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Comprehensive Qualifying

Examination
Presented
by

Subhabrata Das
(A0109984N)
Supervisor: A/Prof. Ting Yen Peng
Department of Chemical & Biomolecular
Engineering,
National University of Singapore.

Basic Information
Title:
Demonstration of a Process for the Conversion of Kraft

Lignin into Vanillin and Methyl Vanillate by Acidic Oxidation


in Aqueous Methanol
Authors:
Tobias Voitl and Philipp Rudolf von Rohr
Source:
Industrial & Engineering Chemistry Research, 2010, 49,

520-525
Impact Factor: 2.206 (2012)
Citations: 26
2

Outline
Introduction
Methodology
Results
Critique
Suggestions for Future work
Conclusion

Introduction
Woody biomass, a renewable feedstock
for value added chemicals and biofuels
Lignin, one of the major component of
woody biomass
Kraft process generates huge amount of
lignin (72 million tons/yr) as low cost by
product (150$/ton)1
Lignin to vanillin (15000$/ton) an
attractive process2

1. Olsson, M. R.; Axelsson, E.; Berntsson, T. Nord. Pulp Pap. Res. J. 2006, 21 (4), 476484.
2. Hermans, I.; Spier, E. S.; Neuenschwander, U.; Turra, N.; Baiker. Top. Catal. 2009, 52 (9), 11621174.

Methodology

Schematic representation of the investigated process


Kraft Lignin Loading
Methanol/water
H3PMo12O40
pH
Temperature
Treatment Time

: 1g/run
: 80 vol. %
: 0.025 mol/L
: 1.13
: 170 oC
: 20 minutes

Results
A stable yield of 7 wt. % achieved after run 5
Decrease in the yield of methyl vanillate from
3.62 wt. % (run 6) to 3.27 wt. % (run 10)

Fig. Yield of monomeric


products

Fig. Course of pH values


6

Results

Fig. Amount of products


recovered from the
process

Fig. Oxygen consumption


and Carbon dioxide
production

65 wt. % of
extracted products
retrieved after the
process reached
stability (run 6)

After five runs solid


fraction yield ~30
wt. %

Fig. Mass balance in runs


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Critique
Key contributions:
Acid oxidation of industrial kraft lignin using H 3PMo12 O40
- To cleave alkali stable bonds
- Promising yield of 7 wt. % w as achieved higher than alkali

oxidation 1 (<4 wt. %)

Use of co-solvent as a radical scavenger to prevent condensation reaction


Extracted product w as free from catalyst and the reaction medium could be recycled
Mass balance illustrated that system attained stability from run 6

1. Villar, J. C.; Caperos, A.; Garcia-Ochoa, F. Wood Sci. Technol. 2001, 35 (3), 245255.

Critique
Choice of extracting solvent

40-50 % of the monomeric product remains in


reaction mixture even after extraction with
chloroform
Chloroform is carcinogenic
Stability of monomeric products

Recommendation:
Ethyl acetate can be considered as an alternative
1
extracting
solvent
1. A. Vigneault, D. K. Johnson, and E. Chornet. The Canadian Journal of Chemical Engineering, 85(6):906916, 2007.

Critique
40 % of the catalyst left the system in the solid
fraction

High Cost of H3PMo12O40 (3000$/kg)1

Difficult to retrieve from solid fraction

Recommendation:
Cheap transition metal salt (CuSO4 and FeCl3) catalyst
can be considered as an alternative catalyst2

1. http://www.sigmaaldrich.com/catalog/product/sial/p7390?lang=en&region=SG
2. Villar, J. C.; Caperos, A.; Garcia-Ochoa, F. Wood Sci. Technol. 2001, 35 (3), 245255.

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Critique
Negative values in the mass balance

Fig. Amount of products


recovered from the process

Fig. Mass balance in runs


1-11

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Critique
Effect of pH and catalyst activity

Increase of pH in the system is not explained


Explanation of high product yield (7 wt. %)
even with the loss of catalyst

Recommendation:
Change in catalyst concentration to study the effect on
yield can give a better insight on catalyst activity

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Critique
Batch oxidation reaction

Takes long time to reach the reaction


temperature and cool down
Risk of operating at high pressure
Waste generation is high

Recommendation:
Use of high pressure continuous mode micro-reactor

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Suggestions for Future


work
Study the effect of different operating condition on
vanillin yield

Treatment time
Operating temperature
pH
Catalyst loading
Lignin loading

Studies on complete utilization of extracted products


Effect of cheap transition metal salt catalyst on the
process
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Conclusion
Acid oxidation in aqueous-methanol using H3PMo12O40
resulted in promising yield of 7 wt. % of vanillin and
methyl vanillate

The reaction mixture could be recycled

Stable working condition was achieved from run 6

Incorporation of the detailed parametric study and the


proper explanations of the results can provide a better
insight

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Thank You

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Backup Slide
Redox reaction

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Backup Slide
FT IR analysis

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Backup Slide
Lignin production and potential lignin derived
products

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Backup Slide
Occurrence of natural lignin

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Backup Slide
Monolignol units

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Backup Slide
Structure of softwood lignin molecule

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Backup Slide
Most frequent linkages in lignin molecule

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Backup Slide
Biosynthesis of lignin

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Backup Slide
Kraft process

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Backup Slide
Structure of kraft lignin

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Backup Slide
Cleavage and condensation of lignin monomers during kraft
pulping

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Backup Slide
Potential routes of lignin utilization

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Backup Slide
Reaction network for the products during acid oxidation of
kraft lignin

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Backup Slide
Extracted mass of lignin oxidation product from different
solvent

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Backup Slide
Vanillin and its properties

Hocking, M. B. Vanillin: Synthetic flavoring from spent sulfite liquor. J. Chem. Educ. 1997, 74 (9), 10551059.

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Backup Slide
Aromatic structure formed during lignin oxidation

Hocking, M. B. Vanillin: Synthetic flavoring from spent sulfite liquor. J. Chem. Educ. 1997, 74 (9), 10551059.

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Backup Slide
Vanillin from ligno-sulphonates

Hocking, M. B. Vanillin: Synthetic flavoring from spent sulfite liquor. J. Chem. Educ. 1997, 74 (9), 10551059.

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Backup Slide
Biomass to vanillin general pathway

Hocking, M. B. Vanillin: Synthetic flavoring from spent sulfite liquor. J. Chem. Educ. 1997, 74 (9), 10551059.

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Backup Slide
Petrochemical method for vanillin production

Hocking, M. B. Vanillin: Synthetic flavoring from spent sulfite liquor. J. Chem. Educ. 1997, 74 (9), 10551059.

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Backup Slide
Amount of products obtained from the oxidation of lignin in
aqueous

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 136
(8-9),
763769..

Backup Slide
GC-MS analysis varying catalyst concentration and solvent
concentration

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 137
(8-9),
763769..

Backup Slide
Effect of POM catalyst

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 138
(8-9),
763769..

Backup Slide
Formation of methyl vanillate from vanillin

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 139
(8-9),
763769..

Backup Slide
Radical coupling during lignin degradation

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 140
(8-9),
763769..

Backup Slide
Degradation and re-polymerization in acid condition

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 141
(8-9),
763769..

Backup Slide
Degradation and re-polymerization in acid condition

Voitl, T.; Rudolf von Rohr, P. Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. ChemSusChem 2008, 142
(8-9),
763769..

Backup Slide
Polyoxometalate

Keggin structure, XM12O40nX = P+5 or Si+4


M= Molybdenum or tungsten
O= Oxygen

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Backup Slide
Effect of transition metal salts

http://e-collection.library.ethz.ch/eserv/eth:7017/eth-7017-02.pdf

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