1. UPGRADING BIOMASS PYROLYSIS VAPOUR OVER FAUJASITE CATALYSTS T.S. NGUYEN, A. IMRAN, L. LEFFERTS, G. BREM, K. SESHAN

2. 21/5/15 2 INTRODUCTION Biomass waste/residue  Biomass is a “Sustainable feedstock”  World fossil reserves are being depleted  Bio-oil allows easier storage and transport Pyrolysis 500˚C, 1 atm,  < 2 sec Bio-oil MOTIVATION

3. 21/5/15 3 INTRODUCTION CONCEPTUAL DESIGN  Integration with crude oil refineries  Generation of green fuel, take advantage of existed infrastructure

4. 21/5/15 4 INTRODUCTION PROBLEMS IDENTIFICATION Characteristic Bio-oil Heavy Fuel Oil Water content (w%) 15-35 0.1 C (w%, dry) 50-64 85 H (w%, dry) 5.2-7 11.1 O (w%, dry) 35-401.0 N (w%, dry) 0.05-0.4 0.3 S (w%, dry) 0.05-0.3 2.3 Energy content (MJ/kg) 16 – 19 * 40 Viscosity (cP at 50 o C) 40-150 180 pH 2.4 -- ● Higher oxygen content in Bio-oil causes the problems

5. 21/5/15 5 INTRODUCTION GOAL ● Catalytic design to selectively remove oxygen from biomass

6. 21/5/15 6 INTRODUCTION EXPERIMENTAL SET-UP IR furnace Catalyst bed Condensers To GC Gas preheater ● Fixed bed reactor/ catalyst mixed with biomass ● H-FAU, Na-FAU and Na 0.2 H 0.8 -FAU, SiO 2 /Al 2 O 3 = 5.2 ● RT – 500 ºC ramp in 8 sec (fast pyrolysis)

7. 21/5/15 7 RESULTS & DISCUSSION PRODUCT YIELDS ● Acid sites facilitated cracking reactions, resulted in the formation of coke and gas

8. 21/5/15 8 RESULTS& DISCUSSION GC-MS ANALYSIS OF BIO-OIL ● Chemical composition of bio-oil were investigated ● Components in bio-oil reflect the decomposition of the three components: cellulose, hemicellulose, and lignin Pyrolysis

9. 21/5/15 9 RESULTS& DISCUSSION HOW ARE THEY FORMED? Furan derivatives Ketones, aldehydes, acids Cellulose

10. 21/5/15 10 RESULTS& DISCUSSION HOW ARE THEY FORMED? Ketones, aldehydes, acids Furan derivatives Hemicellulose Sugars

11. 21/5/15 11 RESULTS& DISCUSSION HOW ARE THEY FORMED? Phenol derivatives Lignin

12. 21/5/15 12 RESULTS& DISCUSSION ACIDITY OF BIO-OIL ● Carboxylic acids, phenols and sugars all contribute to acidity of bio-oil

13. 21/5/15 13 RESULTS& DISCUSSION ACIDITY OF BIO-OIL- WHAT DETERMINES ACIDITY? Acids contribute the most

14. 21/5/15 14 RESULTS& DISCUSSION ACIDITY OF BIO-OIL ● Decrease acidity of bio-oil by decreasing acids and sugars, ● Phenols less acidic but have high energy content ● Hydrogenation is an option + H 2 Pt catalyst

15. 21/5/15 15 RESULTS& DISCUSSION STABILITY OF BIO-OIL- HOW IS AGING HAPPEN? ● During aging process, low-molecular-weight components react with each other to form heavy fraction, increase viscosity. ● In most of the reactions which occurs during this process, aldehydes react with itself or other components such as phenol or alcohol and form water.

16. 21/5/15 16 RESULTS& DISCUSSION STABILITY OF BIO-OIL ● Using the catalysts, the concentration of carbonyls is decreased and hence higher stability is expected

17. 21/5/15 17 RESULTS& DISCUSSION ENERGY CONTENT OF BIO-OIL ● Due to the low H/C in biomass, the obtained HCs in bio-oil are mostly aromatics ● These aromatics are formed from both cellulose, hemicellulose and lignin ● Na 0.2 H 0.8 -FAU favours the formation of HCs and hence improve the energy content of bio-oil

18. 21/5/15 18 CONCLUSIONS& PLANNING BIO-OIL BULK ANALYSIS ● Quality of bio-oil in terms of : stability, acidity and energy content have been improved. ● The extent of the improvement is not high enough. C wt.%H wt.%O wt.%Energy content (MJ/kg) Thermal5264220 Na-FAU5553922 Na 0.2 H 0.8 -FAU5953824 H-FAU5654022

19. 21/5/15 19 CONCLUSIONS& PLANNING SODIUM BASED CATALYSTS- FUTURE PLAN ● With sodium-based catalysts, it is possible to decrease the oxygen content in bio-oil down to 11 wt.% and resulted in a high energy oil (almost fuel oil ~ 40 MJ/kg). ● Future plan: Carry out hydrogenation to further improve quality of bio-oil. Finding another source of cheaper [H] C wt.%H wt.%O wt.%Energy content (MJ/kg) Thermal5264220 Na 0.2 H 0.8 -FAU5953824 Sodium-based8091138

20. 21/5/15 20 ACKNOWLEDGEMENT ● B.G. Geerdink and K. Altena- Schildkamp for technical support ● M. Zabeti and A. Imran for fruitful discussions ● GSPT (STW) for financial support GSPT Green & Smart Process Technologies THANK YOU!

21. 21/5/15 21 RESULTS& DISCUSSION GAS ANALYSIS Gas yield (wt.%) ThermalNa-FAUNa 0.2 H 0.8 -FAUH-FAU CO4.664.898.017.25 CO 2 4.754.377.556.03 HC0.831.103.662.91 H2H2 0.020.030.180.09 ● CO and CO 2 are the main products ● The yield of CO 2 maximized with Na 0.2 H 0.8 -FAU catalyst ● Hydrocarbons can be recycled as a [H] source

22. 21/5/15 22 RESULTS& DISCUSSION COKE AND CHAR ANALYSIS ● Coke and char are oxygen-containing oligomeric species ● Coke is aromatic in nature (molar C:H=7:6) C wt.%H wt.%O wt.%Energy content (MJ/kg) Yield wt.% Coke87.586.056.37301.82 Char78.722.8018.482620.48