a Ghent University, Laboratory for Chemical Technology, Technologiepark 914, 9052 Gent, Belgium

http://www.lct.UGent.beb Laboratorio de Desarrollo de Energías Alternativas, Departamento de Ingeniería Química, Universidad San Francisco de Quito,

Casilla Postal: 17-12-841, Quito, Ecuador

*E-mail: Kevin.VanGeem@UGent.be

Cascatbel Workshop 2016, Chalkidiki, Greece, May 18-20 , 2016

DESIGN AND CONSTRUCTION OF AN EXPERIMENTAL SETUP FOR MEASURING INTRINSIC

KINETICS OF BIOMASS FAST PYROLYSIS Diana C. Vargas a,b, Hilal Ezgi Toraman a, Hans-Heinrich Carstensen a, Daniela Almeida Streitwieser b,

Kevin M. Van Geem a* and Guy B. Marin a

European Research Institute of Catalysis

Biomass

Model compounds of interest

Phenol decomposition (major pathway)

OH OH

H

O

H

H

O

H

H

O

H

H

or

O

H

H

+ CO

cup size

Fuels and chemicals

Lignin: Complex polymer of p-coumaryl alcohol, coniferyl alcohol,

and sinapyl alcohol

Analytics sectionMicro-pyrolyzer

GC×GC - FID/TOF-MS

• Simultaneous identification

and quantification

• High sensitivity TOF-MS with

soft ionization feature

Customized Trace GC 1310

with 3 Detectors

TCD-1

Water, formaldehyde

TCD-2 and PDD

permanent gases incl. H2

C2- components

• Two stage reactor

• Solid, liquid or gas samples

• Isothermal, linear and stepwise

temperature profiles

• Large T-range: 40 - 900 0C

• Multi-shot sample introduction

• Cryo-trap for fast injection

Purpose:

• comprehensive analysis of fast pyrolysis product distribution of polymers incl. biomass

o close mass and elementary balances

• determination of intrinsic rate coefficients for solid to gas transition

o avoid transport limitations

o isothermal conditions

• investigation of gas-phase reactions of expensive solid model substances

o small sample sizes

Pyrolysis

Cryo-trap

Refocusing of

components

GC×GC –

FID/TOF-MSCustomized

Trace GC 1310

Comprehensive 2D

Gas Chromatography

Pyrolysis

1st Reactor 2nd Reactor

This research has been supported by the Belgian Development Cooperation through

VLIR-UOS. VLIR-UOS supports partnerships between universities and university colleges

in Flanders (Belgium) and the South looking for innovative responses to global and local

challenges. Visit www.vliruos.be for more information. The research leading to these

results has received funding from the European Research Council under the European

Union’s Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n°

290793. The SBO proposal “Bioleum” supported by the Institute for promotion of

Innovation through Science and Technology in Flanders (IWT) is acknowledged.

Solid to gas chemistry

- 1st reactor:

800°C, 500°C, 350°C

- No 2nd reactor

- Carrier flow rate

50 mL/min

- Cryo-trap: 1 min @ -1960C

Gas phase pyrolysis

- 1st reactor

100 → 140 → 230°C

steady release of

resorcinol

- 2nd reactor

820°C - 830°C - 850°C

- Carrier flow rate:

50 mL/min

- Cryo-trap: 7 min @ -

1960C

Plug flow regime

Repeat resorcinol experiments to obtain

comprehensive quantitative data

Develop elementary step kinetic models able

to quantitatively describe the gas phase data

Extend study to phenol, catechol,

hydroquinone, syringol, guaiacol, other lignin

model compounds.

Experimental detailsVaporization profiless

Optimized step-wise heating of the

sample in the first reactor provides

almost constant fuel inlet

concentrations for the second

reactor for several minutes

=> semi-batch / plug flow

Temperature profiles in the

reactors

- Temperature profiles obtained for both

reactors at experimental conditions.

- Highest temperature in the first reactor

coincides with location of dropped cup

- Second reactor: isothermal region with

step gradients at the ends clearly

defines the reaction zone.

Solid resorcinol decomposition•

Tandem Micro-pyrolyzer setup

Introduction

Conclusions Future work Acknowledgements

- Product distribution of resorcinol solid chemistry include small hydrocarbons ranging from CH4 to

large polyaromatic hydrocarbons.

- Char formation during pyrolysis indicates that

reactions take place in the condensed phase

TOF- Chromatogram for the thermal decomposition of

resorcinol using the 1st reactor at 800°C

New micro-pyrolyzer successfully used to study solid

and gas phase chemistry of a lignin model compound

Fast heating of solid resorcinol to high temperatures

initiates chemical transformations in the condensed

phase

Substantial amounts of char formed

Gas phase pyrolysis of resorcinol yields cyclopentadiene

Confirmation of the results by Scheer et al.

Decomposition pathways

Resorcinol

Gas phase resorcinol decomposition

- Major resorcinol pyrolysis products are cyclopentadiene and its subsequent reaction products (e.g.

naphthalene, indene).

- CO2 detected but also as background molecule

- No evidence for cyclopentadienone formation

- Concentration profiles are consistent with reported special chemistry

Experiments require very small amounts of substance

50 g/cup

resorcinol

200 g/cup

glass wool

Temperature [ᴼC] Char [%]

800 14.2

500 23.3

350 -2.6

Non-condensable gases

Bio char

Bio oil

Bio oil – highest potential for commercialization

– yield and quality control requires understanding of the chemistry

Previous studies:

• TGA experiments

• Non-isothermal conditions

Lignocellulosic biomass - the most abundant type of renewable biomass

- not competing with the food chain

Tandem Micro-pyrolyzer setup

• Intrinsic kinetic studies

• Well-defined temperature

Motivation of the study

substituted phenols and phenyl ethers

OH

OH

Catechol and Hydroquinone decomposition (major

pathway); analogous to phenol

Resorcinol: Analogous to catechol and hydroquinone ???

O

+ 2H + CO

OH

OH

+ CO2

Expected Reported

OH

OH

OH

OH

OH

+ CO

OH

•+ H + CO•

O

+ 2H + CO