The yield of monosaccharides after two-stage concentrated sulfuric acid hydrolysis of softwood (Scots pine) and hardwood (trembling aspen) was modeled using a generalized severity parameter with a time-independent rate constant. The severity parameter, which combines the major operating variables acid concentration, temperature, and reaction time in the decrystallization stage into a single reaction ordinate, was successfully used to describe monosaccharide yields after a standardized hydrolysis stage. Conversion of cellulose to glucose demanded a higher severity to reach maximum glucose yields than the conversion of hemicelluloses to their respective monosaccharides, and the conversion of pine demanded a higher severity to obtain maximum monosaccharide yields as compared to aspen. The results indicate that the generalized severity parameter can be a useful tool for the prediction of sugar yields in a two-stage concentrated sulfuric acid hydrolysis process.
The effects on sugar yields of acid concentration, temperature, and time in the first (decrystallization) stage of a two-stage concentrated sulfuric acid hydrolysis of softwood (Scots pine) and hardwood (aspen) were investigated. The study focused on the multi-variable effects of the decrystallization stage and applied a statistical modeling with Central Composite Face (CCF) design of experiment to systematically study and simulate the effect of decrystallization reaction conditions on hydrolysis products and degradation products. The models were statistically significant and showed that for both aspen and pine, the reaction temperature and acid concentration were the most influential variables on monosaccharides and total sugar yields compared to the reaction time. The interaction between temperature and acid concentration was the most important for both species. The sugar degradation products were much influenced by the decrystallization temperature on both aspen and pine. The models were validated by a test-set and showed a good agreement between the experimental and predicted values. The optimum predicted total sugar yields were 56 g / 100 g d.w for aspen (74% theoretical) and 64 g / 100 g d.w for pine (91% theoretical).
The fermentability of hydrolyzates derived from two-stage concentrated sulfuric acid hydrolysis of Trembling aspen (Populus tremula) and Scots pine (Pinus sylvestris) were investigated. Three types of hydrolyzates were produced at mild, moderate and high decrystallization severity conditions. Portions of each of the original hydrolyzates were concentrated by vacuum evaporation to increase the sugar fraction to simulate industrial applications. Both sets of hydrolyzates were fermented anaerobically using Saccharomyces cerevisiae ATCC 96581. After 23 hours of fermentation, complete glucose consumption was observed for all the original hydrolyzates, with no signs of inhibition. The ethanol yields from these hydrolyzates ranged from 68% to 90% of theoretical value. Fermentation of concentrated aspen hydrolyzates produced at mild or moderate decrystallization severity showed a significant lag phase, associated with relatively high furfural content in the samples (approximately 2 g/L). No lag phase was apparent for aspen produced at high decrystallization severity or pine hydrolyzates. However, furfural had no adverse effect on the maximum ethanol yield. No inhibitory effect of HMF, acetic acid, formic acid or levulinic acid was detected in the concentrated hydrolyzates due to the relatively low concentrations of these compounds. The ethanol yields from concentrated hydrolyzates were above 97% of theoretical with exception of pine hydrolyzate produced at high severity which had a fairy good yield of 87%. The quantitative analysis of inhibitors and the fermentability investigation showed that both the original and concentrated hydrolyzates from the concentrated sulfuric acid process were readily fermentable, and furfural was singled out as the most important inhibitor in these hydrolyzates.
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