Characterization of LignoBoost lignin to predict possible

utilizationMatyas Kosa07-17-2009

Georgia Institute of TechnologySchool of Chemistry and Biochemistry

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OUTLINE

• The need for biofuels• Lignin as a potential source,

biosynthesis• Kraft-cycle, LignoBoost, 2nd gen.

bioethanol pretreatm.• Results (so far): Purification, GPC,

NMR

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WHY BIOFUELS?• Unpredictable nature of fossil fuel prices?

• Global warming, CO2 emissions…

M. Meinshausen et al, Nature, 2009, 458: 1158-1163

• Energy Independence!

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PHENYLPROPANOID PATHWAY

Wout Boerjan et al, Annu. Rev. Plant Biol., 2003, 54: 519-46Laurence B. Davin et al, Natural Product Reports, 2008, 25: 1015-1090

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LIGNIN POLYMERIZATION

Wout Boerjan et al, Annu. Rev. Plant Biol., 2003, 54: 519-46Laurence B. Davin et al, Natural Product Reports, 2008, 25: 1015-1090

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KRAFT CYCLE-LIGNOBOOST

Johan Gullichsen and Carl-Johan Fogelholm: CHEMICAL PULPING,Papermaking Science and Technology series, Book 6A, 1999, TAPPI

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PULPING CHEMISTRY

Johan Gullichsen and Carl-Johan Fogelholm: CHEMICAL PULPING,Papermaking Science and Technology series, Book 6A, 1999, TAPPI

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ORGANOSOLV PROCESST. J. McDonoughTAPPISolvent Pulping Seminar1992

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SAMPLE PURIFICATION PreliminaryResearchResults

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GPC

Henrik Wallmo, PhD Thesis, Chalmers Univesity of Technology, 1999Ali Moosavifar et al, Nordic Pulp Paper Res. J, 2006, 21: 180-87

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13C-NMR

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1H-NMR

F samples contain significantly higher amounts of –OH groups of all examined types causing possibly their better solubility.

17.441.27.919.86.21.61.7F 9.5

16.752.45.918.74.20.91.1P 9.5

16.944.66.819.65.71.71.2F 10.5

16.049.28.219.73.71.00.8P 10.5

14.445.88.420.26.71.51.3BL

C-CH3C-CH2-OCH2=CH

C-CH2-C

-OCH3

CH-OCH=CHHC-OH-C(O)H-C(O)OH

2.25-0.00 ppm4.05-3.45 ppm6.00-4.05 ppm8.00-6.00 ppm9.35-8.00 ppm10.10-9.35 ppm

13.50-10.50 ppm

AliphaticMethoxylAliphaticAromatic, VinylPhenolicFormylCarboxylic acid

Hydrogen content of selected groups (in mol/mol% relative to all H contraining funct groups)

Sample name

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31P-NMR

Derivatization of phenolic structures with 2–chloro–4,4,5,5–tetramethyl–1,3,2–dioxaphospholane (TMDP).

1.112.551.81.276.74F 9.5

0.591.471.141.114.3P 9.5

0.782.21.571.225.76F 10.5

0.391.030.850.913.18P 10.5

0.692.461.731.496.37BL

136.0-133.8 ppm

140.4-137.6 ppm

144.4-140.4 ppm

149.0-145.6 ppm

149.0-133.8ppm

Carboxylic hydroxylPhenolic @ G position

Phenolic in GAliphatic hydroxyl(mmol g-1)

Hydroxyl content of selected groups (mmol g-1)Total –OH content

Samplename

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PYROLYSIS

14.7842.2542.98P 9.5 purified

0.9267.5531.53P 9.5 crude

1.34 1.121-2H/C molar ratio2.7164.1433.16BL crude

0.260.340O/C molar ratiogascharoilsample

P 9.5 (pur) pyrolysis oil

P 9.5 (pur) ligninGasolinePyrolysis [wt%]

• O/C and H/C molar ratios of purified LignoBoost precipitate lignin and of its pyrolysis oil show promising results

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FURTHER ANALYSIS

• Repeating GPC measurements with smaller Mw standards

EXPERIMENTAL

• Analysis of sugars and possibly short chain fatty acids still present

• Analysis of LignoBoost final products when the process is in equilibrium with Kraft cycle

EDTA

ethers,alcohols

conjugated and non conjugated acids and esters

alkane

Raimo Alen et al, Cellulose Chemistry and Technology, 1985, 19: 537-541Fredrik Ohman et al, Nordic Pulp Paper Res J, 2007, 22:188-193

Silverstein et al, Spectr. Ident. Org. Comp.,7th ed.,Wiley & Sons

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POSSIBLE UTILIZATION

• Pyrolysis showed promising results meaning that further analysis can be fruitful

• Complete analysis and comparison of the outcome of different lignin degrading enzymes and converting microorganisms are ongoing

Thanks for listening!

Questions?