1. Processing Lignins Guozhan Jiang

2. Objectives To find a method to convert Etek and Asian lignins into bio-oils. To characterise the products using PyGC/MS and other chromatographic or spectroscopic methods. To upgrade the bio-oils to valuable chemicals or transportation oils.

3. Outline Component determination PyGC-MS work Preliminary work for run on 150g/h rig Alternative way to pyrolysis Future work

4. Component determination: wet chemistry method Extractives:Extracted using: ethanol/toluene (6hrs) ethanol (4hrs) water (2hrs) Lignin (Klason):0.1M NaOH boiling 1hr 72% H 2 SO 4 treatment 4hrs Cellulose:NaClO 2 bleaching of holocellulose Hemicellulose:17.5% NaOH treatment of cellulose Biomass

5. Results Etek ligninAsian lignin Extractive (%)12.7439.68 Lignin (%)29.20- Cellulose (%)45.70- Hemicellulose (%) 9.32-

6. Component determination The component of Etek lignin can be determined using this method. This method is not suitable for Asian lignin since the extractive free samples can be completely dissolved in 0.1M NaOH. Asian lignin must have a much less cross-linking density in its molecular structure. Conclusions

7. PyGC-MS work Species containing m/z =94 and 78 Asian lignin @600 o C for 15s

8. Etek lignin species containing m/z = 94 and 78 Etek lignin@600 o C for 15s

9. Asian lignin @400 o C for 15s Asian lignin@600 o C for 15s

10. Etek lignin 400 and 600 Etek lignin@400 o C for 15s Etek lignin @600 o C for 15s

11. PyGC-MS work The two lignins can not be pyrolysed effectively at 400 o C. Asian lignin is a ‘real’ lignin. Etek lignin has similar composition to normal biomass. Conclusions

12. Preliminary work for run lignins on 150g/h rig The two lignins are difficult to feed continuously. Two approaches to be adopted for feeding properly (1) Modify feeding system, (2) Modify lignins. Modification of lignins is chosen in this work by pelitization.

13. Pellitization Alcohol extracted compounds as binders Asian lignin Ethanol Suspension Heating up 80 o C “Dough” like Drying Pellet Mixing

14. Pelletization of Asian lignin Before pelletingAfter pelleting

15. Pellet

16. Alternative to pyrolysis Method% dissolved 0.1 M NaOH aqueous, 4hrs boiling, 10%10.2 Ethanol + 0.1 M NaOH, 4hrs boiling, 10%10.5 Isopropanol + 0.1M NaOH, 4hrs boiling, 10%21.2 Isopropanol + 0.1M H 2 SO 4 + Phenol (13.5% wt), 10%28.3 Extracted using ethanol/toluene (6hrs), ethanol (4hrs) and water (2hrs), extractive free samples boiling in 0.1M NaOH, 2% 100 Asian lignin

17. Alternative to pyrolysis Extractive free sample dissolved in 0.1M NaOH, 2%

18. Future work Run Asian and Etek lignins on 150 g/h rig for pyrolysis Hydrogenation of lignin pyrolytic products to produce saturated phenol and phenol substitutes, which may be used to produce phenolic resin. Quantification of mass balance using Py-GC/MS. Hydrogen, steam or alcohol assisted pyrolysis to reduce char formation.