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Speciation of sulfur in biochar produced from pyrolysis and gasification of oak and corn stover.

ABSTRACT: The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600-800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). Biochars produced under pyrolysis conditions at 500-600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77-100%. Biochars produced in gasification conditions at 850 °C contain 73-100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix.

SUBMITTER: Cheah S

PROVIDER: S-EPMC4123929 | biostudies-literature | 2014

REPOSITORIES: biostudies-literature

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Project description:The production of value-added chemicals alongside biofuels from lignocellulosic hydrolysates is critical for developing economically viable biorefineries. Here, the production of propionic acid (PA), a potential building block for C3-based chemicals, from corn stover hydrolysate is investigated using the native PA-producing bacterium Propionibacterium acidipropionici.A wide range of culture conditions and process parameters were examined and experimentally optimized to maximize titer, rate, and yield of PA. The effect of gas sparging during fermentation was first examined, and N2 was found to exhibit improved performance over CO2. Subsequently, the effects of different hydrolysate concentrations, nitrogen sources, and neutralization agents were investigated. One of the best combinations found during batch experiments used yeast extract (YE) as the primary nitrogen source and NH4OH for pH control. This combination enabled PA titers of 30.8 g/L with a productivity of 0.40 g/L h from 76.8 g/L biomass sugars, while successfully minimizing lactic acid production. Due to the economic significance of downstream separations, increasing titers using fed-batch fermentation was examined by changing both feeding media and strategy. Continuous feeding of hydrolysate was found to be superior to pulsed feeding and combined with high YE concentrations increased PA titers to 62.7 g/L and improved the simultaneous utilization of different biomass sugars. Additionally, applying high YE supplementation maintains the lactic acid concentration below 4 g/L for the duration of the fermentation. Finally, with the aim of increasing productivity, high cell density fed-batch fermentations were conducted. PA titers increased to 64.7 g/L with a productivity of 2.35 g/L h for the batch stage and 0.77 g/L h for the overall process.These results highlight the importance of media and fermentation strategy to improve PA production. Overall, this work demonstrates the feasibility of producing PA from corn stover hydrolysate.

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Speciation of sulfur in biochar produced from pyrolysis and gasification of oak and corn stover.

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