GLUCOSE PRODUCTION FROM CELLULOSE IN SUBCRITICAL AND SUPERCRITICAL WATER Taiying Zhang ‘A thesis submitted in partial fulfillment of the requirements for the Doctar of Philosophy degree in Chemical and Biochemical Engineering in the Graduate College of The University of lowa May 2008 Thesis Supervisors: Adjunet Associate Professor Gary A. Aurand Professor Victor G.J. RodgersUMI Number: 3323488 INFORMATION TO USERS The quality of this reproduction is dependant upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UML UM! Microform 3323488 Copyright 2008 by ProQuest LLC. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 E. Eisenhower Parkway PO Box 1346, ‘Ann Arbor, Ml 48106-1346TABLE OF CONTENTS LIST OF TABLES. LIST OF FIGURES CHAPTER 1. PROJECT INTRODUCTION LI Project Overview 1.2 Biomass and Bioret 13 Cellulose. 1.4 Subcritical supercritical LAPTER 2, RESEARCH BACKGROUND. 2.1 Methods for Cellulose Reactions. 2.1.1 Acidh Hydrolysi 2.1.2 Enzymatic Hydrolysis 2.1.3 Hydrothermal Process ature Review of Cellulose Hydrothermal Process . 2.2.1 Hydrothermal Process by Batch Reactor... 2.2.2 Hydrothermal Process by Semi-baich Reactor 2.2.3 Hydrothermal Process by Flow-type Reactor... 2.3 Reaction Pathways of Cellulose Hydroihermal Proce: 2.3.1 Kinetic Model af Cellulose Hydrolysis 2.3.2 Hydrolysis of Cellooligosaccharides, 2°3.3 Kinctie Model af Maltoo! igosacchari 2.3.4 Kinetic Model of Glucase Decamposi 22 2: 2.1 The Simulation of Batch Reactor. CHAPTER 3, RESEARCH OBJECTIVES. 3.1 Experimental Reactions Stud; 3.2 Develop Kinetics Model. 1 Kinetics Model of 3.2.2 Kineties Model af Glucose Decomposition 3.3 Reactions 3.3.1 Reactor Si 3.3.2 Reaction: CHAPTER 4. EXPERIMENTAL STUDY OF CELLULOSE REACTIONS IN SUBCRITICAL AND SUPERCRITICL WATER BY A TUBULAR REACTOR. 4.1 Experimental Methods. 4.1.1 Experimental Selup and the Process 4.1:2 Design of Experiments 4.1.3 Products Analysis Methods 4.1.4 Data Analysis Method... 4.2. CeMUTO5E READ nen 4.2.1 System Error of Cellulose Reaction 4.2.2 Sequential Reactions of Cellulose Liquefaction. 4.2.3 Temperature and Flow Rate Study.4.2.4 Reactant Concentration Study 42:5 Pressure Study 43 Starch Reaction... 43.1 Temperature and Flow Rate Study... 43.2 Reactant Concentration Study... 43.3 Pressure Study 4.4 Glucose Reaction... 44.1 System Error of Glucose Reaction 44-2 Temperature and Flow Rate Study 4.4.3 Reactant Concentration Study... 4.4.4 Pressure Study 4.5 Summary of Experimes CHAPTER 5. EXPERIMENTAL STUDY OF KINETICS PARAMETERS OF THE REACTIONS IN SUBCRITICAL WATER BY A MICROREACTOR., 5.1 Experiments method... 5.1. Experimental setup. 5.1.2 Design of Experiments and Data Analysis. 5.1.3 Data Analysis Method: $8.2 Kinetics Model for Glucose and Fructase Decompasition, 5.2.1 Glucose Reaction: 5.2.2 Fructose Reactions... 53.3 Kineties Model for Maltotetranse.... 5.3.4 Summary of above oligomers. 5.4 Kinetics Model for Cellulose Reaction. Sa. 1 Kinetics Model nsec 5.4.2 Kinetics Model for Cel CHAPTER 6, REACTIONS SIMULATION ...- oo so Mass and Heat Transfer of the Two Reactors 2 Simulation Result and Conclusions, ulation of Cellotriose Reaction in Different Type Reactors. 6.4 Summary of Reaction Simulation. CHAPTER 7, IMPACT AND FUTURE WORK.. APPENDIX A. TOP VALUE-ADDED CHEMICALS FROM BIOMASS APPENDIX 8, T-TEST METHOD FOR THE DATA ANALY’ APPENDIX C, THE RESULTS OF CELLULOSE REPEATED EXPERIMENGLUCOSE PRODUCTION FROM CELLULOSE, IN SUBCRITICAL AND SUPERCRITICAL WATER by Taiying Zhang A thesis submitted in partial Fulfillment of the requirements for the Docior of Philosophy degree in Chemical and Biochemical Engineering, im the Graduate College af “The University of lows May 2008 8: Adjunct Associate Professor Gary A. Aurand Professor Victor G. J. RodgersAPPENDIX D, THE RESULTS OF GLUCOSE REPEATED EXPERIMENTS ........146 APPENDIX E, THE RESULTS OF DIFFERENT COEFFICENT OF CONVECTIVE AND RADIATIVE COMBINATION..... REFERENCESLIST OF TABLES Table I. Critical temperature and pressure of substances Table 2. Recent publications on hydrolys or cellulosic materials... Table 3. Activation energies of cellulose hydrothermal process Table 4. Comparison of cellobiose kinetics model, ‘Table 5. Kineties results of maltooligasaecharides. Table 6. Summary of results of glucose degradation kinetics Table 7. Cellulose repeated experiments results. ‘Table 8. Cellulose sequential experiments results... ‘Table 9. Products of cellulase reaction at different teniperatures (flow rate 5 g/min) . Table 10, Products of cellulose reaction at different temperatures (flow rate 15 gi Table 11, Cellulose reaction product at different temperatures (pressure 6600 psi). Table 12. Cellulose reaction product at different temperatures (pressure 7500 psi)... Table 13 Glucose repeated experiments results analysis, Table 14, Reaction rate constant of glucose decomposition at different temperatures ..99° ‘Table 15. Reaction rate constant of fructose decomposition at different temperatures. Table 16, Summary of Armhenius plat of glucose and fructose decomposition. ‘Table 17. Summary and Comparison with literature results. ‘Table 18, Reaction rate constant of Cellobiese and Maltose decompositio ‘Table 19, Reaction rate constant of Cellotriose and Maltotriose decomposition at different temperatures, ‘Table 20. to for all the reactants at different temperatures ‘Table 21, Summary of Arthenius plot of oligomers decomposition Table 22. Reactions of cellotriose hydrolysis in suberitical water .LIST OF FIGURES: Figure 1. Arrangement of cellulose molecules and hydrogen bonds in fibrils. Figure 2. Pressure-temperature phase diggram for pure water... Figure 3. Pressure-density phase diagram for pure water... Figure 4, The dielectric constant s of water with respect to pressure and temperatire Figure 5, fon product of water at low pressur Figure 6. lon product of water at high pressut Figure 7. Two types af cellulase decomposition pathway.. settee WD Figure 8. Cellulose degradation in subcritical and supercritical Witter... ernecnn Figure 9. Glucose degradation in subcritical and supercritical Water ..occoonensennennnS Figure 10. Simplified reaction scheme of liquefaction andlor gasification enon 19 Figure 11. The pathway of firseorder cellulose reaction eens nnsnrnnennn Figure 12. Arshenius plot of the decomposition eens OS Suboritical and superritical water Figure 13. Main pathways of cetlobinse decomposition-| sccm Figure 14, Main pathways of cellabiose decomposition-2 Figure 15, Chain conformations of maltooligosaccharides Figure 16. Simplified glucase decomposition scheme in subcritical and SUPERETIIET WALCE creme Figure 17. Arthenius plot for glucose decomposition rate canstant Figure 18, Reaction pathways of glucose decomposition in subcritical and supercritical water. Figure 19, Experimental setup of the tubuilar reactor Figure 20. The scheme of the tubulae reactor... Figure 21. Evaluation of system error for cellukose reaction.. Figure 22. Cellulose reaction product at different temperatures. Figure 23. Cellulose reaction product at different temperatures with the dferent flow rates... venFigure 24. Water density at different temperatures with the constant pressure S000 psi Figure 25. Water viscosity at different temperatures with the constant pressure: S000 psi Figure 26. Cellulose reaction product at different temperatures with different cellulose concentrations, - Figure 27. Cellulose reaction product at different temperatures with the pressures. sure 28, Water density at different pressures. Figure 29. Water viscasity at different pressures. Figure 30, Starch reaction product at different temperatures with the flow rates, Figure 31. Starch reaction product at different temperatures with different concentrations, Figure 32, Starch reaction product at different temperatures with different pressures Figure 33. Glucose repeated reaction with feed at 10 gimin. rvnnsnnennneee Figure 34. Glucose reaction product at different temperatures with the Row rates ......83 Figure 35, Glucose reaction product at different exit temperatures with feed concentrations. Figure 36. Glucose reaction product at different exit temperatures with different pressures.. Figure 37. Cellulose reaction mechanism... Figure 38. The schem: Figure 39, Experimental setup of the microreaetor of the microreactor Figure 40. The mechanism of glucose decompasition in this study’... Figure 41. The mechanism of fructose decomposition ...c.cnccseeee Figure 42, The reaction rate constants of glucose degradation in suberitical water. Figure 43. The resction rate constants of fructose degradation in suberitical water .....100" Figure 44, Arrhenius plot of glucose decomposition reaction . Figure 45. Arrhenius plot of fructose decomposition reaction Figure 46, Archenius plot of detailed glucose decomposition reaction . veel OB Figure 47. Archenius plot of detailed fiuctose decomposition reaction......nsccnee 103