DESIGN AND CONSTRUCTION OF AN EXPERIMENTAL … · KINETICS OF BIOMASS FAST PYROLYSIS Diana C....
Transcript of DESIGN AND CONSTRUCTION OF AN EXPERIMENTAL … · KINETICS OF BIOMASS FAST PYROLYSIS Diana C....
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: [email protected]
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