RESUMO
Physicochemical processes, such as the Lo-cat and Amine-Claus process, are commonly used to remove hydrogen sulfide from hydrocarbon gas streams such as landfill gas, natural gas, and synthesis gas. Biodesulfurization offers environmental advantages, but still requires optimization and more insight in the reaction pathways and kinetics. We carried out experiments with gas lift bioreactors inoculated with haloalkaliphilic sulfide-oxidizing bacteria. At oxygen-limiting levels, that is, below an O(2)/H(2)S mole ratio of 1, sulfide was oxidized to elemental sulfur and sulfate. We propose that the bacteria reduce NAD(+) without direct transfer of electrons to oxygen and that this is most likely the main route for oxidizing sulfide to elemental sulfur which is subsequently oxidized to sulfate in oxygen-limited bioreactors. We call this pathway the limited oxygen route (LOR). Biomass growth under these conditions is significantly lower than at higher oxygen levels. These findings emphasize the importance of accurate process control. This work also identifies a need for studies exploring similar pathways in other sulfide oxidizers such as Thiobacillus bacteria.
Assuntos
Bactérias/metabolismo , Reatores Biológicos/microbiologia , Recuperação e Remediação Ambiental/instrumentação , Recuperação e Remediação Ambiental/métodos , Redes e Vias Metabólicas , Oxigênio/química , Sulfetos/metabolismo , Álcalis/metabolismo , Bactérias/crescimento & desenvolvimento , Biodegradação Ambiental , Biomassa , Halogênios/metabolismo , Sulfeto de Hidrogênio/metabolismo , Concentração de Íons de Hidrogênio , Oxirredução , Consumo de Oxigênio , Especificidade da Espécie , Thiobacillus/metabolismoRESUMO
In a biotechnological process for hydrogen sulfide (H2S) removal from gas streams, operating at natronophilic conditions, formation of thiosulfate (S2O3(2-)) is unfavorable, as it leads to a reduced sulfur production. Thiosulfate formation was studied in gas-lift bioreactors, using natronophilic biomass at [Na+] + [K+] = 2 mol L(-1). The results show that at sulfur producing conditions, selectivity for S2O3(2-) formation mainly depends on the equilibrium between free sulfide (HS(-)) and polysulfide (Sx(2-)), which can be controlled via the pH. At pH 8.6, 21% of the total dissolved sulfide is present as Sx(2-) and selectivity for S2O3(2-) formation is 3.9-5.5%. At pH 10, 87% of the total dissolved sulfide is present as Sx(2-) and 20-22% of the supplied H2S is converted to S2O3(2-), independent of the H2S loading rate. Based on results of bioreactor experiments and biomass activity tests, a mechanistic model is proposed to describe the relation between S2O3(2-) formation and pH.
Assuntos
Biotecnologia , Sulfeto de Hidrogênio/isolamento & purificação , Concentração de Íons de Hidrogênio , Tiossulfatos/síntese química , BiomassaRESUMO
An integrated physicochemical and biological technique for NO(x) removal from flue gas, the so-called BioDeNO(x) process, combines the principles of wet absorption of NO in an aqueous Fe(II)EDTA(2-) solution with biological reduction of the sorbed NO in a bioreactor. The biological reduction of NO to di-nitrogen gas (N(2)) takes place under thermophilic conditions (55 degrees C). This study demonstrates the technical feasibility of this BioDeNO(x) concept in a bench-scale installation with a continuous flue gas flow of 650 l.h(-1) (70-500 ppm NO; 0.8-3.3% O(2)). Stable NO removal with an efficiency of at least 70% was obtained in case the artificial flue gas contained 300 ppm NO and 1% O(2) when the bioreactor was inoculated with a denitrifying sludge. An increase of the O(2) concentration of only 0.3% resulted in a rapid elevation of the redox potential (ORP) in the bioreactor, accompanied by a drastic decline of the NO removal efficiency. This was not due to a limitation or inhibition of the NO reduction, but to a limited biological iron reduction capacity. The latter leads to a depletion of the NO absorption capacity of the scrubber liquor, and thus to a poor NO removal efficiency. Bio-augmentation of the reactor mixed liquor with an anaerobic granular sludge with a high Fe(III) reduction capacity successfully improved the bioreactor efficiency and enabled to treat a flue gas containing at least 3.3% O(2) and 500 ppm NO with an NO removal efficiency of over 80%. The ORP in the bioreactor was found to be a proper parameter for the control of the ethanol supply, needed as electron donor for the biological regeneration process. The NO removal efficiency as well as the Fe(III)EDTA(-) reduction rate were found to decline at ORP values higher than -140 mV (pH 7.0). For stable BioDeNO(x) operation, the supply of electron donor (ethanol) can be used to control the ORP below that critical value.