Oligomer saccharide reduction during dilute acid pretreatment co-catalyzed with Lewis acids on corn stover biomass

John Degenstein, Srinivas Reddy Kamireddy, Melvin P. Tucker, Yun Ji

Abstract


The dilute sulfuric acid pretreatment of lignocellulosic biomass is a well understood process that significantly enhances the yield of glucose after enzymatic saccharification. The goal of this research was to perform a systematic study to evaluate the yield of fermentable sugars during dilute sulfuric acid pretreatment that is co-catalyzed with the transition metal Lewis acid salts: AlCl3, FeCl2, FeCl3, and La(OTf)3. All Lewis acids apart from FeCl2 reduced the presence of xylo-oligomers by a large margin when compared to the non-co-catalyzed control sample pretreatments. The presence of these xylo-oligomers acts as inhibitors during enzymatic saccaharification step. The Lewis acids AlCl3, FeCl3, and La(OTf)3 were also able to marginally increase the overall enzymatic digestibility specifically for corn stover pretreated at 160°C with 10 mM of Lewis acids. The hard Lewis acid such as AlCl3 increased the formation inhibitory products such as furfural and 5-hydroxymethylfurfural (HMF). There was good correlation between reduction of xylo-oligomers and increased concentration furfural with increase in Lewis acid hardness.

Keywords


pretreatment, corn stover, biomass, biofuel, enzymatic saccharification, Lewis acid, transition metal

Full Text:

PDF

References


Dale B. Biofuels: Thinking clearly about the issues. Journal of Agricultural Food Chemistry, 2008; 56(11): 3885-3891.

Kumar R, Wyman C E. Cellulase adsorption and relationship to features of corn stover solids produced by leading pretreatments. Biotechnology Bioenergy, 2009; 103(2): 252-267.

Zheng Y, Pan Z L, Zhang R H. Overview of biomass pretreatment for cellulosic ethanol production. International Journal of Agriculture & Biological Engineering, 2009; 2(3): 51-68.

Dien B S, Sarath G, Pedersen J F, Sattler S E, Chen H, Funnell-Harris D L, et al. Improved sugar conversion and ethanol yield for forage sorghum (Sorghum bicolor L. Moench) lines with reduced lignin contents. Bioenergy Resource, 2009; 2(3): 153-164.

Mosier N S, Wyman C, Dale B. Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresource Technology, 2005; 96(6): 673-686.

Kootstra A M J, Beeftink H H. Comparison of dilute mineral and organic acid pretreatment for enzymatic hydrolysis of wheat straw. Biochemical Engineering, 2009; 46(2): 126-131.

Harmsen P, Huijgen W, Bermudez L, Bakker R. Literature review of physical and chemical pretreatment processes for lignocellulosic biomass. Biosynergy, 2010; 1184(10): 1-53.

Daniel J S, Farmer J, Newman M, McMillan J D. Dilute–Sulfuric acid pretreatment of corn stover in pilot scale reactor. Applied Biochemistry and Biotechnology, 2003; 105-108: 69-85.

Modig T, Lidén G, Taherzadeh M J. Inhibition effects of furfural on alcohol dehydrogenase, aldehyde dehydrogenase and pyruvate dehydrogenase. Journal of Biochemistry, 2002; 363(3): 769-776.

Qing Q, Yang B, Wyman C E. Xylooligomers are strong inhibitors of cellulose hydrolysis by enzymes. Bioresource Technology, 2010; 101(24): 9624-9630.

Humbird D, Davis R, Tao L, Kinchin C, Hsu D, Aden A. Process design and economics for biochemical conversion of lignocellulosic biomass to ethanol: Dilute-acid pretreatment and enzymatic hydrolysis of corn stover. NREL Report, 2011; TP-5100-47764.

Wei H, Donohoe B S, Vinzant T B, Ciesielski P N, Wang W, Gedvilas L M, et al. Elucidating the role of ferrous ion co-catalyst in enhancing dilute acid pretreatment of lignocellulosic biomass. Biotechnology for Biofuels, 2011; 4: 48-64.

Weiss N D, Farmer J D, Schell D J. Impact of corn stover composition on hemicellulose conversion during dilute acid pretreatment and enzymatic cellulose digestibility of the pretreated solids. Bioresource Technology, 2010; 101(2): 674-678.

Degenstein J C, Kamireddy S R, Tucker M P, Ji Y. Novel batch reactor for the dilute acid pretreatment of lignocellulosic feedstocks with improved heating and cooling kinetics. International Journal of Chemical Reactor Engineering, 2011; 9(1): 1-9.

Scarlata C, Hyman D. Development and validation of a fast high pressure liquid chromatography method for the analysis of lignocellulosic biomass hydrolysis and fermentation products. American Journal of Chromatography, 2010; 1217(14): 2082-2087.

Kamireddy R S, Schaefer C, Defrese M, Degenstein J C, Ji, Y. Pretreatment and enzymatic hydrolysis of sunflower hulls for fermentable sugar production. International Journal of Agricultural and Biological Engineering, 2012; 5(1): 62-70.

Donkoh E, Degenstein J, Tucker M, Ji Y. Optimization of enzymatic hydrolysis of dilute acid pretreated sugar beet pulp using response surface design. Journal of Sugar Beet Research, 2012; 49(1&2): 26-37.

Nguyen Q A. Tucker M P. Dilute acid/metal salt hydrolysis of lignocellulosics. Patent: 2002; US 6423145.

Fringuelli F, Pizzo F, Vaccaro L. Lewis-acid catalyzed organic reactions in water. The case of AlCl3, TiCl4, and SnCl4 believed to be unusable in aqueous medium. The Journal of Organic Chemistry, 2001; 66(13): 4719-4722.

Kobayashi S, Nagayama S, Busujima T. Lewis acid catalysts stable in water. Correlation between catalytic activity in water and hydrolysis constants and exchange rate constants for substitution of inner-sphere water ligands. Journal of the American Chemical Society, 1998; 120(32): 8287-8298.

Liu L, Sun J S, Cai C Y, Wang S H, Pei H S, Zhang J S. Corn stover pretreatment by inorganic salts and its effects on hemicellulose and cellulose degradation. Bioresource Technology, 2009; 100(23): 5865-5871.

Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D. Determination of sugars, byproducts, and degradation products in liquid fraction process samples. NREL Report, 2008; TP-510-42623.

Qing Q, Wyman C E. Hydrolysis of different chain length xylooliogmers by cellulase and hemicellulase. Bioresource Technology, 2011; 102(2): 1359-1366.

Choudhary V, Sandler S I, Vlachos D G. Conversion of xylose to furfural using Lewis and Brønsted acid catalysts in aqueous media. ACS Catalysis, 2012; 2(9): 2022-2028.

Yang Y, Hu C W, Abu-Omar M M. Synthesis of furfural from xylose, xylan, and biomass using AlCl3•6 H2O in biphasic media via xylose isomerization to xylulose. ChemSusChem, 2012; 5(2): 405-410.

Pearson R. Hard and soft acids and bases. Journal of American Chemical Society, 1963; 85(22): 3533-3539.

Zhao H, Holladay J E, Brown H, Zhang Z C. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science, 2007; 316(5831): 1597- 600.

Qi W, Zhang S P, Xu Q L, Ren Z W, Yan Y J. Degradation kinetics of xylose and glucose in hydrolyzate containing dilute sulfuric acid. The Chinese Journal of Process Engineering, 2008; 8(6): 1132-1137.

Weil J R, Dien B, Bothast R, Hendrickson R, Mosier N S, Ladisch M R. Removal of fermentation inhibitors formed during pretreatment of biomass by polymeric adsorbents. Industrial Engineering and Chemistry Research, 2002; 41(24): 6132-6138.

Kamireddy S R, Li J, Degenstein J, Tucker M, Ji Y. Effects and mechanism of metal chlorides salts on pretreatment and enzymatic digestibility of corn stover. Industrial Engineering and Chemistry Research, 2013; 52(5): 1775- 1782.

Parr R, Pearson R. Absolute hardness: Companion parameter to absolute electronegativity. Journal of American Chemical Society, 1983; 105(26): 7512-7516.

Peng L C, Lin L, Zhang J H, Zhuang J P, Zhang B X, Gong Y. Catalytic conversion of cellulose to levulinic acid by metal chlorides. Molecules, 2010; 15(8): 5258-5272.




Copyright (c)



2023-2026 Copyright IJABE Editing and Publishing Office