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


Upgrading biomass pyrolysis vapour over faujasite catalysts

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

Introduction

Conceptual design

  • Integration with crude oil refineries

  • Generation of green fuel, take advantage of existed infrastructure


Upgrading biomass pyrolysis vapour over faujasite catalysts

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 50oC) 40-150 180

pH 2.4 --

  • Higher oxygen content in Bio-oil causes the problems


Upgrading biomass pyrolysis vapour over faujasite catalysts

introduction

goal

  • Catalytic design to selectively remove oxygen from biomass


Upgrading biomass pyrolysis vapour over faujasite catalysts

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)


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results & discussion

Product yields

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

Abundance

Pyrolysis

TIC: US wood 01.D\data.ms

750000

700000

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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


Upgrading biomass pyrolysis vapour over faujasite catalysts

Ketones, aldehydes, acids

Results& Discussion

How are they formed?

Cellulose

Furan derivatives


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results& Discussion

How are they formed?

Sugars

Ketones, aldehydes,

acids

Furan derivatives

Hemicellulose


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results& Discussion

How are they formed?

Phenol derivatives

Lignin


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results& Discussion

Acidity of bio-oil

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results& Discussion

Acidity of bio-oil- what determines acidity?

  • Acids contribute the most


Upgrading biomass pyrolysis vapour over faujasite catalysts

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

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.


Upgrading biomass pyrolysis vapour over faujasite catalysts

Results& Discussion

Stability of bio-oil

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

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.


Upgrading biomass pyrolysis vapour over faujasite catalysts

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]


Upgrading biomass pyrolysis vapour over faujasite catalysts

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!


Upgrading biomass pyrolysis vapour over faujasite catalysts

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


Upgrading biomass pyrolysis vapour over faujasite catalysts

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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