Isolation of lignins from hardwood and softwood biomass samples, containing 26.1% and 28.1% lignin, respectively, has been performed with the use of alkaline and organosolv pretreatment methods. The effect of catalyst loading, ethanol content, particle size, and pretreatment time on the yields and properties of the isolated lignins were investigated. Alkaline lignins had higher carbohydrate contentup to 30% and exhibited higher molecular weights in the range of 3000 Da, with a maximum phenolic hydroxyl content of 1 mmol g −1 for birch and 2 mmol g −1 for spruce. Organosolv lignins, on the other hand, showed high purity93% or higherdespite the more extensive biomass dissolution into the pretreatment medium; they also exhibited a lower range of molecular weights between 600 and 1600 Da depending on the source and pretreatment conditions. Due to the lower molecular weight, phenolic hydroxyl content was also increased, reaching as high as 4 mmol g −1 with a simultaneous decrease in aliphatic hydroxyl content as low as 0.6 mmol g −1 . Efficient lignin dissolution of 62% for spruce and 69% for birch, achieved at optimal pretreatment conditions, was combined with extensive hemicellulose removal.
Aromatic monomer yields from lignin depolymerization can be predicted using quantifiable lignin properties.
BackgroundStrategies to improve copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment of hybrid poplar were investigated. These improvements included a combination of increasing hydrolysis yields, while simultaneously decreasing process inputs through (i) more efficient utilization of H2O2 and (ii) the addition of an alkaline extraction step prior to the metal-catalyzed AHP pretreatment. We hypothesized that utilizing this improved process could substantially lower the chemical inputs needed during pretreatment.ResultsHybrid poplar was pretreated utilizing a modified process in which an alkaline extraction step was incorporated prior to the Cu-AHP treatment step and H2O2 was added batch-wise over the course of 10 h. Our results revealed that the alkaline pre-extraction step improved both lignin and xylan solubilization, which ultimately led to improved glucose (86 %) and xylose (95 %) yields following enzymatic hydrolysis. An increase in the lignin solubilization was also observed with fed-batch H2O2 addition relative to batch-only addition, which again resulted in increased glucose and xylose yields (77 and 93 % versus 63 and 74 %, respectively). Importantly, combining these strategies led to significantly improved sugar yields (96 % glucose and 94 % xylose) following enzymatic hydrolysis. In addition, we found that we could substantially lower the chemical inputs (enzyme, H2O2, and catalyst), while still maintaining high product yields utilizing the improved Cu-AHP process. This pretreatment also provided a relatively pure lignin stream consisting of ≥90 % Klason lignin and only 3 % xylan and 2 % ash following precipitation. Two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR and size-exclusion chromatography demonstrated that the solubilized lignin was high molecular weight (Mw ≈ 22,000 Da) and only slightly oxidized relative to lignin from untreated poplar.ConclusionsThis study demonstrated that the fed-batch, two-stage Cu-AHP pretreatment process was effective in pretreating hybrid poplar for its conversion into fermentable sugars. Results showed sugar yields near the theoretical maximum were achieved from enzymatically hydrolyzed hybrid poplar by incorporating an alkaline extraction step prior to pretreatment and by efficiently utilizing H2O2 during the Cu-AHP process. Significantly, this study reports high sugar yields from woody biomass treated with an AHP pretreatment under mild reaction conditions.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-016-0442-0) contains supplementary material, which is available to authorized users.
For this work, four hardwoods (silver birch, sugar maple, a hybrid poplar, and a hybrid aspen) and one cultivar of switchgrass were treated with increasing levels of NaOH. The recovered cell wall biopolymers were characterized based on total extraction, precipitation using ethanol or acidification, xylan content, and molar mass of the recovered precipitates. The extractability of cell wall polymers was clearly shown to be a function of the biomass type with more than 50% of the cell walls of switchgrass solubilized by alkali while only up to 20% of the maple was solubilized under comparable conditions. Precipitation with ethanol resulted in high recovery yields of hemicelluloses from the original biomass for silver birch and switchgrass, and most notably, the birch precipitates contained double the hemicellulose content of the precipitates from other feedstock alkali extracts (80% versus 30−50%). The molar masses of the recovered hemicellulosic polysaccharides were characterized using size exclusion chromatography (SEC) and an assay to quantify polysaccharide reducing ends. SEC analysis showed that the biopolymers exhibited a strong tendency to self-associate during elution and that this aggregation could be eliminated through sonication. The reducing end method showed an increase in the number-average degree of polymerization toward an asymptotic maximum with increasing extraction pH, and this value was significantly increased by bleaching the precipitate to remove interference by nonpolysaccharides.
BackgroundWhen applied to recalcitrant lignocellulosic feedstocks, multi-stage pretreatments can provide more processing flexibility to optimize or balance process outcomes such as increasing delignification, preserving hemicellulose, and maximizing enzymatic hydrolysis yields. We previously reported that adding an alkaline pre-extraction step to a copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in improved sugar yields, but the process still utilized relatively high chemical inputs (catalyst and H2O2) and enzyme loadings. We hypothesized that by increasing the temperature of the alkaline pre-extraction step in water or ethanol, we could reduce the inputs required during Cu-AHP pretreatment and enzymatic hydrolysis without significant loss in sugar yield. We also performed technoeconomic analysis to determine if ethanol or water was the more cost-effective solvent during alkaline pre-extraction and if the expense associated with increasing the temperature was economically justified.ResultsAfter Cu-AHP pretreatment of 120 °C NaOH-H2O pre-extracted and 120 °C NaOH-EtOH pre-extracted biomass, approximately 1.4-fold more total lignin was solubilized (78% and 74%, respectively) compared to the 30 °C NaOH-H2O pre-extraction (55%) carried out in a previous study. Consequently, increasing the temperature of the alkaline pre-extraction step to 120 °C in both ethanol and water allowed us to decrease bipyridine and H2O2 during Cu-AHP and enzymes during hydrolysis with only a small reduction in sugar yields compared to 30 °C alkaline pre-extraction. Technoeconomic analysis indicated that 120 °C NaOH-H2O pre-extraction has the lowest installed ($246 million) and raw material ($175 million) costs compared to the other process configurations.ConclusionsWe found that by increasing the temperature of the alkaline pre-extraction step, we could successfully lower the inputs for pretreatment and enzymatic hydrolysis. Based on sugar yields as well as capital, feedstock, and operating costs, 120 °C NaOH-H2O pre-extraction was superior to both 120 °C NaOH-EtOH and 30 °C NaOH-H2O pre-extraction.Electronic supplementary materialThe online version of this article (10.1186/s13068-018-1124-x) contains supplementary material, which is available to authorized users.
Livestock and fish farming are rapidly growing industries facing the simultaneous pressure of increasing production demands and limited protein required to produce feed. Bacteria that can convert low-value non-food waste streams into singe cell protein (SCP) present an intriguing route for rapid protein production. The oleaginous bacterium Rhodococcus opacus serves as a model organism for understanding microbial lipid production. SCP production has not been explored using an organism from this genus. In the present research, R. opacus strains DSM 1069 and PD630 were fed three agro-waste streams: (1) orange pulp, juice, and peel; (2) lemon pulp, juice, and peel; and (3) corn stover effluent, to determine if these low-cost substrates would be suitable for producing a value-added product, SCP for aquafarming or livestock feed. Both strains used agro-waste carbon sources as a growth substrate to produce protein-rich cell biomass suggesting that that R. opacus can be used to produce SCP using agro-wastes as low-cost substrates.
The bioconversion of second-generation cellulosic ethanol waste streams into biodiesel via oleaginous bacteria, Rhodococcus, is a novel optimization strategy for biorefineries with substantial potential for rapid development.
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