Upgrading biomass pyrolysis vapour over faujasite catalysts
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Upgrading biomass pyrolysis vapour over faujasite catalysts. T.S. Nguyen, A. Imran, L. Lefferts, G. Brem, K. Seshan. Introduction. Motivation. Pyrolysis. 500˚C, 1 atm,  < 2 sec. World fossil reserves are being depleted. Bio-oil. Biomass is a “Sustainable feedstock”.

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Upgrading biomass pyrolysis vapour over faujasite catalysts

Upgrading biomass pyrolysis vapour over faujasite catalysts

T.S. Nguyen, A. Imran, L. Lefferts, G. Brem, K. Seshan


Introduction

Motivation

Pyrolysis

500˚C, 1 atm,

 < 2 sec

  • World fossil reserves are being depleted

Bio-oil

  • Biomass is a “Sustainable feedstock”

Biomass waste/residue

  • Bio-oil allows easier storage and transport


Introduction

Conceptual design

  • Integration with crude oil refineries

  • Generation of green fuel, take advantage of existed infrastructure


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) 35-40 1.0

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 50oC) 40-150 180

pH 2.4 --

  • Higher oxygen content in Bio-oil causes the problems


introduction

goal

  • Catalytic design to selectively remove oxygen from biomass


Introduction

Experimental set-up

Gas preheater

IR furnace

To GC

Catalyst bed

Condensers

  • Fixed bed reactor/ catalyst mixed with biomass

  • H-FAU, Na-FAU and Na0.2H0.8-FAU, SiO2/Al2O3 = 5.2

  • RT – 500 ºC ramp in 8 sec (fast pyrolysis)


Results & discussion

Product yields

  • Acid sites facilitated cracking reactions, resulted in the formation of coke and gas


Abundance

Pyrolysis

TIC: US wood 01.D\data.ms

750000

700000

650000

600000

550000

500000

450000

400000

350000

300000

250000

200000

150000

100000

50000

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

Time-->

GC-MS analysis of bio-oil

Results& Discussion

  • Chemical composition of bio-oil were investigated

  • Components in bio-oil reflect the decomposition of the three components: cellulose, hemicellulose, and lignin


Ketones, aldehydes, acids

Results& Discussion

How are they formed?

Cellulose

Furan derivatives


Results& Discussion

How are they formed?

Sugars

Ketones, aldehydes,

acids

Furan derivatives

Hemicellulose


Results& Discussion

How are they formed?

Phenol derivatives

Lignin


Results& Discussion

Acidity of bio-oil

  • Carboxylic acids, phenols and sugars all contribute to acidity of bio-oil


Results& Discussion

Acidity of bio-oil- what determines acidity?

  • Acids contribute the most


Results& Discussion

Acidity of bio-oil

Pt catalyst

+ H2

  • Decrease acidity of bio-oil by decreasing acids and sugars,

  • Phenols less acidic but have high energy content

    • Hydrogenation is an option


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.


Results& Discussion

Stability of bio-oil

  • Using the catalysts, the concentration of carbonyls is decreased and hence higher stability is expected


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

  • Na0.2H0.8-FAU favours the formation of HCs and hence improve the energy content of bio-oil


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.


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]


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!


Results& Discussion

Gas analysis

  • CO and CO2 are the main products

  • The yield of CO2 maximized with Na0.2H0.8-FAU catalyst

  • Hydrocarbons can be recycled as a [H] source


Results& Discussion

Coke and Char analysis

  • Coke and char are oxygen-containing oligomeric species

  • Coke is aromatic in nature (molar C:H=7:6)


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