. In order to determine accurate values of the CAL* in the current work, a set of experiments were devised and a correlation between CAL* and the gas phase ozone concentration of the form CAL*(mol/L) = 0.0456 CO3 (g/m3 NTP) was obtained at 20°C. This work has also revealed that t-butanol did not only inhibit hydroxyl radical reactions but also increased mass transfer due to it increasing the specific surface area (aL). Values of the aL were determined to be 2.7 and 3.5 m2/m3 in the absence and presence of t-butanol respectively. It was noticed that the volumetric mass transfer coefficient (kLa) has increased following the addition of t-butanol. Ozone decomposition was studied at pH values of 2 to 9 in a 500 mL reactor initially saturated with ozone. Ozone decomposition was found to follow a second order reaction at pH values less than 7 whilst it was first order at pH 9. When the t-butanol was added, the decomposition of ozone progressed at a lower reaction order of 1.5 for pH values less than 7 and at the same order without t-butanol at pH 9. Ozone decomposition was found significant at high pHs due to high hydroxide ion concentration, which promotes ozone decomposition at high pHs. The reaction rate constant (k) of RO16 ozonation in the absence of t-butanol was determined. The result suggests that RO16 degradation occurs solely by molecular ozone and indirect reactions by radicals are insignificant. The chemical reaction of triclocarban with ozone was found to follow second order reaction kinetics. The degradation of naphthalene using the liquid/gas-ozone (LGO) system was studied. This result showed that hydroxyl radicals seemed to have limited effect on naphthalene degradation which was also observed when a radical scavenger (t-butanol) was used. Reaction rate constants were calculated and were found around 100 times higher than values reported in the literature due to differences in experimental conditions. From the results of the experimental investigation on the degradation of methanol by ozone it was found that the rate constant (k) of the degradation reaction increased at pH 9. The reaction stoichiometry was found to have a value of 1 mol/mol. The two steps of the liquid/solid-ozone (LSO) system were studied on beds of silica gel and a zeolitic material (D915) and the ozone adsorption process was modeled and found that particle rate controls ozone adsorption step but liquid rate controls the water treatment step. Ozone desorption with pure deionised water was studied. The water flow rate was found to accelerate the desorption rates but pH was found to decrease the desorption rates. In contrast, the effect of pH was insignificant in the presence of t-butanol. Determination of the adsorption isotherms for RO16, naphthalene and methanol revealed that RO16 did not exhibit adsorption on silica gel, but both naphthalene and methanol showed adsorption on D915 described by Langmuir model.

In this master thesis, the feasibility of Fenton-oxidation for the decolorization of reactive dyed cotton is investigated as a potentially environmental-friendly preparatory treatment for mechanical/chemical recycling. Raw, knitted cotton is dyed with a black and a blue dye, whereafter preliminary tests are performed to investigate the influence of increasing Fenton- solution concentrations and different iron-sources on the efficiency of the discoloration, without carrying out complete optimization of the process-parameters. Based on the preliminary test-results, Fenton-treatments of the reactive-dyed cotton are upscaled, with discoloration efficiencies of 62 and 73% (for the black- and blue-dyed cotton respectively). Thermal analysis (TGA, DSC and FTIR) and mechanical analysis (tensile tests and shredding of the fabric) of the upscaled treated samples are performed, and the results indicate no major alterations of the main cellulosic structure of the cotton fibers. However, besides the degradation of the dye-molecules, also some oxidation (and therefore damage) of the cellulose-chains of the cotton fibers occurs, leading to reduced mechanical properties. Although this facilitates the mechanical recycling process, it possibly also reduces the quality of the re-spun yarns. Nevertheless, the Fenton-oxidation in the context of decolorization of reactive-dyed cotton forms an interesting future research-topic with many opportunities and prospects for increasing the efficiency and sustainability of the recycling process, and therefor increasing the sustainability of the textile industry in general.

This work was concerned with the determination of mass transfer and kinetic parameters of ozone reactions with four organic compounds from different families, namely reactive dye RO16, triclocarban, naphthalene and methanol. In order to understand the mechanisms of ozone reactions with the organic pollutants, a radical scavenger (t-butanol) was used and the pH was varied from 2 to 9. Ozone solubility (CAL*) is an important parameter that affects both mass transfer rates and chemical reaction kinetics. In order to determine accurate values of the CAL* in the current work, a set of experiments were devised and a correlation between CAL* and the gas phase ozone concentration of the form CAL*(mol/L) = 0.0456 CO3 (g/m3 NTP) was obtained at 20°C. This work has also revealed that t-butanol did not only inhibit hydroxyl radical reactions but also increased mass transfer due to it increasing the specific surface area (aL). Values of the aL were determined to be 2.7 and 3.5 m2/m3 in the absence and presence of t-butanol respectively. It was noticed that the volumetric mass transfer coefficient (kLa) has increased following the addition of t-butanol. Ozone decomposition was studied at pH values of 2 to 9 in a 500 mL reactor initially saturated with ozone. Ozone decomposition was found to follow a second order reaction at pH values less than 7 whilst it was first order at pH 9. When the t-butanol was added, the decomposition of ozone progressed at a lower reaction order of 1.5 for pH values less than 7 and at the same order without t-butanol at pH 9. Ozone decomposition was found significant at high pHs due to high hydroxide ion concentration, which promotes ozone decomposition at high pHs. The reaction rate constant (k) of RO16 ozonation in the absence of t-butanol was determined. The result suggests that RO16 degradation occurs solely by molecular ozone and indirect reactions by radicals are insignificant. The chemical reaction of triclocarban with ozone was found to follow second order reaction kinetics. The degradation of naphthalene using the liquid/gas-ozone (LGO) system was studied. This result showed that hydroxyl radicals seemed to have limited effect on naphthalene degradation which was also observed when a radical scavenger (t-butanol) was used. Reaction rate constants were calculated and were found around 100 times higher than values reported in the literature due to differences in experimental conditions. From the results of the experimental investigation on the degradation of methanol by ozone it was found that the rate constant (k) of the degradation reaction increased at pH 9. The reaction stoichiometry was found to have a value of 1 mol/mol. The two steps of the liquid/solid-ozone (LSO) system were studied on beds of silica gel and a zeolitic material (D915) and the ozone adsorption process was modeled and found that particle rate controls ozone adsorption step but liquid rate controls the water treatment step. Ozone desorption with pure deionised water was studied. The water flow rate was found to accelerate the desorption rates but pH was found to decrease the desorption rates. In contrast, the effect of pH was insignificant in the presence of t-butanol. Determination of the adsorption isotherms for RO16, naphthalene and methanol revealed that RO16 did not exhibit adsorption on silica gel, but both naphthalene and methanol showed adsorption on D915 described by Langmuir model. / Education Service Department of the Libyan Government

Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-04-25T20:20:41Z No. of bitstreams: 1 Carolina_Miyashiro_2017 .pdf: 1779339 bytes, checksum: f6b6d1ffc4073370161792334748de1b (MD5) / Made available in DSpace on 2018-04-25T20:20:41Z (GMT). No. of bitstreams: 1 Carolina_Miyashiro_2017 .pdf: 1779339 bytes, checksum: f6b6d1ffc4073370161792334748de1b (MD5) Previous issue date: 2017-12-11 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / A magnetic biocoagulant (Fe3O4-MO) was produced by the association of nanoparticles of iron oxide (Fe3O4) and Moringa Oleífera Lam (MO) extract in different concentrations (0.5%, 1% and 2%), aiming to evaluate its performance in removal of the reactive dye black 5 (RP5) in aqueous medium (synthetic waste water) and real textile effluent. The MO protein was extracted with saline solution and the nanoparticles were synthesized by the coprecipitation method. The biocoagulant was characterized by X-ray diffractometry (XRD), vibration magnetometry, Fourier Infrared Transformer (FTIR) spectroscopy, scanning electron microscopy with X-ray energy dispersion spectroscopy (SEM / EDS) and transmission electron microscopy (MET). For the coagulation / flocculation / sedimentation process (C/F/S), the operational parameters studied were sedimentation time, biocoagulant concentration and pH. The efficiency of the C/F/S process was determined by the analysis of the apparent color, absorbance, zeta potential and total organic carbon (TOC). After determining the best conditions (concentration of 0.5% MO, dosage of 100 mg L-1 and pH 7) of the C/F/S process, sedimentation kinetic studies for synthetic wastewater (ARS), real effluent (ERT), both with and without magnetic field and the sludge recovered and regenerated with the saline extract of MO (with magnetic field). At the 100 mgL-1 dosage of magnetic biocoagulant at a concentration of 0.5% MO saline, 89% apparent color removals were obtained in the time of 20 min. The C / F / S process shows dependence on the pH of the reaction medium, because at pH 7 color removal values of 83% and 84% were obtained in reaction time 20 and 40 min, respectively. / Um biocoagulante (Fe3O4-MO) magnético foi produzido pela associação de nanopartículas de óxido ferro (Fe3O4) e extrato de Moringa Oleífera Lam (MO) em diferentes concentrações (0,5%, 1% e 2%), para avaliar sua performance na remoção do corante reativo preto 5 (RP5) em meio aquoso (água residuária sintética) e efluente real têxtil. A proteína da MO foi extraída com solução salina e as nanopartículas foram sintetizadas pelo método de coprecipitação. O biocoagulante foi caracterizado por difratometria de raio-X (DRX), magnetometria vibratória, spectroscopia por transformada de Fourier (FTIR), microscopia eletrônica de varredura com espectroscopia por dispersão de energia de Raios-X (MEV/EDS) e microscopia eletrônica de transmissão (MET). Para o processo de coagulação/floculação/sedimentação (C/F/S) os parâmetros operacionais estudados foram tempo de sedimentação, concentração do biocoagulante e pH. A eficiência do processo C/F/S foi determinada pela análise da cor aparente, absorbância, potencial zeta e carbono orgânico total (COT). Após determinar as melhores condições (concentração de MO 0,5%, dosagem de biocoagulante 100 mg L-1 e pH 7) do processo C/F/S, foram realizados estudos cinéticos de sedimentação para água residuária sintética (ARS), efluente real têxtil (ERT), ambos com e sem campo magnético e o lodo recuperado e regenerado com o extrato salino de MO (com campo magnético). Na dosagem 100 mgL-1 de biocoagulante magnético em concentração de 0,5% de solução salina de MO foram obtidos remoções de cor aparente 82% no tempo de 20 min. O processo C/F/S apresenta dependencia em relação ao pH do meio reacional, pois em pH 7 foram obtidos valores de remoção de cor de 83 % e 84 % em tempo de sedimentação 20 e 40 min., respectivamente. Demonstrando-se um materialpromissor na remoção de RP5 e no tratamento de ERT pois possui alta eficiência, preparo simples e condizentes com questões ambientais.

Les effluents industriels issus des activités de textile présentent souvent une importante charge polluante colorante difficilement biodégradable. Des travaux antérieurs ont montré le potentiel des argiles naturelles non traitées à dépolluer ces effluents teinturiers alors qu’ils sont généralement composés de colorants anioniques difficilement adsorbables sur ces supports. Or, les effluents contiennent également d’autres composés chimiques utilisés dans les différentes étapes du procédé de teinture, et qui sont de natures variées (sels, acides, bases, détergents, dérivés enzymatiques, etc…). Il semblerait que ces produits auxiliaires jouent un rôle dans l'adsorption de colorants anioniques sur l'argile non traitée. Cependant, aucune étude connue à ce jour, n'a porté sur l'effet des additifs de teinture dans le processus de décoloration par des absorbants en général, et par les argiles en particulier. Cette étude est la première à s’intéresser au système colorant-additif-argile. Des tests d’adsorption / désorption en batch ont été menés en considérant différents systèmes colorant-additif-argile. Les résultats des tests montrent que les additifs de type enzymatique favorisent l’adsorption de colorant anionique sur l’argile en neutralisant les charges négatives et en renforçant les liaisons argile-colorant. D’autres additifs ont un effet contraire mais n’annulent pas l’effet positif des additifs enzymatiques lorsqu’ils sont mélangés dans l’effluent. Des hypothèses d’interactions mises en jeu lors de l’adsorption de colorant ont été faites en s’aidant des résultats de la spectrométrie infra-rouge et de masse, de la zétamétrie et de la modélisation des isothermes d’adsorption. / Industrial effluents from textile activities often have a high pollution load readily biodegradable. Previous work has shown the potential of natural untreated clays to clean up these dyers effluents although anionic dyes are not easily absorbable on these media. The effluents also contain other chemical compounds used in the different stages of the dyeing process, and which are of various natures (salts, acids, bases, detergents, enzyme derivatives, etc ...). It appears that these auxiliary products play a role in the adsorption of anionic dyes on untreated clay. However, no currently known study has examined the effect of the additives from the dyeing process on the adsorption of dye onto clay. This is the first study to focus on the dye-clay-additive system. Adsorption / desorption batch tests were conducted considering different dye additive-clay systems. The tests’ results show that the enzyme like additives enhance the adsorption of anionic dye on the clay by neutralizing the negative charges and reinforcing clay-dye links. Other additives have the opposite effect, but do not offset the positive effect of enzyme like additives when mixed in the effluent. Assumptions of interactions involved in dye adsorption were made with the help of the results of infrared and mass spectrometry, zetametry and the modeling of adsorption isotherms.

Background: As a company it is more important than ever to consider the environmental sustainability aspect within the whole supply chain and all the stakeholders. Studies show that people's concerns about environmental sustainability increases and will continue to grow in the future. The wet dyeing process is the part of the textile production that consists of liquor and contains three main steps which are pretreatment, coloration and finishing. This process is presented as the most water, energy and chemicals consuming process within the textile industry and because of that, it is important to investigate it to be able to improve the environmental sustainability.  Purpose: The purpose of the thesis is to increase the understanding of IKEA’s suppliers' current usage of water, energy and chemicals within the wet dyeing process. Followed by an identification of opportunities for improvements in the wet dyeing process, aiming to become more environmentally sustainable.  Method: Through interviews with two suppliers, information regarding IKEA’s current wet dyeing processes will be collected. After that, data from relevant theoretical sources will be collected to analyze possible improvements of methods and colorants that can be relevant for IKEA as well as other companies within the textile industry to implement.  Conclusion: For research question 1, the researchers reach the conclusion that IKEA’s supplier number one has a more environmentally sustainable wet dyeing process compared to the second supplier.. A conclusion is nevertheless drawn that improvements within both suppliers wet dyeing processes should be considered to become more environmentally sustainable. For research question 2, the researchers come to the conclusion that Spray dyeing is the best alternative method to implement for improving environmental sustainability within the wet dyeing process. The researchers also recommend companies to actively become a part of the development of bacterial colorants, the future of coloration.

Made available in DSpace on 2017-07-10T18:08:00Z (GMT). No. of bitstreams: 1 Mauricio M Sinhorim Monarin.pdf: 2075451 bytes, checksum: 650d176482da90355f19fcef0fa451d4 (MD5) Previous issue date: 2012-02-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The dyes are present in many plants, producing toxic and carcinogenic effluents that significantly affecting the environment when disposed of untreated. The most commonly used methods for dye removing are biological treatment, coagulation / flocculation / membranes and adsorption processes. The present study aims to evaluate the adsorption of reactive dye textile Crimson HEXL, used in industrial plants (mainly laundries) using two commercial activated carbons: the origin of bovine bones (CAO) and bituminous minerals (CAM). To compare the potential application of these two types of carbons, experiments were performed characterization and adsorption in batch system and in duplicate, consisting of the following steps: i) obtaining from the point of zero charge (pHpzc) for each carbon, ii) evaluate the influence the pH of the dye solution, iii) determine the optimal particle size of the adsorbent, iv) to investigate the influence of the stirring rate in the adsorption process, data acquisition and modeling using kinetic models available in the literature, of obtaining data of equilibrium and modeling at different temperatures using literature modeling, v) desorption of the dye in the best conditions for the particular adsorption system carbon-dye (pH and type of eluent). The experiments showed the best conditions of particle size (approximately 20-30 mesh), shaking (100 rpm) and pH of 2. The kinetic data showed a contact time of 48 hours for the system to reach equilibrium. The kinetic model Pseudo-First-Order, Pseudo-Second-Order and intra-particle diffusion showed good fits of the experimental data with high coefficients of determination and high degree of significance for each parameter in the models studied (p-level < 0,05) for the experimental equilibrium data for systems Crimson HEXL CAO and Crimson HEXL CAM, except for the model of intra-particle diffusion at 100 mg/L of system Crimson HEXL CAO. The simulation using the Langmuir model using as adsorbent CAO represented satisfactorily equilibrium data experimental temperatures of 20, 30, 40 and 50 ° C, unlike the Freundlich model which had adjustment only for the temperature of 20 ° C. To the system Crimson HEXL - CAM did not obtain a proper fit for simulating the experimental data using the equilibrium model isotherm Langmuir and Freundlich. The thermodynamic parameters &#916;Hº, &#916;Gº and &#916;Sº were evaluated and demonstrated that the adsorption of the reactive dye Crimson HEXL in CAO and CAM is an endothermic and spontaneous process. The recovery of activated carbons with reactive dyes had poor results for the recovery of the adsorbent for reuse in adsorption processes. / Os corantes estão presentes em muitas unidades industriais, gerando efluentes que são carcinogênicos e tóxicos afetando significativamente o meio ambiente quando descartados sem tratamento prévio. Os métodos mais empregados para a remoção de corantes são: tratamento biológico, coagulação / floculação / membranas e processos de adsorção. O presente trabalho pretende avaliar a adsorção do corante reativo têxtil Crimson HEXL, utilizado em unidades industriais (lavanderias principalmente) utilizando-se dois carvões comerciais ativados: de origem de ossos bovinos (CAO) e mineral betuminosa (CAM). Para comparar o potencial de aplicação destes dois tipos de carvão, experimentos foram realizados de caracterização e adsorção em sistema batelada e em duplicata, consistindo nas seguintes etapas: i) obtenção do ponto de carga zero (pHpcz) para cada carvão; ii) avaliar influência do pH da solução do corante; iii) determinar o melhor tamanho de partícula do material adsorvente; iv) investigar a influência da velocidade de agitação no processo de adsorção: obtenção de dados cinéticos e modelagem utilizando modelos disponíveis na literatura; obtenção de dados de equilíbrio em diferentes temperaturas e modelagem usando modelos da literatura; v) dessorção do corante nas melhores condições de adsorção determinadas para o sistema carvão-corante (pH e tipo de eluente). Os experimentos realizados indicaram as melhores condições de granulometria (aproximadamente 20-30 mesh), agitação (100 rpm) e pH da solução de 2. Os dados cinéticos apresentaram um tempo de contato de 48 horas para o sistema alcançar o equilíbrio. O modelo cinético de Pseudo-Primeira-Ordem, Pseudo-Segunda-Ordem e Difusão Intra-partícula apresentaram bons ajustes dos dados experimentais com elevados valores dos coeficientes de determinação e elevado grau de significância para cada parâmetro nos modelos estudados (p-level<0,05) para os dados de equilíbrio experimentais para os sistemas Crimson HEXL CAO e Crimson HEXL CAM, exceto para o modelo de Difusão Intra-partícula à 100 mg/L do sistema Crimson HEXL CAO. A simulação realizada utilizando o modelo de Langmuir empregando como adsorvente o CAO representou satisfatoriamente os dados de equilíbrio experimentais para as temperaturas de 20, 30, 40 e 50 ºC, ao contrário do modelo de Freundlich que apresentou ajuste apenas para a temperatura de 20 ºC. Para o sistema Crimson HEXL CAM não se obteve um ajuste adequado para a simulação dos dados experimentais empregando o modelo de isoterma de equilíbrio de Langmuir e Freundlich Os parâmetros termodinâmicos &#916;H0, &#916;G0 e &#916;S0 foram avaliados e mostraram que a adsorção do corante reativo Crimson HEXL em CAO e CAM é um processo endotérmico e espontâneo. A recuperação de carvões ativados com corantes reativos obtiveram resultados pouco satisfatórios para recuperação do adsorvente para reutilização em processos de adsorção.