1. EVALUATION OF SOFTWOOD KRAFT AND ORGANOSOLV LIGNIN AS FEEDSTOCK FOR BIOFUELS AND BIOMATERIALS Oihana Gordobil Donostia, 26 th May 2015

2. Contents Objectives Methodology Results Chemical composition and molecular weight Functional groups ( 31 P NMR / 13 C NMR) Thermal properties Proximate analysis Conclusions

3. Objectives Chemical, structural and thermal characterization of organosolv and Kraft Spruce lignins to compare their potential use as feedstock in different applications like bioenergy or biomaterials.

4. Methodology Isolation of lignins ORGANOSOLV KRAFT Ethanol-water (50%wt) H =1:7 (w/w) T = 180°C t = 60 min H 2 SO 4 (1.2 %wt) SPRUCE Lignoboost process Characterization of lignins Chemical composition (Klason and soluble lignin, ashes, sugar and sulfur content) SEC (Molecular weight ) 31 P NMR (Aliphatic and phenolic hydroxyls content) 13 C NMR (Degree of condensation) DSC (Glass transition temperature T g ) TGA (Thermal stability, % of volatiles, Fixed Carbon, Organic matter and Heat capacity) Chemical Structure Thermal properties

5. OSKS Klason Lignin (%)94.388.5 Acid soluble lignin (%)3.12.3 Ash (%)3.22.5 Total Sugars (%)0.51.0 C (%)67.365.5 H (%)5.05.4 N (%)0.090.11 S (%)0.040.22 MnMn 11291624 MwMw 31307215 PDI2.84.5 Results Chemical composition and molecular weight Thiol groups (R-SH)

6. Functional groups (mmol/g)OSKS Aliphatic OH0.751.75 Phenolic OH2.994.04 S a OHND G a OH1.792.56 Condensed G b 1.201.48 β-50.380.66 5-5´0.590.91 4-O-50.350.47 Total OH 3.745.79 COOH 0.230,40 Degree of condesation a 1.121.40 Results Functional groups 31 P NMR/ 13 C NMR OH (aliphatic and phenolic) Condensed Structure KS a Determined by 13 C NMR (3.00-I 123-106 )

7. [200-600] °CResidue at 800 °C SamplesT 5% db (°C )wt (%)T max (°C)Weight (%) OS243.2 43.8 382.246.9 KS262.052.8390.738.8 Results Thermal properties DSCTGA KS OH (aliphatic and phenolic) Molecular weight Degree of condensation TgTg

8. SampleVolatiles %Fixed carbon %Organic matter % HHV (MJ/Kg) [1][2] OS55.0 ± 0.241.7 ± 0.096.7 ± 0.324.024.2 KS63.9 ± 2.033.5 ± 2.597.4 ± 0.023.022.8 Results Proximate analysis [1] R.García, C. Pizarro, A.G. Lavín, J.L. Bueno, Spanish biofuels heating value estimation. Part II: Proximate analysis Data, Fuel. 117 (2014) 1139-1147. [2] T. Cordero, F. Marquez, J. Rodriguez-Mirasol, J.J. Rodriguez, Predicting heating values of lignocellulosic and carbonaceous materials from proximate analysis, Fuel. 80 (2011) 1567-1571. Commercial fuelAsh %Volatile %Fixed carbon % HHV (MJ/Kg) Almond shell2.28215.818.3 Olive stone1.478.320.417.8 Wood chip1.568.629.915.2

9. Both isolated lignins presented different structure and thermal properties because of the used extraction process. Both lignins showed high purity. Kraft Lignin (KS) presented the highest sulfur content. KS had higher M w than OS and higher molecular weight resulted in higher T g and thermal stability. KS had more condensed structure (β-5, 5-5´ ) than OS which is generated during the last stage of Kraft process and higher content of aliphatic and phenolic hydroxyl groups due to the cleavage of α-aryl and β-aryl ether linkages in native lignin during the Kraft process. The total content of OH groups was generally high for both lignins, making them a suitable raw material for chemical modifications. The content of phenolic OH groups was higher for Kraft lignin. Both lignins can be suitable to use in bioenergy applications because they showed appropriate values in the proximate analysis. Conclusions

10. Thank you for your attention!