The impacts of deacetylation prior to dilute acid pretreatment on the bioethanol process

<p>Abstract</p> <p>Background</p> <p>Dilute acid pretreatment is a promising pretreatment technology for the biochemical production of ethanol from lignocellulosic biomass. During dilute acid pretreatment, xylan depolymerizes to form soluble xylose monomers and oligomers. Because the xylan found in nature is highly acetylated, the formation of xylose monomers requires two steps: 1) cleavage of the xylosidic bonds, and 2) cleavage of covalently bonded acetyl ester groups.</p> <p>Results</p> <p>In this study, we show that the latter may be the rate limiting step for xylose monomer formation. Furthermore, acetyl groups are also found to be a cause of biomass recalcitrance and hydrolyzate toxicity. While the removal of acetyl groups from native corn stover by alkaline de-esterification prior to pretreatment improves overall process yields, the exact impact is highly dependent on the corn stover variety in use. Xylose monomer yields in pretreatment generally increases by greater than 10%. Compared to pretreated corn stover controls, the deacetylated corn stover feedstock is approximately 20% more digestible after pretreatment. Finally, by lowering hydrolyzate toxicity, xylose utilization and ethanol yields are further improved during fermentation by roughly 10% and 7%, respectively. In this study, several varieties of corn stover lots were investigated to test the robustness of the deacetylation-pretreatment-saccharification-fermentation process.</p> <p>Conclusions</p> <p>Deacetylation shows significant improvement on glucose and xylose yields during pretreatment and enzymatic hydrolysis, but it also reduces hydrolyzate toxicity during fermentation, thereby improving ethanol yields and titer. The magnitude of effect is dependent on the selected corn stover variety, with several varieties achieving improvements of greater than 10% xylose yield in pretreatment, 20% glucose yield in low solids enzymatic hydrolysis and 7% overall ethanol yield.</p

Kinetic Modelling and Experimental Studies for the Effects of Fe2+ Ions on Xylan Hydrolysis with Dilute-Acid Pretreatment and Subsequent Enzymatic Hydrolysis

High-temperature (150–170 °C) pretreatment of lignocellulosic biomass with mineral acids is well established for xylan breakdown. Fe2+ is known to be a cocatalyst of this process although kinetics of its action remains unknown. The present work addresses the effect of ferrous ion concentration on sugar yield and degradation product formation from corn stover for the entire two-step treatment, including the subsequent enzymatic cellulose hydrolysis. The feedstock was impregnated with 0.5% acid and 0.75 mM iron cocatalyst, which was found to be optimal in preliminary experiments. The detailed kinetic data of acid pretreatment, with and without iron, was satisfactorily modelled with a four-step linear sequence of first-order irreversible reactions accounting for the formation of xylooligomers, xylose and furfural as intermediates to provide the values of Arrhenius activation energy. Based on this kinetic modelling, Fe2+ turned out to accelerate all four reactions, with a significant alteration of the last two steps, that is, xylose degradation. Consistent with this model, the greatest xylan conversion occurred at the highest severity tested under 170 °C/30 min with 0.75 mM Fe2+, with a total of 8% xylan remaining in the pretreated solids, whereas the operational conditions leading to the highest xylose monomer yield, 63%, were milder, 150 °C with 0.75 mM Fe2+ for 20 min. Furthermore, the subsequent enzymatic hydrolysis with the prior addition of 0.75 mM of iron(II) increased the glucose production to 56.3% from 46.3% in the control (iron-free acid). The detailed analysis indicated that conducting the process at lower temperatures yet long residence times benefits the yield of sugars. The above kinetic modelling results of Fe2+ accelerating all four reactions are in line with our previous mechanistic research showing that the pretreatment likely targets multiple chemistries in plant cell wall polymer networks, including those represented by the C–O–C and C–H bonds in cellulose, resulting in enhanced sugar solubilization and digestibility

MOESM1 of Techno-economic analysis of the deacetylation and disk refining process: characterizing the effect of refining energy and enzyme usage on minimum sugar selling price and minimum ethanol selling price

Additional file 1 Additional infomation on design of experiments and process simulation using Aspen plus

Improved ethanol yield and reduced Minimum Ethanol Selling Price (MESP) by modifying low severity dilute acid pretreatment with deacetylation and mechanical refining: 1) Experimental

<p>Abstract</p> <p>Background</p> <p>Historically, acid pretreatment technology for the production of bio-ethanol from corn stover has required severe conditions to overcome biomass recalcitrance. However, the high usage of acid and steam at severe pretreatment conditions hinders the economic feasibility of the ethanol production from biomass. In addition, the amount of acetate and furfural produced during harsh pretreatment is in the range that strongly inhibits cell growth and impedes ethanol fermentation. The current work addresses these issues through pretreatment with lower acid concentrations and temperatures incorporated with deacetylation and mechanical refining.</p> <p>Results</p> <p>The results showed that deacetylation with 0.1 M NaOH before acid pretreatment improved the monomeric xylose yield in pretreatment by up to 20% while keeping the furfural yield under 2%. Deacetylation also improved the glucose yield by 10% and the xylose yield by 20% during low solids enzymatic hydrolysis. Mechanical refining using a PFI mill further improved sugar yields during both low- and high-solids enzymatic hydrolysis. Mechanical refining also allowed enzyme loadings to be reduced while maintaining high yields. Deacetylation and mechanical refining are shown to assist in achieving 90% cellulose yield in high-solids (20%) enzymatic hydrolysis. When fermentations were performed under pH control to evaluate the effect of deacetylation and mechanical refining on the ethanol yields, glucose and xylose utilizations over 90% and ethanol yields over 90% were achieved. Overall ethanol yields were calculated based on experimental results for the base case and modified cases. One modified case that integrated deacetylation, mechanical refining, and washing was estimated to produce 88 gallons of ethanol per ton of biomass.</p> <p>Conclusion</p> <p>The current work developed a novel bio-ethanol process that features pretreatment with lower acid concentrations and temperatures incorporated with deacetylation and mechanical refining. The new process shows improved overall ethanol yields compared to traditional dilute acid pretreatment. The experimental results from this work support the techno-economic analysis and calculation of Minimum Ethanol Selling Price (MESP) detailed in our companion paper.</p

A highly efficient dilute alkali deacetylation and mechanical (disc) refining process for the conversion of renewable biomass to lower cost sugars

Abstract Background The deconstruction of renewable biomass feedstocks into soluble sugars at low cost is a critical component of the biochemical conversion of biomass to fuels and chemicals. Providing low cost high concentration sugar syrups with low levels of chemicals and toxic inhibitors, at high process yields is essential for biochemical platform processes using pretreatment and enzymatic hydrolysis. In this work, we utilize a process consisting of deacetylation, followed by mechanical refining in a disc refiner (DDR) for the conversion of renewable biomass to low cost sugars at high yields and at high concentrations without a conventional chemical pretreatment step. The new process features a low temperature dilute alkaline deacetylation step followed by disc refining under modest levels of energy consumption. Results The proposed process was demonstrated using a commercial scale Andritz double disc refiner. Disc refined and deacetylated corn stover result in monomeric glucose yields of 78 to 84% and monomeric xylose yields of 71 to 77% after enzymatic hydrolysis at process-relevant solids and enzyme loadings. The glucose and xylose yields of the disc refined substrates in enzymatic hydrolysis are enhanced by 13% and 19%, respectively. Fermentation of the DDR substrates at 20% total solids with Z.mobilis utilized almost all sugars in 20hrs indicating the sugar hydrolyzate produced from the DDR process is highly fermentable due to low levels of chemical contaminants. The ethanol titer and ethanol process yield are approximately 70 g/L and 90% respectively. Conclusions The proposed new process has been demonstrated using pilot scale deacetylation and disc refiners. The deacetylated and disc refined corn stover was rapidly deconstructed to monomeric sugars at 20% wt solids with enzymatic hydrolysis. High process sugar conversions were achieved, with high concentrations of monomeric sugars that exceeded 150 g/L. The sugar syrups produced were found to have low concentrations of known major fermentation inhibitors: acetic acid, furfural and HMF. The low levels of these fermentation inhibitors lead to high fermentation yields. The results suggest that this process is a very promising development for the nascent cellulosic biofuels industry