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Doctoral Thesis
DOI
https://doi.org/10.11606/T.18.2012.tde-04052012-092252
Document
Author
Full name
Bruna de Souza Moraes
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2012
Supervisor
Committee
Foresti, Eugenio (President)
Barana, Ana Cláudia
Pessoa, Sávia Gavazza dos Santos
Rodrigues, José Alberto Domingues
Zaiat, Marcelo
Title in Portuguese
Desnitrificação autotrófica com o uso de sulfeto e integração com o processo de nitrificação em um único reator
Keywords in Portuguese
Desnitrificação autotrófica
Doador de elétrons
Esgoto sanitário
Parâmetros cinéticos intrínsecos
Remoção de nitrogênio em única etapa
Sulfeto
Abstract in Portuguese
A remoção de nitrogênio acoplada à oxidação de sulfeto pode ser uma opção adequada para o pós-tratamento de efluentes de reatores anaeróbios, os quais contêm nitrogênio amoniacal, que deve ser nitrificado, e sulfeto, que poderia ser utilizado como doador de elétrons endógeno para a desnitrificação autotrófica. Com base nessa constatação, esta pesquisa propôs a aplicação da nitrificação e desnitrificação autotrófica acoplada à oxidação de sulfeto, em um único reator, para a remoção de nitrogênio de efluentes de reatores anaeróbios tratando esgoto sanitário. Visto que existem lacunas na literatura referente ao processo desnitrificante autotrófico citado, as bases teóricas para a determinação das condições operacionais partiram da caracterização cinética e de aspectos fundamentais da desnitrificação autotrófica com uso de sulfeto como doador de elétrons. Numa primeira etapa, avaliou-se o efeito da concentração de sulfeto na desnitrificação, com uso de nitrato e nitrito como receptores de elétrons, em reatores verticais de leito fixo. Os resultados revelaram que compostos intermediários de enxofre foram principalmente formados quando se aplicou excesso de sulfeto, fato que foi mais evidente com o uso de nitrato. Evidências visuais sugeriram que enxofre elementar foi o principal intermediário formado, o qual também estava sendo utilizado quando aplicadas concentrações estequiométricas de sulfeto relativas a nitrato/nitrito. De modo geral, a desnitrificação autotrófica não foi afetada pela desnitrificação heterotrófica residual via atividade endogênica. Numa segunda etapa, determinou-se a cinética intrínseca da desnitrificação autotrófica via nitrato e nitrito com uso de diferentes concentrações de sulfeto em reatores diferenciais de leito fixo. Este bioprocesso pôde ser descrito por modelo cinético de ordem ½ para biofilmes. As constantes cinéticas variaram entre 0,425-0,658 mg N1/2 / L1/2 h para desnitrificação via nitrito e entre 0,190-0,609 mg N1/2 / L1/2 h para desnitrificação via nitrato. Neste último, o menor valor foi devido ao uso de elétrons doados a partir de compostos intermediários de enxofre formados. Numa terceira etapa, utilizou-se um reator de leito fixo operado em batelada alimentada seqüencial, com ciclos de 8 horas, submetido à aeração intermitente e empregando a desnitrificação autotrófica com uso de sulfeto presente no efluente sanitário, pré-tratado anaerobiamente, como doador de elétrons. O prévio estabelecimento da nitrificação com posterior aplicação de baixas concentrações de sulfeto foi a melhor estratégia de partida do reator. A alimentação em batelada alimentada com aplicação de sulfeto em excesso apenas nos períodos anóxicos foi a melhor estratégia de alimentação, proporcionando eficiência média de 85,7% e 53,0% para nitrificação e desnitrificação, respectivamente. O acúmulo de nitrito foi observado após aplicação de carga de choque de sulfeto, que inibiu as bactérias oxidadoras de nitrito. No entanto, houve dificuldade em se estabelecer a desnitrificação via nitrito em função da toxicidade deste composto aos organismos desnitrificantes instalados no reator. A baixa eficiência global de remoção de nitrogênio e algumas restrições operacionais indicaram que a desnitrificação autotrófica usando sulfeto em um único reator operado em bateladas seqüenciais não foi adequada para a proposta desta pesquisa.
Title in English
Autotrophic denitrification with sulphide and the use of integration with the process of nitrification in a single reactor
Keywords in English
Autotrophic denitrification
Domestic sewage
Electron donor
Single step nitrogen removal
Sulfide
Abstract in English
Nitrogen removal coupled with sulfide oxidation may be suitable for the post treatment of effluents from anaerobic reactors. These effluents contain ammonium, which must be nitrified, and sulfide, which could be used as an endogenous electron donor for autotrophic denitrification. Since there are gaps in literature regarding the mentioned autotrophic denitrifying process, the theoretical basis for determination of operating conditions came from the characterization of kinetics and fundamentals aspects of autotrophic denitrification using sulfide as electron donor. In a first step, the effect of sulfide concentration on this bioprocess using nitrate and nitrite as electron acceptors in vertical fixed-bed reactors was evaluated. The results showed that intermediary sulfur compounds were mainly produced when excess of electron donor was applied, which was more evident when nitrate was used. Visual evidences suggested that elemental sulfur was the intermediary compound produced. There was also evidence that the elemental sulfur previously formed was being used when sulfide was applied in stoichiometric concentration relative to nitrate/nitrite. For all conditions assayed, autotrophic denitrification was not affected by residual heterotrophic denitrification via endogenic activity, occurring as a minor additional nitrogen removal process. In a second step, the intrinsic kinetics of sulfide-oxidizing autotrophic denitrification via nitrate and nitrite in systems containing attached cells was determined. Differential reactors were fed with nitrified synthetic domestic sewage and different sulfide concentrations. This bioprocess could be described by a half-order kinetic model for biofilms. The half-order kinetic coefficients ranged from 0.425 to 0.658 mg N1/2 / L1/2 h for denitrification via nitrite and from 0.190 to 0.609 mg N1/2 / L1/2 h for denitrification via nitrate. In this latter, the lower value was due to the use of electrons donated from intermediary sulfur compounds formed. In a third step, a sequencing fed-batch biofilm reactor of 8-h cycles was operated under intermittent aeration, applying autotrophic denitrification using sulfide present in the sanitary effluent, anaerobically pre-treated, as electron donor. The effect of the start-up period and the feeding strategy were evaluated. The previous establishment of nitrification process with subsequent application of sulfide in low concentrations was the best start-up strategy. The fed-batch mode with sulfide application in excess only in the anoxic periods was the best feeding strategy, providing average efficiencies of 85.7% and 53.0% for nitrification and denitrification, respectively. Nitrite accumulation was observed after application of shock loading of sulfide, which inhibited nitrite-oxidizing bacteria. However, it was difficult to establish denitrification via nitrite due to the toxicity of this compound to denitrifying organisms developed inside the reactor. The low overall efficiency of nitrogen removal and some operational constraints indicated that autotrophic denitrification using sulfide in a single sequencing fed-batch reactor was not suitable for the purpose of this research.
 
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Publishing Date
2012-05-11
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • MORAES, B. S., Moraes, B.S., and FORESTI, E. Determination of the intrinsic kinetic parameters of sulfide-oxidizing autotrophic denitrification in differential reactors containing immobilized biomass [doi:10.1016/j.biortech.2011.11.050]. Bioresource Technology [online], 2012, vol. 104, p. 250-256.
  • Moraes, B. S., Souza, T. S. O., and FORESTI, E. Characterization and kinetics of sulfide-oxidizing autotrophic denitrification in batch reactors containing suspended and immobilized cells [doi:10.2166/wst.2011.700]. Water Science and Technology [online], 2011, vol. 64, p. 731.
  • MORAES, B.S., and FORESTI, E.. Determination of the intrinsic kinetic parameters of sulfide-oxidizing autotrophic denitrification in differential reactors containing immobilized biomass [doi:10.1016/j.biortech.2011.11.050]. Bioresource Technology [online], 2012, vol. 104, p. 250-256.
  • MORAES, B.S., ORRÚ, J.G.T., and FORESTI, E. Nitrogen and sulfide removal from effluent of UASB reactor in a sequencing fed-batch biofilm reactor under intermittent aeration [doi:10.1016/j.jbiotec.2012.06.032]. Journal of Biotechnology [online], 2012, vol. 164, n. 3, p. 378-385.
  • MORAES, B.S., SOUZA, T.S.O., and FORESTI, E.. Effect of sulfide concentration on autotrophic denitrification from nitrate and nitrite in vertical fixed-bed reactors [doi:10.1016/j.procbio.2012.05.008]. Process Biochemistry [online], 2012, vol. 47, n. 9, p. 1395-1401.
  • MORAES, B. S., et al. Effect of sulfide concentration on autotrophic denitrification from nitrate and nitrite in vertical fixed-bed reactors [doi:10.1016/j.procbio.2012.05.008]. Process Biochemistry (1991) [online], 2012, vol. 47, p. 1395-1401.
  • MORAES, B. S., et al. Nitrogen and sulfide removal from effluent of UASB reactor in a sequencing fed-batch biofilm reactor under intermittent aeration [doi:10.1016/j.jbiotec.2012.06.032]. Journal of Biotechnology [online], 2013, vol. 164, p. 378-385.
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