CENTRE FOR RESEARCH AND ΤECHNOLOGY-HELLAS
CHEMICAL PROCESS ENGINEERING RESEARCH INSTITUTE
Characterization studies of Waste- bio-derived feedstocks
C. Michailof, E.F. Iliopoulou,K. Kalogiannis, M. Pachnos, M. Emmanouilidou and A.A. Lappas
Exploring established and new emerging heterogeneous catalytic technologiesfor the production of aviation and road transportation fuels (i.e., gasoline,kerosene, diesel) via hydroprocessing (hydro-isomerization, hydrocracking orhydrodeoxygenation) of renewable feeds.
Development of new and selective catalytic systems for diesel or aviation fuelproduction via hydroconversion of waste bio-feedstocks:
Bio-oil Algea oil Vegetable oils F-T waxes
PROJECT : WAVES - WAste bio-feedstocks hydro-Valorisation processES
CPERI’s Contribution
Fundamental Prerequisite
PROJECT SCOPE
Detailed analysis of the feedstock
Bio-Oil (Pyrolysis oil)
carboxylic acids
aldehydes & ketones
sugars
phenols, guaiacols, syringols
Bio-oil
Biomass Pyrolysis Thermal decomposition of biomass T>500oC
Complex mixture, different classes of compounds
Requires analytical techniques with increased separation and resolution
Gases Bio-oil
(liquid product) Char
(solid product)
aromatic hydrocarbons
Bio-Oils studied
PineCardoon Olive Kernel Jatropha Miscanthus
Selected biomasses for Thermal (non-catalytic) pyrolysis
Elemental analysis (%) Ash(%)
Extractives (%)
Lignin(%)
Cellulose(%)
Hemicellulose(%)C H O
Pine 45,54 6,37 47,79 0,30 1,33 29,40 40,46 23,72Cardoon 38,11 5,27 41,20 15,42 3,22 34,94 34,01 28,02
Olive kernel 51,97 7,80 37,83 2,40 3,07 25,10 38,75 29,05Jatropha 46,39 6,04 42,48 5,09 9,74 43,98 22,63 28,30
Miscanthus 45,55 6,00 45,88 2,57 2,25 28,21 39,68 27,29
Two dimensional Gas Chromatography coupled with Time-of-Flight Mass Spectrometry
GC x GC = ?
The separation (boiling point) achieved in the first column is preserved&additional separation (polarity) in the second column is accomplished
Advantages of GC x GC -ToFMS
• Improved Chromatographic Resolution
• Increased Peak Capacity
• Enhanced Signal to Noise
• More Effective Automated Qualitative and Quantitative Data Processing
• More Information per Analyzed Sample
• ‘Mapping’ of the samples for an initial estimation of its composition
Two dimensional Gas Chromatography coupled with Time-of-Flight Mass Spectrometry
Separation and identification of more
than 500 peaks per sample
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Qualitative analysis - Identification of compounds based on NIST05 library
Quantitative analysis employing Internal Standard methodology using a standardsolution of 53 compounds
Internal standard: phenol-d6
Standard solutions at 5 concentration levels, each solution analysed at least 5 times
Determination of the RRF (Relative Response Factor) for each compound
ANOVA and WLSLR (Weighted Least Square Linear Regression) for statistical analysisand validation of the calibration
Regular verification of the calibration curves
iis
iis
CA
ACRRF
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Pine bio-oil
Compound % w/w GroupTotal
%w/w
Acetic acid 3,552(5H)-Furanone 1,98 AR 0,04
Phenol, 2-methoxy- 1,45 ALI 0,101,2-Benzenediol 1,39 PH 8,633-Furaldehyde 0,97 FUR 0,85
2-Cyclopenten-1-one, 2-hydroxy- 0,60 AC 3,552-Cyclopenten-1-one 0,55 EST
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Olive kernel bio-oil
Compound % w/w GroupTotal
%w/wAcetic acid 4,72
1,2-Benzenediol 0,83 AR 0,32Phenol, 2-methoxy- 0,35 ALI 0,73
1,2-Benzenediol, 3-methoxy- 0,30 PH 5,04Phenol, 2,6-dimethoxy- 0,28 FUR 0,29
Phenol 0,27 AC 4,72Phenol, 3-methyl- 0,22 EST 0,12
Hydroquinone 0,19 AL
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Cardoon bio-oil
Compound % w/w GroupTotal
%w/wAcetic acid 6,42
Hydroquinone 0,87 AR 0,281,2-Benzenediol 0,76 ALI 0,04
Phenol 0,45 PH 4,502(5H)-Furanone 0,41 FUR 0,11
2-Cyclopenten-1-one, 2-methyl- 0,31 AC 6,42Phenol, 4-ethenyl-, acetate 0,26 EST 0,26
Phenol, 3-methyl- 0,17 AL
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Jatropha bio-oil
Compound % w/w GroupTotal
%w/wAcetic acid 3,88
1,2-Benzenediol 0,81 AR 0,30Phenol 0,43 ALI 0,15
Phenol, 2-methoxy- 0,41 PH 4,39Phenol, 3-methyl- 0,33 FUR 0,39
Hydroquinone 0,21 AC 3,88Phenol, 2,6-dimethoxy- 0,21 EST
Chromatographic analysis of bio-oils by GCxGC - ToFMS
Miscanthus bio-oil
Compound % w/w GroupTotal
%w/wAcetic acid 8,65
1,2-Benzenediol 1,19 AR 0,06Phenol, 4-ethenyl-, acetate 0,99 ALI 0,08
Phenol, 3-ethyl- 0,57 PH 6,89Phenol 0,53 FUR 0,47
3-Furaldehyde 0,51 AC 8,652(5H)-Furanone 0,46 EST 1,00
Phenol, 2-methoxy- 0,46 AL 0,04Phenol, 2,6-dimethoxy- 0,34 ETH 0,09
Hydroquinone 0,32 ALD 1,041,2-Benzenediol, 3-methoxy- 0,32 KET 2,41
2-Cyclopenten-1-one 0,30 PAH >0,01
Phenol, 3-methyl- 0,25
2-Methoxy-4-vinylphenol 0,19
2-Cyclopenten-1-one, 2-hydroxy- 0,16
2-Furanmethanol 0,14
Benzaldehyde, 4-hydroxy- 0,13
1,2-Benzenediol, 3-methyl- 0,12
Phenol, 2-methyl- 0,12
2-Cyclopenten-1-one, 2-methyl- 0,12
Vanillin 0,11
Total Top 20 compounds (wt.%) 15,97
Determined wt.% of total bio-oil 20,65
Determined wt.% of organic phase 38,09
Including the H2O content, 66.4% of the bio-oil is characterizedHigh acetic acid concentrationIncreased phenolic contentMany esters detected
Conclusions
Pine Olive kernel Cardoon Jatropha Miscanthus
Group Total %w/w Total %w/wTotal
%w/wTotal
%w/wTotal %w/w
AR 0,04 0,32 0,28 0,30 0,06ALI 0,10 0,73 0,04 0,15 0,08PH 8,63 5,04 4,50 4,39 6,89
FUR 0,85 0,29 0,11 0,39 0,47AC 3,55 4,72 6,42 3,88 8,65EST
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CHEMICAL PROCESS ENGINEERING RESEARCH INSTITUTE
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