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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