CHEME 1110 Lignocellulose Chemistry Introduction Tapani Vuorinen Contents

CHEM-E 1110 Lignocellulose Chemistry Introduction Tapani Vuorinen

Contents • Chemical structure, physicochemical properties and chemical reactivity of cellulose, hemicelluloses, lignin and extractives • Emphasis on reactivity and reaction mechanisms and kinetics • Preparative fractionation of lignocellulose to its constituents • Extractives, holocellulose, hemicelluloses • Chemical characterization of the fractions by spectroscopy and chromatography • FTIR and Raman spectroscopy • Solid and liquid state NMR spectroscopy • Gas chromatography-mass spectroscopy 2

Learning outcomes • Knowledge on characteristic reactions of the polysaccharides and lignin • Ability to intercorrelate the components’ chemical structure with their physicochemical properties and chemical reactivity • Laboratory skills to • Fractionate lignocellulose to its main constituents (extractives, hemicelluloses, cellulose, lignin) • Characterize the chemical structure of the constituents by chromatography and spectroscopy 3

Workload and schedules • Lectures, weeks 44 -49, L 2/PUU 1 (Vuorimiehentie 1), lecture notes/learning diary • Wednesdays at 13: 15 -15: 00 (weeks 44 -48) • Thursdays at 12: 15 -14: 00 (weeks 44 -49) • Tuesday at 10: 15 -12: 00 (week 49) • Laboratory works, weeks 44 -49, PUU 1 teaching laboratory, a single report in the end • Fridays at 13: 00 -17: 00 (weeks 44 -48) • Friday at 11: 00 -15: 00 (week 49) • Presentation of lecture notes and end discussion, week 50 • Times to be agreed separately by each group 4

Topics of lectures (changes are possible) Date Time Contents 1/11 13: 15 -15: 00 Introduction, fractionation and analysis of lignocellulose 2/11 12: 15 -14: 00 Basics of carbohydrates – structure, functionality 8/11 13: 15 -15: 00 Basics of lignin – formation, structure, functionality 9/11 12: 15 -14: 00 Basics of kinetics, aryl alkyl ether bond cleavage in non-phenolic lignin 15/11 13: 15 -15: 00 Aryl alkyl ether bond cleavage in phenolic and oxidized lignin 16/11 12: 15 -14: 00 Radical, electrophilic and nucleophilic oxidation of lignin 22/11 13: 15 -15: 00 No lecture 23/11 12: 15 -14: 00 Glycoside and ester hydrolysis 29/11 13: 15 -15: 00 Endwise degradation of 1, 4 -linked polysaccharides 30/11 12: 15 -14: 00 Catalytic and non-catalytic oxidation of polysaccharides 5/12 10: 15 -12: 00 Phenol-aldehyde condensation and lignin-carbohydrate complexes 7/12 12: 15 -14: 00 Alkylation and esterification of lignocellulose, summary 5

Supporting reading • Papermaking Science and Technology book series at https: //ebooks. papereng. fi/ebooks/aalto/ • Volume 3: Forest Products Chemistry • Volume 20: Biorefining of Forest Resources 6

Topics of lab works (changes are possible) Date Time Contents 3/11 13: 00 -17: 00 Own sample preparation for fractionation; detection and quantification of carbohydrates and reducing sugars by absorption spectroscopy 10/11 13: 00 -17: 00 Acetone extraction of own sample; solid and liquid state 13 C and 1 H NMR spectroscopy of selected (lignocellulose and lignin) samples 17/11 13: 00 -17: 00 Holocellulose preparation and quantification of dissolved carbohydrates; FTIR spectroscopy and GC-MS (after methanolysis) of acetone extracts 24/11 13: 00 -17: 00 Isolation of hemicelluloses; FTIR spectroscopy of acetone extracted lignocellulose and holocellulose; UVRR spectroscopy of holocellulose 1/12 13: 00 -17: 00 Catalytic oxidation of cellulose monitored by iodometric titration, quantification of aldehyde and carboxylate groups by iodometric and coductometric titration, respectively; FTIR spectroscopy of hemicelluloses 8/12 11: 00 -15: 00 Degradation of hemicelluloses in acid and alkali monitored for reducing sugars and total carbohydrates, respectively 7

Guidelines for laboratory works • Passing CHEM’s laboratory safety training is required to work in the laboratory (teacher Kirsi Yliniemi) • Study at https: //mycourses. aalto. fi/course/view. php? id=15279 • Be present in time (PUU 1, lobby) • Take your own lab coat with you if you have one • Works in groups of ca. 3 students • Stay always with your own group 8