1. LIQUEFACTION OF WOOD AND ITS APPLICATION FOR THE PRODUCTION OF THERMOSETTING MOLDING MATERIALS TUFAN SALAN KAHRAMANMARAS SUTCU IMAM UNIVERSITY, DEPARTMENT OF MATERIAL SCIENCE AND ENGINEERING KAHRAMANMARAS, TURKEY 1 COST Action FP1105 WoodCellNet workshop in San Sebastian Polytechnic School of San Sebastian, University of The Basque Country 26-27 May 2015 San Sebastian, Spain

2. Introduction Today, lignocellulosic biomass can be converted to a broad range of value-added:  Fine chemicals  Biofuels  Green polymeric materials via Biorefinery Concept. 2

3. Biorefinery Conversion Methods  PHYSICAL UPGRADING METHODS (drying, pulverisation, briquetting, and pelletizing)  CHEMICAL AND BIOCHEMICAL METHODS (hydrolysis followed by fermentation or chemical conversion)  THERMOCHEMICAL METHODS (torrefaction, pyrolysis, gasification, liquefaction, and combustion)  OTHER METHODS (e.g., production of composites or fractionation followed by chemical conversion - cellulose derivatives) 3

4. Biorefinery Concept For The Liquefaction of Biomass 4

5. Liquefaction of Wood 5  Solvolysis liquefaction one of the thermochemical method dissolves wood in an organic solvent (e.g. phenol) with an acidic (e.g. hydrochloric, sulfuric, phosphoric acid) or alkaline (e.g. NaOH, MgSO 4 ) catalyst at moderate temperatures (80-150 °C) or without catalyst at elevated temperatures (240-270 °C) and atmospheric pressure.

6. Composition of Wood 6 …which has plenty hydroxyl groups. Hydroxyl groups make it possible to convert liquefied wood into biopolymers.

7. Applications of Liquefied Wood 7 PU Foams Phenolic Resins Adhesives Carbon Fibers Polyesters Moldings

8. Phenelation of Wood and Its Resinification  With the increasing requirements for a more extensive utilization of the abundant and renewable biomass resources, liquefaction of wood in the presence of phenol and its application to thermosetting materials is a promising technique.  During liquefaction (phenolation), carbohydrate and lignin content converted to small fragments or monomolecular compounds via hydrolysis, degradation, and decomposition reactions and after this they react with phenol to form derivatives. 8

9. 9 Phenelation of Wood

10.  Condensation reaction of liquefied wood and formaldehyde is an efficient way to use the unreacted free phenol left behind after the liquefaction process.  Phenol-liquefied products can easily react with formaldehyde; to form novalac or resol type phenol- formaldehyde resins.  Also, formaldehyde does not react only with free phenol but also with liquefied wood components having reactive sites. 10

11. 11 Resinification of Wood

12. Resins Synthesized in the Presence of Acid Catalysts  Sulfiric, Hydrochloric, Phosphoric, Oxalic acid…  Sulfuric acid seemed to be the most effective catalyst on the phenolation of unmodified wood at moderate temperatures.  Phenolysis of wood components in the presence of an acidic catalyst resulted in dozens or even hundreds of different reactions that compete with each other.  Due to the cleavage of lignin in the presence of phenol, a variety of phenolic compounds such as coniferyl alcohol, vanilin, etc. are formed. 12

13. 13 Resinified phenolated wood Hexamethylenetetramine (HMTA) (as curing agent) Zinc Stearate (as lubricating agent) Calcium Hydroxide (as accelerating agent). Wood Powder Hot Pressing (190 ˚C, 40 MPa, 5 min) Molding Material Tests Mechanical and Physical Tests Mechanical and Physical Thermosetting Molding Production

14. Thank You 14