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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

A study of the degradation products of lignin after irradiation with ultraviolet light

Hulbert, William G. (William Glen) 01 January 1942 (has links)
No description available.
2

Photochemical Degradation of a Phenyl-urea Pesticide Chlorotoluron / Photochemical Degradation of a Phenyl-urea Pesticide Chlorotoluron

ZEMANOVÁ, Martina January 2008 (has links)
Chlorotoluron photochemical degradation in homogeneous phase (aqueous solutions) was studied. Photolysis by UV radiation, influence of metal (ferric, ferrous) ions, pH, and solvent composition on the reaction rate was investigated. Photosensitizing effect of humic samples was tested. Kinetic characteristics (rate constants, overall quantum yield), products of reactions and extent of mineralization was evaluated.
3

Photochemical Degradation of Chlorobenzene

Sycz, Mateusz 30 April 2013 (has links)
Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.
4

Photochemical Degradation of Chlorobenzene

Sycz, Mateusz 30 April 2013 (has links)
Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.
5

Degradation of atrazine by homogeneous photocatalysis using Fe(III)/UV/air system and evaluation of potential toxicity of atrazine and its metabolites

KELTNEROVÁ, Lucie January 2016 (has links)
Atrazine photochemical degradation in homogeneous phase using Fe(III)/UV/air system was studied. Two toxicity assessments, a Lemna minor growth inhibition test and a Daphnia magna acute immobilisation test, were employed to test potential toxicity of atrazine and its degradation products. The occurrence of atrazine in rivers from the Vltava River basin was evaluated from the analyses performed by Povodí Vltavy, State Enterprise.
6

Estudo da degradação fotoquímica de soluções aquosas de polietilenoglicol, poliacrilamida e polivinilpirrolidona. / Photochemical degradation study of aqueous solutions of polyrthyleneglicol, polyacrylamide and polyvinylpyrrolidone.

Giroto, Jeanne Aparecida 13 July 2007 (has links)
Este trabalho visa estudar a viabilidade do emprego de processos oxidativos avancados na degradacao de solucoes aquosas de polimeros que sao comumente utilizados em aplicacoes industriais e estao presentes em seus efluentes. Para maior entendimento das reacoes envolvidas no processo oxidativo utilizou-se modelagem molecular nos calculos de constantes cineticas. Na parte experimental estudou-se a degradacao de polietilenoglicol (PEG), polivinilpirrolidona (PVP) e poliacrilamida (PAM) pelos processos foto-Fenton e UV/H2O2. Realizaram-se analises de carbono organico dissolvido (COD), cromatografia liquida de alto desempenho (HPLC) e cromatografia de permeacao em gel (GPC). Observou-se separacao de fases para PVP e PAM, o que contribuiu para uma remocao final de COD de ate 85%. Nas analises de HPLC foram detectados como intermediarios da reacao os acidos: oxalico, formico, malonico e acetico. Os resultados de GPC indicaram comportamentos distintos das distribuicoes de pesos moleculares em funcao do tempo de reacao para os processos UV/H2O2 e foto- Fenton. No conjunto, os resultados comprovam a viabilidade dos processos estudados na degradacao destes polimeros, embora a analise de intermediarios para PAM nao tenha sido conclusiva quanto a formacao de acrilamida. A modelagem molecular confirma que a reacao de abstracao de hidrogenio de uma cadeia polimerica pelos radicais alquilperoxila e de fato a etapa mais lenta do processo oxidativo para PEG e PAM. Para PAM os resultados da modelagem mostram que o ataque dos radicais hidroxila acontece preferencialmente no hidrogenio ligado ao carbono terciario e que a abstracao de hidrogenio do grupo lateral amida parece pouco viavel, ou acontece por um mecanismo diferente do modelado. A reacao de formacao da acrilamida de acordo com o mecanismo proposto tambem apresentou uma constante cinetica muito baixa, o que esta de acordo com os resultados experimentais, ja que nao foi detectada acrilamida como produto da degradacao de poliacrilamida pelos processos foto-Fenton e UV/H2O2, com limite de deteccao de 50 ppb. / The aim of this work is to apply advanced oxidative processes to study the degradation of industrial wastewater containing water-soluble polymers. Kinetic constants of reactions involved in the oxidation processes were calculated by molecular modeling. In the experimental part the degradation of polyvinylpirrolidone (PVP), polyacrylamide (PAM) and polyethyleneglycol (PEG) was studied by photo-Fenton and UV/H2O2 processes. Intermediates of the degradation processes were identified by HPLC and the molecular weight distribution was monitored by GPC. In the experiments with PAM and PVP phase separation was observed, and more than 85% of the DOC was removed. The following intermediate acids were identified: acetic, malonic, formic and oxalic. The molecular weight distribution curves measured by GPC indicate that distinct reaction paths exist for each process studied, although the analysis of intermediates formed during the degradation of PAM was not conclusive with respect to acrylamide formation. The kinetic constants for the reactions involving hydrogen abstraction from PEG chain by hydroxyl and alkylperoxy radicals were calculated. The molecular modeling results confirm that hydrogen abstraction from polymeric chain by alkylperoxy radicals is the determinant step in the oxidation process for PEG and PAM. Polyacrylamide possesses three sites for attack by hydroxyl radicals and the favored path is the abstraction of tertiary hydrogen atom, followed by secondary hydrogen. The abstraction of the amide hydrogen was more difficult. The mechanism proposed for acrylamide formation was not the preferential reaction path. This was expected since acrylamide was not detected in the experiments with a limit detection of 50 ppb.
7

Estudo e otimização da degradação dos herbicidas hexazinona e diuron utilizando processos oxidativos avançados (POA): H2O2/UV e foto-Fenton / Study and optimization of the degradation of the herbicides diuron and hexazinone using advanced oxidation processes (AOP): H2O2/UV and photo-Fenton

Alysson Stefan Martins 27 February 2013 (has links)
Agrotóxicos são frequentemente relatados na literatura em contaminações de ambientes aquáticos, sendo provenientes do lixiviamento de solos, do descarte inadequado de embalagens agrícolas, dentre outros. Nesse contexto, os processos oxidativos avançados (POA) têm sido estudados como alternativa para o tratamento desses compostos em meio aquoso. Os POA consistem na oxidação de compostos orgânicos pela formação de radicais livres com alto poder oxidante. Diante desses aspectos, o presente trabalho teve como proposta o estudo da degradação dos herbicidas hexazinona e diuron, aliada ao planejamento experimental do tipo composto central, a fim de otimizar o processo de degradação. Para tanto, realizaram-se as degradações através dos processos H2O2/UV e foto-Fenton em concentrações iniciais próximas a 7 e 20 mg L-1 para a hexazinona e diuron, respectivamente. Os experimentos foram conduzidos em um reator fotoquímico (200 mL a 25 °C) com aplicação de irradiação UV, proveniente de uma lâmpada de Hg (degradação H2O2/UV) e de luz negra (degradação foto-Fenton). No processo via H2O2/UV foram avaliadas a concentração de H2O2 (0,65 a 13,34 mmol L-1) e pH (2,77 a 11,23), e para o processo foto-Feton avaliou-se a concentração de H2O2 (0,09 a 29,1 mmol L-1) e Fe (II) (0,01 a 0,92 mmol L-1). Como variável independente, utilizou-se a remoção de Carbono Orgânico Total (COT) nos dois casos. A eficiência na degradação dos herbicidas foi determinada através das técnicas de Espectroscopia UV-Vis, Cromatografia Líquida de Alta Eficiência (HPLC/UV), remoção de Carbono Orgânico Total e Cromatografia de Íons. A análise dos modelos matemáticos, obtidos a partir dos planejamentos, possibilitou a avaliação da influência das variáveis, determinando as melhores condições. No processo H2O2/UV observou-se que a influência da variável H2O2 é maior comparada ao pH. A melhor condição de degradação apresentou concentrações de H2O2 iguais a 7 mmol L-1 e valores de pH de 2,8. Como resultado, obteve-se 96 % de remoção do COT e a não detecção de ambos os herbicidas após 2 minutos de reação. No processo foto-Fenton, a realização de três planejamentos foi necessária para a otimização do sistema. Primeiro e segundo planejamentos indicaram a melhor condição, enquanto que o terceiro planejamento revelou que concentrações elevadas de H2O2 e Fe2+ não garantem maior eficiência. As condições ideais encontradas foram iguais a 0,291 mmol L-1 para o Fe2+ e 2,91 mmol L-1 para o H2O2, obtendo-se 76 % de remoção do COT e não detecção dos herbicidas nos primeiros minutos de degradação. Em ambas as degradações não foi possível observar diferenças em relação a cinética de degradação para os herbicidas. A degradação via H2O2/UV mostrou melhor desempenho, pois apresentou maior taxa de mineralização além de não necessitar o emprego do íon Fe(II). / Pesticides are often reported in the literature on aquatic environments contamination, being a result of soil leaching, improper disposal of agricultural packages, among others. In this context, advanced oxidation processes (AOP) have been studied as an alternative to treat these compounds in aqueous medium. The AOP consist in the oxidation of organic compounds through the formation of free radicals with a high oxidizing power. Considering these aspects, the present work aimed to study degradation of the herbicides diuron and hexazinone, coupled with an experimental setup as central compost, in order to optimize the degradation process. For this purpose, the degradation was carried out by H2O2/UV and photo-Fenton processes at initial concentrations close to 7 and 20 mg L-1 to hexazinone and diuron, respectively. The experiments were conducted in a photochemical reactor (200 mL at 25 ° C) with application of UV irradiation from Hg lamp (H2O2/UV degradation) and black-light (photo-Fenton degradation). In the H2O2/UV process, the concentrations of H2O2 (0.65 to 13.34 mmol L-1) and pH (2.77 to 11.23) were evaluated, and in the photo-Fenton process, the concentrations of H2O2 (0.09 to 29.1 mmol L-1) and Fe (II) (0.01 to 0.92 mmol L-1) were analyzed. In both processes, the removal of Total Organic Carbon (TOC) was used as an independent variable. The efficiency of the herbicide degradation was determined by UV/Vis spectroscopy, high performance liquid chromatography (HPLC/UV), removal of the Total Organic Carbon and ion chromatography. The analysis of the mathematical models obtained from the experimental setup allowed the evaluation of the variables influence ,determining the best conditions. The H2O2/UV process showed that the influence of the H2O2 is higher compared to that of the pH. The best degradation condition presented H2O2 concentrations of 7 mmol L-1 and a pH value of 2.8. As a result, 96% TOC removal was observed, and none of the herbicides were detected after 2 minutes of reaction. In the photo-Fenton process, the conduction of three setups was necessary to confirm the best condition. The first and second setups indicated the best condition, while the third one showed that high concentrations of H2O2 and Fe2+ do not guarantee a greater degradation efficiency. Ideal conditions were equal to 0.291 mmol L-1 for Fe2+ and 2.91 mmol L-1 for H2O2, where 76% of TOC removal was obtained and also no herbicides detection was seen in the early minutes of degradation. In both processes, it was not possible to observe differences in the degradation kinetics of the herbicides. The H2O2/UV degradation showed better performance because of a greater mineralization rate besides not requiring the ion Fe (II) use.
8

Estudo e otimização da degradação dos herbicidas hexazinona e diuron utilizando processos oxidativos avançados (POA): H2O2/UV e foto-Fenton / Study and optimization of the degradation of the herbicides diuron and hexazinone using advanced oxidation processes (AOP): H2O2/UV and photo-Fenton

Martins, Alysson Stefan 27 February 2013 (has links)
Agrotóxicos são frequentemente relatados na literatura em contaminações de ambientes aquáticos, sendo provenientes do lixiviamento de solos, do descarte inadequado de embalagens agrícolas, dentre outros. Nesse contexto, os processos oxidativos avançados (POA) têm sido estudados como alternativa para o tratamento desses compostos em meio aquoso. Os POA consistem na oxidação de compostos orgânicos pela formação de radicais livres com alto poder oxidante. Diante desses aspectos, o presente trabalho teve como proposta o estudo da degradação dos herbicidas hexazinona e diuron, aliada ao planejamento experimental do tipo composto central, a fim de otimizar o processo de degradação. Para tanto, realizaram-se as degradações através dos processos H2O2/UV e foto-Fenton em concentrações iniciais próximas a 7 e 20 mg L-1 para a hexazinona e diuron, respectivamente. Os experimentos foram conduzidos em um reator fotoquímico (200 mL a 25 °C) com aplicação de irradiação UV, proveniente de uma lâmpada de Hg (degradação H2O2/UV) e de luz negra (degradação foto-Fenton). No processo via H2O2/UV foram avaliadas a concentração de H2O2 (0,65 a 13,34 mmol L-1) e pH (2,77 a 11,23), e para o processo foto-Feton avaliou-se a concentração de H2O2 (0,09 a 29,1 mmol L-1) e Fe (II) (0,01 a 0,92 mmol L-1). Como variável independente, utilizou-se a remoção de Carbono Orgânico Total (COT) nos dois casos. A eficiência na degradação dos herbicidas foi determinada através das técnicas de Espectroscopia UV-Vis, Cromatografia Líquida de Alta Eficiência (HPLC/UV), remoção de Carbono Orgânico Total e Cromatografia de Íons. A análise dos modelos matemáticos, obtidos a partir dos planejamentos, possibilitou a avaliação da influência das variáveis, determinando as melhores condições. No processo H2O2/UV observou-se que a influência da variável H2O2 é maior comparada ao pH. A melhor condição de degradação apresentou concentrações de H2O2 iguais a 7 mmol L-1 e valores de pH de 2,8. Como resultado, obteve-se 96 % de remoção do COT e a não detecção de ambos os herbicidas após 2 minutos de reação. No processo foto-Fenton, a realização de três planejamentos foi necessária para a otimização do sistema. Primeiro e segundo planejamentos indicaram a melhor condição, enquanto que o terceiro planejamento revelou que concentrações elevadas de H2O2 e Fe2+ não garantem maior eficiência. As condições ideais encontradas foram iguais a 0,291 mmol L-1 para o Fe2+ e 2,91 mmol L-1 para o H2O2, obtendo-se 76 % de remoção do COT e não detecção dos herbicidas nos primeiros minutos de degradação. Em ambas as degradações não foi possível observar diferenças em relação a cinética de degradação para os herbicidas. A degradação via H2O2/UV mostrou melhor desempenho, pois apresentou maior taxa de mineralização além de não necessitar o emprego do íon Fe(II). / Pesticides are often reported in the literature on aquatic environments contamination, being a result of soil leaching, improper disposal of agricultural packages, among others. In this context, advanced oxidation processes (AOP) have been studied as an alternative to treat these compounds in aqueous medium. The AOP consist in the oxidation of organic compounds through the formation of free radicals with a high oxidizing power. Considering these aspects, the present work aimed to study degradation of the herbicides diuron and hexazinone, coupled with an experimental setup as central compost, in order to optimize the degradation process. For this purpose, the degradation was carried out by H2O2/UV and photo-Fenton processes at initial concentrations close to 7 and 20 mg L-1 to hexazinone and diuron, respectively. The experiments were conducted in a photochemical reactor (200 mL at 25 ° C) with application of UV irradiation from Hg lamp (H2O2/UV degradation) and black-light (photo-Fenton degradation). In the H2O2/UV process, the concentrations of H2O2 (0.65 to 13.34 mmol L-1) and pH (2.77 to 11.23) were evaluated, and in the photo-Fenton process, the concentrations of H2O2 (0.09 to 29.1 mmol L-1) and Fe (II) (0.01 to 0.92 mmol L-1) were analyzed. In both processes, the removal of Total Organic Carbon (TOC) was used as an independent variable. The efficiency of the herbicide degradation was determined by UV/Vis spectroscopy, high performance liquid chromatography (HPLC/UV), removal of the Total Organic Carbon and ion chromatography. The analysis of the mathematical models obtained from the experimental setup allowed the evaluation of the variables influence ,determining the best conditions. The H2O2/UV process showed that the influence of the H2O2 is higher compared to that of the pH. The best degradation condition presented H2O2 concentrations of 7 mmol L-1 and a pH value of 2.8. As a result, 96% TOC removal was observed, and none of the herbicides were detected after 2 minutes of reaction. In the photo-Fenton process, the conduction of three setups was necessary to confirm the best condition. The first and second setups indicated the best condition, while the third one showed that high concentrations of H2O2 and Fe2+ do not guarantee a greater degradation efficiency. Ideal conditions were equal to 0.291 mmol L-1 for Fe2+ and 2.91 mmol L-1 for H2O2, where 76% of TOC removal was obtained and also no herbicides detection was seen in the early minutes of degradation. In both processes, it was not possible to observe differences in the degradation kinetics of the herbicides. The H2O2/UV degradation showed better performance because of a greater mineralization rate besides not requiring the ion Fe (II) use.
9

Estudo da degradação fotoquímica de soluções aquosas de polietilenoglicol, poliacrilamida e polivinilpirrolidona. / Photochemical degradation study of aqueous solutions of polyrthyleneglicol, polyacrylamide and polyvinylpyrrolidone.

Jeanne Aparecida Giroto 13 July 2007 (has links)
Este trabalho visa estudar a viabilidade do emprego de processos oxidativos avancados na degradacao de solucoes aquosas de polimeros que sao comumente utilizados em aplicacoes industriais e estao presentes em seus efluentes. Para maior entendimento das reacoes envolvidas no processo oxidativo utilizou-se modelagem molecular nos calculos de constantes cineticas. Na parte experimental estudou-se a degradacao de polietilenoglicol (PEG), polivinilpirrolidona (PVP) e poliacrilamida (PAM) pelos processos foto-Fenton e UV/H2O2. Realizaram-se analises de carbono organico dissolvido (COD), cromatografia liquida de alto desempenho (HPLC) e cromatografia de permeacao em gel (GPC). Observou-se separacao de fases para PVP e PAM, o que contribuiu para uma remocao final de COD de ate 85%. Nas analises de HPLC foram detectados como intermediarios da reacao os acidos: oxalico, formico, malonico e acetico. Os resultados de GPC indicaram comportamentos distintos das distribuicoes de pesos moleculares em funcao do tempo de reacao para os processos UV/H2O2 e foto- Fenton. No conjunto, os resultados comprovam a viabilidade dos processos estudados na degradacao destes polimeros, embora a analise de intermediarios para PAM nao tenha sido conclusiva quanto a formacao de acrilamida. A modelagem molecular confirma que a reacao de abstracao de hidrogenio de uma cadeia polimerica pelos radicais alquilperoxila e de fato a etapa mais lenta do processo oxidativo para PEG e PAM. Para PAM os resultados da modelagem mostram que o ataque dos radicais hidroxila acontece preferencialmente no hidrogenio ligado ao carbono terciario e que a abstracao de hidrogenio do grupo lateral amida parece pouco viavel, ou acontece por um mecanismo diferente do modelado. A reacao de formacao da acrilamida de acordo com o mecanismo proposto tambem apresentou uma constante cinetica muito baixa, o que esta de acordo com os resultados experimentais, ja que nao foi detectada acrilamida como produto da degradacao de poliacrilamida pelos processos foto-Fenton e UV/H2O2, com limite de deteccao de 50 ppb. / The aim of this work is to apply advanced oxidative processes to study the degradation of industrial wastewater containing water-soluble polymers. Kinetic constants of reactions involved in the oxidation processes were calculated by molecular modeling. In the experimental part the degradation of polyvinylpirrolidone (PVP), polyacrylamide (PAM) and polyethyleneglycol (PEG) was studied by photo-Fenton and UV/H2O2 processes. Intermediates of the degradation processes were identified by HPLC and the molecular weight distribution was monitored by GPC. In the experiments with PAM and PVP phase separation was observed, and more than 85% of the DOC was removed. The following intermediate acids were identified: acetic, malonic, formic and oxalic. The molecular weight distribution curves measured by GPC indicate that distinct reaction paths exist for each process studied, although the analysis of intermediates formed during the degradation of PAM was not conclusive with respect to acrylamide formation. The kinetic constants for the reactions involving hydrogen abstraction from PEG chain by hydroxyl and alkylperoxy radicals were calculated. The molecular modeling results confirm that hydrogen abstraction from polymeric chain by alkylperoxy radicals is the determinant step in the oxidation process for PEG and PAM. Polyacrylamide possesses three sites for attack by hydroxyl radicals and the favored path is the abstraction of tertiary hydrogen atom, followed by secondary hydrogen. The abstraction of the amide hydrogen was more difficult. The mechanism proposed for acrylamide formation was not the preferential reaction path. This was expected since acrylamide was not detected in the experiments with a limit detection of 50 ppb.
10

Degrada??o fotoqu?mica de hidrocarbonetos da gasolina em efluentes aquosos / Photochemical degradation of the gasoline of hydrocarbons in wastewaters

Silva, Douglas do Nascimento 10 October 2002 (has links)
Made available in DSpace on 2014-12-17T15:01:16Z (GMT). No. of bitstreams: 1 DouglasNS.pdf: 627007 bytes, checksum: b05193ec4ef1bbecaf4b2d739179e597 (MD5) Previous issue date: 2002-10-10 / Photo-oxidation processes of toxic organic compounds have been widely studied. This work seeks the application of the photo-Fenton process for the degradation of hydrocarbons in water. The gasoline found in the refinery, without additives and alcohol, was used as the model pollutant. The effects of the concentration of the following substances have been properly evaluated: hydrogen peroxide (100-200 mM), iron ions (0.5-1 mM) and sodium chloride (200 2000 ppm). The experiments were accomplished in reactor with UV lamp and in a falling film solar reactor. The photo-oxidation process was monitored by measurements of the absorption spectra, total organic carbon (TOC) and chemical oxygen demand (COD). Experimental results demonstrated that the photo-Fenton process is feasible for the treatment of wastewaters containing aliphatic hydrocarbons, inclusive in the presence of salts. These conditions are similar to the water produced by the petroleum fields, generated in the extraction and production of petroleum. A neural network model of process correlated well the observed data for the photooxidation process of hydrocarbons / Processos de fotooxida??o de compostos org?nicos t?xicos t?m sido bastante estudados. Este trabalho trata da aplica??o do processo foto-Fenton para a degrada??o de hidrocarbonetos em ?gua. A gasolina de refinaria, sem aditivos e ?lcool, foi usada como poluente modelo. O efeito das concentra??es dos seguintes compostos foi avaliado: per?xido de hidrog?nio (100-200mM), ?ons ferrosos (0,5-1,0mM) e cloreto de s?dio (200-2000ppm). Os experimentos foram realizados em um reator com l?mpada UV e em um reator solar tipo filme descendente. O processo de foto-oxida??o foi monitorado por medidas do espectro de absor??o, carbono org?nico total (TOC) e demanda qu?mica de oxig?nio (DQO). Os resultados experimentais demonstram que o processo foto-Fenton ? vi?vel para o tratamento de efluentes contendo hidrocarbonetos alif?ticos, inclusive na presen?a de sais, sob condi??es similares ?s das ?guas de produ??o de campos de petr?leo, geradas na extra??o e produ??o de petr?leo. Um modelo do processo, baseado em redes neurais, correlacionou bem os dados observados para o processo de fotooxida??o de hidrocarbonetos

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