Dilute acid catalysed hydrolysis of cellulose – extension to formic acid

New methods are being sought for the production of chemicals, fuels and energy from renewable biomass. Lignocellulosic biomass consists mainly of cellulose, hemicellulose and lignin. Cellulose and hemicellulose can be converted to their building blocks, i.e. sugars, via hydrolysis. This thesis is focused on glucose production from cellulose by dilute acid hydrolysis. Acid hydrolysis has the drawback of limited glucose yields, but it has the potential to become a shortterm solution for biochemical production. During acid hydrolysis, the cellulose chain is split into glucose, which undergoes further decomposition reactions to hydroxymethylfurfural, levulinic acid, formic acid and by-products like insoluble humins. The present thesis aims to increase our knowledge on complicated acidcatalysed hydrolysis of cellulose. Glucose decomposition and cellulose hydrolysis were studied independently in laboratory experiments. Kinetic modelling was used as a tool to evaluate the results. The effect of the hydrogen ion on the reactions was evaluated using formic or sulphuric acid as a catalyst. This thesis provides new knowledge of cellulose hydrolysis and glucose decomposition in formic acid, a novel catalyst for high-temperature dilute acid hydrolysis. Glucose yields from cellulose hydrolysed in formic or in sulphuric acid were comparable, indicating that a weak organic acid could function as a cellulose hydrolysis catalyst. Biomass fibres in the form of wheat straw pulp were hydrolysed more selectively to glucose than a model component, microcrystalline cellulose, using formic acid. Glucose decomposition took place similarly in formic and sulphuric acid when the temperature dependence of the hydrogen ion concentration was taken into account, but a significant difference was found between the reaction rates of cellulose hydrolysis in formic acid and in sulphuric acid. The observations can be explained by changes in the cellulose hydrolysis mechanism. Thus, it is proposed in this thesis that side-reactions from cellulose to non-glucose compounds have a more significant role in the system than has earlier been understood.

[1]  F. Lichtenthaler.  Carbohydrates as Organic Raw Materials , 2010 .

[2]  Jay H. Lee,et al.  Multivariate statistical analysis of X-ray data from cellulose: a new method to determine degree of crystallinity and predict hydrolysis rates. , 2010, Bioresource technology.

[3]  David R. Thompson,et al.  Design and Evaluation of a Plug Flow Reactor for Acid Hydrolysis of Cellulose , 1979 .

[4]  W. L. Marshall,et al.  Second Dissociation Constant of Sulfuric Acid from 25 to 350° Evaluated from Solubilities of Calcium Sulfate in Sulfuric Acid Solutions1,2 , 1966 .

[5]  Giuseppe Destino,et al.  Positioning in wireless networks : non-cooperative and cooperative algorithms , 2012 .

[6]  Johanna Ketonen.  Equalization and channel estimation algorithms and implementations for cellular MIMO-OFDM downlink , 2012 .

[7]  G. M. Panchenkov,et al.  Chemical kinetics and catalysis , 1976 .

[8]  Andrew Porteous,et al.  Kinetics of the acid hydrolysis of cellulose found in paper refuse , 1971 .

[9]  Y. Bigot,et al.  Formic acid pulping of rice straw , 2001 .

[10]  Hongwei Wu,et al.  Understanding the Primary Liquid Products of Cellulose Hydrolysis in Hot-Compressed Water at Various Reaction Temperatures , 2010 .

[11]  Design and Economic Evaluation of Cellulose Hydrolysis Processes , 1987 .

[12]  N. Bakhshi,et al.  Kinetic studies of wheat straw hydrolysis using sulphuric acid , 1985 .

[13]  Myung-Hwa Kim,et al.  Temperature dependence of dissociation constants for formic acid and 2,6-dinitrophenol in aqueous solutions up to 175 °C , 1996 .

[14]  J. F. Harris,et al.  Kinetic Model for the Dilute Sulfuric Acid Saccharification of Lignocellulose , 1985 .

[15]  E. C. Sherrard,et al.  Review of Processes in the United States Prior to World War II , 1945 .

[16]  J. Tanskanen,et al.  Distinct Effect of Formic and Sulfuric Acids on Cellulose Hydrolysis at High Temperature , 2012 .

[17]  J. Tanskanen,et al.  Hydrolysis of organosolv wheat pulp in formic acid at high temperature for glucose production. , 2012, Bioresource technology.

[18]  B. Kuster,et al.  The influence of the initial and catalyst concentrations on the dehydration of d-fructose , 1977 .

[19]  V. Santos,et al.  Study of formic acid as an agent for biomass fractionation , 2002 .

[20]  Hannu Kukka,et al.  Case studies in human information behaviour in smart urban spaces , 2012 .

[21]  Michael R Ladisch,et al.  Characterization of acid catalytic domains for cellulose hydrolysis and glucose degradation. , 2002, Biotechnology and bioengineering.

[22]  Qian Xiang,et al.  Kinetics of glucose decomposition during dilute-acid hydrolysis of lignocellulosic biomass , 2004, Applied biochemistry and biotechnology.

[23]  G. Zacchi,et al.  Simplistic modeling approach to heterogeneous dilute-acid hydrolysis of cellulose microcrystallites , 2003, Applied biochemistry and biotechnology.

[24]  M. Kober,et al.  Hydration of microcrystalline cellulose and milled cellulose studied by sorption calorimetry. , 2008, The journal of physical chemistry. B.

[25]  Rajeev K Sukumaran,et al.  Formic Acid as a Potential Pretreatment Agent for the Conversion of Sugarcane Bagasse to Bioethanol , 2010, Applied biochemistry and biotechnology.

[26]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[27]  Jussi-Pekka Jansson.  A stabilized multi-channel CMOS time-to-digital converter based on a low frequency reference , 2012 .

[28]  Stephen J. Miller,et al.  Switchgrass pretreatment and hydrolysis using low concentrations of formic acid , 2011 .

[29]  E. Hirst.  The Chemistry of Cellulose , 1946, Nature.

[30]  David K. Johnson,et al.  Glucose reversion reaction kinetics. , 2010, Journal of agricultural and food chemistry.

[31]  G. N. Richards,et al.  Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose an sucrose. , 1990, Carbohydrate research.

[32]  Mika Körkkö,et al.  On the analysis of ink content in recycled pulps , 2012 .

[33]  Jaakko Suutala,et al.  Learning discriminative models from structured multi-sensor data for human context recognition , 2012 .

[34]  David K. Johnson,et al.  Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin , 2007 .

[35]  Enyong Ding,et al.  Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups , 2007 .

[36]  H. H. Beeftink,et al.  Differential effects of mineral and organic acids on the kinetics of arabinose degradation under lignocellulose pretreatment conditions , 2009 .

[37]  Meng Wang.  Polymer integrated Young interferometers for label-free biosensing applications , 2012 .

[38]  Maria Strømme,et al.  Moisture sorption by cellulose powders of varying crystallinity. , 2004, International journal of pharmaceutics.

[39]  R. Sun,et al.  Formic acid based organosolv pulping of bamboo (Phyllostachys acuta): Comparative characterization of the dissolved lignins with milled wood lignin , 2012 .

[40]  Leon P.B.M. Janssen,et al.  A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid , 2006 .

[41]  G. T. Tsao,et al.  CORRELATION OF GLUCOSE (DEXTROSE) DEGRADATION AT 90 TO 190°C IN 0.4 TO 20% ACID , 1987 .

[42]  Tapani Koivukangas,et al.  Methods for determination of the accuracy of surgical guidance devices : a study in the region of neurosurgical interest , 2012 .

[43]  S. Adachi,et al.  Isomerization of hexoses in subcritical water , 2007 .

[44]  Yukiyasu Asaoka,et al.  Hydrothermal saccharification of cotton cellulose in dilute aqueous formic acid solution , 2011 .

[45]  Davide Macagnano,et al.  Multitarget localization and tracking : active and passive solutions , 2012 .

[46]  Lu Lin,et al.  Hydrolysis behavior of bamboo fiber in formic acid reaction system. , 2010, Journal of agricultural and food chemistry.

[47]  Leon P.B.M. Janssen,et al.  Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid , 2007 .

[48]  Junkal Landaburu-Aguirre.  Micellar-enhanced ultrafiltration for the removal of heavy metals from phosphorous-rich wastewaters : from end-of-pipe to clean technology , 2012 .

[49]  Leon P.B.M. Janssen,et al.  Green Chemicals: A Kinetic Study on the Conversion of Glucose to Levulinic Acid , 2006 .

[50]  Marc Londo,et al.  Bioenergy: a sustainable and reliable energy source. A review of status and prospects. , 2009 .

[51]  Jian Xu,et al.  Pretreatment on corn stover with low concentration of formic acid. , 2009, Journal of microbiology and biotechnology.

[52]  R. M. Izatt,et al.  Thermodynamic quantities for the interaction of SO42− with H+ and Na+ in aqueous solution from 150 to 320°C , 1988 .

[53]  W. Qi,et al.  Model for Continual Depolymerization of Biomass Catalyzed by Dilute Sulfuric Acid , 2009 .

[54]  Beatriz Lorenzo Veiga.  New network paradigms for future multihop cellular systems , 2012 .

[55]  F. Schenck.  Glucose and Glucose-Containing Syrups , 2006 .

[56]  Jerome F. Saeman,et al.  Kinetics of Wood Saccharification - Hydrolysis of Cellulose and Decomposition of Sugars in Dilute Acid at High Temperature , 1945 .

[57]  Mark F. Davis,et al.  Ab initio molecular dynamics simulations of β-d-glucose and β-d-xylose degradation mechanisms in acidic aqueous solution , 2005 .

[58]  Shinichi Takahashi,et al.  Reaction of cellulose with formic acid and stability of cellulose formate , 1986 .

[59]  Simo Hietakangas.  Design methods and considerations of supply modulated switched RF power amplifiers , 2012 .

[60]  Y. Y. Lee,et al.  Fundamental Aspects of Dilute Acid Hydrolysis/Fractionation Kinetics of Hardwood Carbohydrates. 1. Cellulose Hydrolysis , 2000 .

[61]  Avelino Corma,et al.  Chemical Routes for the Transformation of Biomass into Chemicals , 2007 .

[62]  Shijie Liu,et al.  Hydrolysis of cotton fiber cellulose in formic acid , 2007 .

[63]  R. P. Overend,et al.  Characterization of depolymerized cellulosic residues , 1989, Wood Science and Technology.

[64]  A. Katz,et al.  Unexpected phosphate salt-catalyzed hydrolysis of glycosidic bonds in model disaccharides: Cellobiose and maltose , 2010 .

[65]  R. J. Mcilroy.  Introduction to carbohydrate chemistry , 1967 .

[66]  A. Ault.  General Acid and General Base Catalysis , 2007 .

[67]  R. Overend,et al.  Dilute acid depolymerization of cellulose in aqueous phase: Experimental evidence of the significant presence of soluble oligomeric intermediates , 1986 .

[68]  Sushil K. R. Patil,et al.  Formation and Growth of Humins via Aldol Addition and Condensation during Acid-Catalyzed Conversion of 5-Hydroxymethylfurfural , 2011 .

[69]  W. K. Farr.  The Chemistry of Cellulose , 1936 .

[70]  Jaakko Soini.  Effects of environmental variations in Escherichia coli fermentations , 2012 .

[71]  J. Araki,et al.  Influence of surface charge on viscosity behavior of cellulose microcrystal suspension , 1999, Journal of Wood Science.

[72]  Sami Myllymäki.  Capacitive antenna sensor for user proximity recognition , 2012 .

[73]  H. Grethlein,et al.  Kinetics of acid hydrolysis of corn stover , 1982 .

[74]  J. F. Harris,et al.  Chemical Conversion of Wood Residues , Part V Kinetics of the Acid Catalyzed Conversion of Glucose to 5-Hydroxymethyl-2-Furadehyde and Levulinic Acid 1 , 2007 .

[75]  E. Koukios,et al.  Dilute acid hydrolysis of lignocellulosics: An application to medium consistency suspensions of hardwoods using a plug flow reactor , 1990 .

[76]  L. F. Hawley,et al.  The chemistry of wood , 1926 .

[77]  Christophe Blecker,et al.  Optimization of formic/acetic acid delignification of Miscanthus × giganteus for enzymatic hydrolysis using response surface methodology , 2012 .

[78]  M. Wolfrom,et al.  Acid Reversion Products from D-Glucose , 1954 .

[79]  P. McCarty,et al.  Thermochemical pretreatment of lignocellulose to enhance methane fermentation: I. Monosaccharide and furfurals hydrothermal decomposition and product formation rates , 1988, Biotechnology and bioengineering.

[80]  J. Tanskanen,et al.  Kinetics of glucose decomposition in formic acid , 2011 .

[81]  Oleg Davidyuk.  Automated and interactive composition of ubiquitous applications , 2012 .

[82]  Michal Green,et al.  Kinetics of dilute acid hydrolysis of cellulose originating from municipal solid wastes , 1992 .

[83]  M. Taherzadeh,et al.  Acid-based hydrolysis processes for ethanol from lignocellulosic materials: A review , 2007, BioResources.

[84]  Kimmo Halunen,et al.  Hash function security:cryptanalysis of the Very Smooth Hash and multicollisions in generalised iterated hash functions , 2012 .

[85]  Xiuyang Lu,et al.  Fructose decomposition kinetics in organic acids-enriched high temperature liquid water , 2009 .

[86]  G. Shelef,et al.  The effect of the neutralizing capacity of cellulosic materials on the kinetics of cellulose dilute acid hydrolysis , 1988 .

[87]  M. Antal,et al.  Productive and parasitic pathways in dilute acid-catalyzed hydrolysis of cellulose , 1992 .

[88]  L. Lucia,et al.  Kinetic modeling of formic acid pulping of bagasse. , 2008, Journal of agricultural and food chemistry.

[89]  A. Curvelo,et al.  Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst , 2012 .

[90]  J. Tanskanen,et al.  Comparison of Formic and Sulfuric Acids as a Glucose Decomposition Catalyst , 2010 .