The purpose of this research was to investigate the relationship between the oxidation-reduction potential (ORP) measurement and volatile fatty acid (VFA) production in the acid-phase anaerobic digestion process under different conditions of temperature and residence time. Two identical anaerobic digesters were operated while VFAs, SCOD, VSS, alkalinity, ORP and pH were measured. In digester 1, VFA production of 5,556 mg/L was generated with an ORP of -315 mv at a 10 day SRT; while 5,400 mg/L of VFA with an ORP of -389 mv was recorded in digester 2. The SRT was adjusted at 5, 8, 10, 12 and 15 days and the optimum SRT was 10 days in both digesters. The results of this study indicate there were no tight relationship between VFA production and ORP values, thus ORP by itself is not a good predictor of the amount of VFAs generated. However, ORP combined with temperature had good linear relationship with VFA production. An ORP range of -315 to -390 mv was desirable for maximizing VFA production in both anaerobic digesters. Different temperatures (14, 29 and 37 ℃) were trialed and the results indicate that the conditions at 29 ℃ and 37 ℃ were not significantly different in terms of VFA production, however, less VFAs were generated at the lowest temperature of 14 ℃.

Acidogenic codigestion of fats, oils, and greases (FOG) was studied at 37"C using suspended sludge digesters operated as sequencing batch reactors (SBRs). Volatile fatty acid (VFA) production was found to increase with larger FOG loading rates, although this increase was insignificant compared the theoretical VFA production from FOG addition. Long chain fatty acids (LCFAs) were found to have accumulated in the reactor vessel in semi-solid balls that were primarily composed of saturated LCFAs. Adding high FOG loadings to an APD not acclimated to LCFAs allowed for a mass balance calculation and resulted in near complete saturation of unsaturated LCFAs and significant accumulation of LCFA material in the digester, which was found to be mostly 16:0, 18:0, and 18:1. While 18:2 and 18:3 LCFAs were nearly completely removed, 18:0 and 14:0 LCFAs were produced, most likely from the degradation of 18:2 and 18:3 LCFAs. The APD pH was found to have a significant impact on the amount of accumulated LCFA material present, with higher pH levels resulting in less accumulated material. Two-phase codigestion of FOG was also studied using an APD followed by gas-phase (GPD) digesters. The two-phase systems were compared by FOG addition to the APD versus GPD. FOG addition to the APD resulted in 88% destruction of LCFAs, whereas FOG addition to the GPD resulted in 95% destruction of LCFAs. Accumulated LCFAs in the APD receiving FOG were composed mostly of stearic acid (18:0). The low pH of the APD is likely the cause of LCFA accumulation due to saturation of unsaturated LCFAs. / Master of Science

Lactic acid is a fermentation-derived organic acid used in a wide range of industries, such as food processing and pharmaceuticals. Its market is expected to expand due to the worldwide concern for the environment, as it is an essential feedstock for biodegradable polymers. However, fermentation product is a very dilute, multicomponent aqueous solution. Subsequent separation, purification and concentration of organic acids is difficult because of high affinity of the acids for water. Reactive extraction is a viable alternative to classical separation techniques. Amine extractants dissolved in organic diluents are suitable agents with reasonable ranges of viscosity and density of the solvent phase. The product is obtained in an organic phase after reactive extraction. The aim of this study is to obtain equilibrium data of back extraction of lactic acid into appropriate aqueous solutions from the organic phase. Aqueous solutions of NaCl, NaOH, Na2SO4, NaNO3 and Na2CO3 were examined as back extractant in various initial concentrations (0.005 &ndash / 3 M). The organic phase consists of tri-n-octylmethylammonium lactate (TOMA(La)) dissolved in either oleyl alcohol or octanol with initial concentrations between 0.1 and 0.3 M. According to results of the experiments, the level of back extraction generally increased with increasing initial salt concentration in aqueous phase and decreased with increasing initial TOMA(La) concentration in organic phase. For all salts investigated, considerable levels of back extraction were obtained. NaOH was considered as the most suitable back extractant among the salts investigated since it exhibits higher distribution coefficients, regenerates tri-n-octylmethylammonium hydroxide (TOMAOH) in the organic phase and has no adverse effect on fermentation medium when forward and backward extraction steps are coupled with the fermentation. The effect of diluent type of TOMA(La) was also investigated during the experiments and it was concluded that octanol is a better diluent since it gives higher equilibrium distribution coefficients in addition to its higher solvating power and lower viscosity. The present work is a part of a comprehensive research program aiming to collect data and develop knowledge for the design of an industrial reactive extraction process coupling forward and backward extraction of lactic acid in a single unit and integrating fermentation and product separation. The kinetic parameters should be obtained as the next step for the design of such a process.

O tratamento de água residuária rica em sulfato por via de processo anaeróbio é um grande desafio, devido ao potencial de redução do sulfato pela via biológica a sulfeto, o que pode inviabilizar o aproveitamento do biogás e afetar o tratamento por seus efeitos tóxicos e inibitórios. Neste contexto, o presente trabalho investigou a potencial aplicação da separação de fase para minimizar tais problemas de operação. A operação de reator de primeira fase visa estabelecer um ambiente sulfetogênico sob condições acidogênicas. Os efeitos da pré-acidificação da água residuária sobre a produção de metano foram avaliados por meio do monitoramento de dois reatores metanogênicos, um sistema de fase única alimentado com água residuária rica em sulfato e um sistema de duas fases alimentado com água residuária acidificada. Em todos os casos foram utilizados reatores anaeróbios de leito estruturado, aplicada condições termofílica de temperatura (55°C). Para o sistema de primeira fase, dois reatores com diferentes materiais foram comparados: reator com cilindros de polietileno de baixa densidade (RAS-PEBD) com cinco etapas de operação (13 subetapas) e outro reator com cubos de espuma de poliuretano (RAS-PU) com quatro etapas de operação. As principais estratégias operacionais para otimização da redução do sulfato a variação do tempo de detenção hidráulica (TDH: 6-15 h RAS-PEBD; 12 - 16 h RAS-PU ), carga orgânica volumétrica (COVafl: 10 - 20,0 kg-DQO m-3 d-1 - RAS-PEBD; 15 - 20 kg-DQO m-3 d-1 - RAS-PU), carga de sulfato volumétrica (CSV: 3,2-16,0 kg-SO4 m-3 d-1 - RAS-PEBD; 4 - 8 kg-SO4 m-3 d-1 - RAS-PU) e velocidade ascensional (Va: 0,06 3,35 m h-1 - RAS-PEBD; 3,42 7,9 m h-1 - RAS-PU). Após longo período de adaptação da biomassa no RAS-PEBD, verificou-se o aumento da eficiência e stripping do sulfeto. A recirculação controlada do efluente foi um fator chave para melhoria do sistema. O mesmo não foi obtido em RAS-PU, apresentando perda de desempenho devido a problemas de colmatação e subsequente aparecimento de vias preferenciais. O efluente do reator de primeira fase com carga de sulfato residual menor que 7% (COVefl de 15,12 kg-DQO m-3d-1 e sulfeto de 256 mg L-1, subetapa X) foi aplicado em reator metanogênico de segunda fase (RMI). Considerando a comparação entre os sistemas metanogênicos, fixou-se uma carga orgânica (CO) inicial de 2,5 g-DQO d-1, sendo aumentada até 5 g d-1. A partida do reator de fase única apresentou limitações, requerendo aplicação de baixos valores de CO, o que demandou 140 dias até a estabilização para a carga de 5 g-DQO d-1. Por sua vez, o sistema com duas fases necessitou de 102 dias e apresentou maior geração de metano (RMI 1,95 L-CH4 d-1 e RMII 1,76 L-CH4 d-1). A separação de fases permitiu a geração de efluente acidificado com menores concentrações de sulfato residual, resultando em maior produção de metano e reduzida concentração de sulfeto no biogás no sistema de duas fases, quando comparado ao sistema de fase única. / The treatment of sulfate-rich wastewater via anaerobic processes is challenging, due to the potential biological sulfate reduction to sulfide, which limits biogas use and affect treatment performance due to toxic and inhibitory effects. In this context, this study investigated the potential application of phase separation to minimize such operating problems. The operation of the first-stage reactor aimed to establish a sulfidogenic environment under acidogenic conditions. The effects of pre-acidifying the wastewater over methane production was further assessed through monitoring two methanogenic reactors, i.e., one single-phased system fed with raw sulfate-rich wastewater and one two-phased system fed with acidified wastewater. In all cases anaerobic structured-bed reactors were used as well as thermophilic temperature conditions were applied (55ºC). For the first-phase system, two reactors with different materials were compared: reactor with low density polyethylene cylinders (RAS-PEBD) with five operating steps (13 sub-stages) and another reactor with polyurethane foam cubes (RAS-PU) with four operating steps. The main operational strategies for the optimization of sulfate reduction were the variation of hydraulic retention time (HRT: 6-15 h RAS-PEBD; 12-16 h RAS-PU:), organic loading rate (OLRinfl: 10-20 kg-COD m-3 d-1 - RAS-PEBD; 15-20 kg-COD m-3 d-1 - RAS-PU), sulfate loading rate (SLR: 3.2-16.0 kg-SO4 m-3 d-1 - RAS-PEBD; 4 - 8 kg-SO4 m-3 d-1 RAS-PU), and upflow velocity (Vu: 0.06 - 3.35 m h-1 - RAS-PEBD ; 3.42-7.9 m h-1-RAS-PU). After a long period of biomass adaptation in RAS-PEBD, increasing efficiency patterns and sulfide stripping were observed. Controlling effluent recirculation was the key-factor to improve system performance. The same pattern was not obtained in RAS-PU, which presented performance losses due to clogging-related problems and the subsequent establishment of preferential pathways. The effluent from the first-phase reactor with residual sulfate load rate of less than 7% (OLRefl of 15.12 kg m-3 d-1 and sulfide of 256 mg L-1, sub-step X) was applied to a second-phase methanogenic reactor. Considering the comparison between the methanogenic systems, an initial organic load (OL) of 2.5 g-COD d-1 was set, which was further increased up to 5 g d-1. The start-up of the single-phase reactor presented limitations, requiring the application of lower OL values, in order to require 140 days up to the stabilization of the load of 5 g-COD d-1. In turn, the two-phase system required 102 days and presented higher methane generation rates metano (RMI 1,95 L-CH4 d-1 and RMII 1,76 L-CH4 d-1). Phase separation enabled the generation of an acidified effluent with lower residual sulfate concentrations, leading to higher methane production and low sulfide concentration in the biogas in the two-phase system, when compared to the single phase system.

O tratamento de água residuária rica em sulfato por via de processo anaeróbio é um grande desafio, devido ao potencial de redução do sulfato pela via biológica a sulfeto, o que pode inviabilizar o aproveitamento do biogás e afetar o tratamento por seus efeitos tóxicos e inibitórios. Neste contexto, o presente trabalho investigou a potencial aplicação da separação de fase para minimizar tais problemas de operação. A operação de reator de primeira fase visa estabelecer um ambiente sulfetogênico sob condições acidogênicas. Os efeitos da pré-acidificação da água residuária sobre a produção de metano foram avaliados por meio do monitoramento de dois reatores metanogênicos, um sistema de fase única alimentado com água residuária rica em sulfato e um sistema de duas fases alimentado com água residuária acidificada. Em todos os casos foram utilizados reatores anaeróbios de leito estruturado, aplicada condições termofílica de temperatura (55°C). Para o sistema de primeira fase, dois reatores com diferentes materiais foram comparados: reator com cilindros de polietileno de baixa densidade (RAS-PEBD) com cinco etapas de operação (13 subetapas) e outro reator com cubos de espuma de poliuretano (RAS-PU) com quatro etapas de operação. As principais estratégias operacionais para otimização da redução do sulfato a variação do tempo de detenção hidráulica (TDH: 6-15 h RAS-PEBD; 12 - 16 h RAS-PU ), carga orgânica volumétrica (COVafl: 10 - 20,0 kg-DQO m-3 d-1 - RAS-PEBD; 15 - 20 kg-DQO m-3 d-1 - RAS-PU), carga de sulfato volumétrica (CSV: 3,2-16,0 kg-SO4 m-3 d-1 - RAS-PEBD; 4 - 8 kg-SO4 m-3 d-1 - RAS-PU) e velocidade ascensional (Va: 0,06 3,35 m h-1 - RAS-PEBD; 3,42 7,9 m h-1 - RAS-PU). Após longo período de adaptação da biomassa no RAS-PEBD, verificou-se o aumento da eficiência e stripping do sulfeto. A recirculação controlada do efluente foi um fator chave para melhoria do sistema. O mesmo não foi obtido em RAS-PU, apresentando perda de desempenho devido a problemas de colmatação e subsequente aparecimento de vias preferenciais. O efluente do reator de primeira fase com carga de sulfato residual menor que 7% (COVefl de 15,12 kg-DQO m-3d-1 e sulfeto de 256 mg L-1, subetapa X) foi aplicado em reator metanogênico de segunda fase (RMI). Considerando a comparação entre os sistemas metanogênicos, fixou-se uma carga orgânica (CO) inicial de 2,5 g-DQO d-1, sendo aumentada até 5 g d-1. A partida do reator de fase única apresentou limitações, requerendo aplicação de baixos valores de CO, o que demandou 140 dias até a estabilização para a carga de 5 g-DQO d-1. Por sua vez, o sistema com duas fases necessitou de 102 dias e apresentou maior geração de metano (RMI 1,95 L-CH4 d-1 e RMII 1,76 L-CH4 d-1). A separação de fases permitiu a geração de efluente acidificado com menores concentrações de sulfato residual, resultando em maior produção de metano e reduzida concentração de sulfeto no biogás no sistema de duas fases, quando comparado ao sistema de fase única. / The treatment of sulfate-rich wastewater via anaerobic processes is challenging, due to the potential biological sulfate reduction to sulfide, which limits biogas use and affect treatment performance due to toxic and inhibitory effects. In this context, this study investigated the potential application of phase separation to minimize such operating problems. The operation of the first-stage reactor aimed to establish a sulfidogenic environment under acidogenic conditions. The effects of pre-acidifying the wastewater over methane production was further assessed through monitoring two methanogenic reactors, i.e., one single-phased system fed with raw sulfate-rich wastewater and one two-phased system fed with acidified wastewater. In all cases anaerobic structured-bed reactors were used as well as thermophilic temperature conditions were applied (55ºC). For the first-phase system, two reactors with different materials were compared: reactor with low density polyethylene cylinders (RAS-PEBD) with five operating steps (13 sub-stages) and another reactor with polyurethane foam cubes (RAS-PU) with four operating steps. The main operational strategies for the optimization of sulfate reduction were the variation of hydraulic retention time (HRT: 6-15 h RAS-PEBD; 12-16 h RAS-PU:), organic loading rate (OLRinfl: 10-20 kg-COD m-3 d-1 - RAS-PEBD; 15-20 kg-COD m-3 d-1 - RAS-PU), sulfate loading rate (SLR: 3.2-16.0 kg-SO4 m-3 d-1 - RAS-PEBD; 4 - 8 kg-SO4 m-3 d-1 RAS-PU), and upflow velocity (Vu: 0.06 - 3.35 m h-1 - RAS-PEBD ; 3.42-7.9 m h-1-RAS-PU). After a long period of biomass adaptation in RAS-PEBD, increasing efficiency patterns and sulfide stripping were observed. Controlling effluent recirculation was the key-factor to improve system performance. The same pattern was not obtained in RAS-PU, which presented performance losses due to clogging-related problems and the subsequent establishment of preferential pathways. The effluent from the first-phase reactor with residual sulfate load rate of less than 7% (OLRefl of 15.12 kg m-3 d-1 and sulfide of 256 mg L-1, sub-step X) was applied to a second-phase methanogenic reactor. Considering the comparison between the methanogenic systems, an initial organic load (OL) of 2.5 g-COD d-1 was set, which was further increased up to 5 g d-1. The start-up of the single-phase reactor presented limitations, requiring the application of lower OL values, in order to require 140 days up to the stabilization of the load of 5 g-COD d-1. In turn, the two-phase system required 102 days and presented higher methane generation rates metano (RMI 1,95 L-CH4 d-1 and RMII 1,76 L-CH4 d-1). Phase separation enabled the generation of an acidified effluent with lower residual sulfate concentrations, leading to higher methane production and low sulfide concentration in the biogas in the two-phase system, when compared to the single phase system.