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Daniel J. Nowakowski Daniel J. Nowakowski BERG lignin seminar BERG lignin seminar Analytical (PY-GC-MS) pyrolysis of lignin Analytical (PY-GC-MS) pyrolysis of lignin
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Daniel J. NowakowskiDaniel J. Nowakowski
BERG lignin seminarBERG lignin seminar
Analytical (PY-GC-MS) pyrolysis of ligninAnalytical (PY-GC-MS) pyrolysis of lignin
Pectin
Cross- linkinghem icellulo seCellu lose
m icrofibrils
M idd leLam ella
P rim aryCell W all
P lasm am em brane
BioEnergy Research Group seminar 17th September 2007 2/9
Lignin is usually considered as a polyphenolic material having an amorphous structure, which arises from an enzyme-initiated dehydrogenative polymerisation of coniferyl (a), sinapyl (b) and trans-p-coumaryl (c) alcohols.
OH
OH
OMe
a
OH
OH
MeO OMe
b
OH
OH
c
Lignin chemistry
Structure of plant cell wall
O
O
OR
RO
HO
O
OR
-O-4
O
O
OH
OR
HO
HO
O
OR
OH
1
3
4
13
4
Arylether(50-60% of total structure)
OO
OO
RR
Tetrahydrofuran
(THF type)
OH
O
OR
H
O
OR
O
Alcohol Aldehyde
(End-groups)
R
O
O OH
Side chain
O
OHO
O
OR
O
R
R
O
Dibenzodioxocin(Ocyagonal structure)
O
OH
O
O
R
O
R
-5 (Benzofuran)(Phenylcoumaran)
(Resinol type)
O
O
O
O
R
O
O
R
HO
O
OR
HO
O
OR
-1-bond(Stabile form)
Lignin chemistry
Dimmers and trimeres structures of lignin with the main types of linkages connecting phenylpropane units
BioEnergy Research Group seminar 17th September 2007 3/9
BioEnergy Research Group 17th September 2007 4/9
Main degradation productsof Organosolv lignin:- 1,2,3-trimethoxybenzene- 2,6-dimethoxy phenol- 2-methoxy-4-methyl phenol- 2-methoxy phenol
- furanaldehyde and carboxfuranaldehyse
- 1,2,3-trimethoxy-5-methylbenzene
- 2,6-dimethoxy-4-(2-propenyl)-phenol
C14-C22 acids, its
methyl or ethyl esters
O
O
O
OH
O O
OH
O
HO
O
OO
O
O
O
O
O
OH
O O
OH
O
O
PY-GC-MS analysis of Organosolv lignin
[commercially available lignin]
Py-GC-MS chromatogram, pyrolysis at 600oC, pyrolysis time 15 sec.
Main degradation productsof Etek lignin:- 2-methoxy-4-methyl phenol- 2-methoxy phenol
- 2-methoxy-4-vinylphenol
- 4-hydroxy-2-methoxy-benzaldehyde
- furfural, cyclopentane/hexane derivatives
- levoglucosan
- anhydrosugars (traces)
OO
HO
HO
OH
O
O
O
OH
OO
O
OH
O
O
O
HO
OH
O
HO
O
OO
OH
O
O
O
OH
O
O
HO
HO
OO
[commercially available lignin,
by-product from EtOH production]
PY-GC-MS analysis of Etek lignin
BioEnergy Research Group seminar 17th September 2007 5/9
BioEnergy Research Group 17th September 2007 6/9
[by-product from paper industry]
PY-GC-MS analysis of Asian lignin
Main pyrolysis productsof Asian lignin:- 2-methoxy-4-vinyl phenol- 2-methoxy-4-methyl phenol- 2-methoxy phenol- 2,6-dimethoxy phenol- 1,2,3-trmethoxybenzene- 1,2,3-trimethoxy-5-methylbenzene- 2,6-dimethoxy-4-(2-propenyl)-phenol- 2,5-dimethyl furan
OH
O
OH
O
HO
O
O
OH
O O
O
O
O
O
O
O
OH
O O
SiOSi
O
Si
O
SiO
Si O Si OSi
O
Si
O
SiO
SiO
tetracosamethyl-cyclodeca siloxane
SiOSi
O
Si
OSi O Si
O
Si
O
SiO
tetracosamethyl-cyclohepta siloxane
PY-GC-MS analysis of bio-oil from fast pyrolysis of:
Etek lignin
Asian lignin
Main compounds identified inliquids:- acetic acid- 2-cyclopentane-1,4-dione- 2-hydroxy-2-cyclopenten-1-one- phenol- 2-methoxy phenol- levoglucosan + traces of anhydro- and dianhydro- sugars
- phenol- 2-methoxy phenol- 4-ethyl phenol- 4-ethyl-2-methoxy phenol
BioEnergy Research Group seminar 17th September 2007 7/9
BioEnergy Research Group 17th September 2007 8/9
> Characterisation of lignin samples using pyrolysis-gas chromatography-mas spectrometry (PY-GC-MS) at different temperatures (400oC & 500oC; Lignovalue project)
> Pyrolysis studies of lignin samples using thermogravimetric analysis (TGA) up to 900oC, heating rates: 5 and 25oC/min.
-11
-9
-7
-5
-3
-1
1
0 100 200 300 400 500 600 700 800
temp., oC
dm
/dt;
%/m
in.
Future work
DTG profile for lignin (Organosolv) pyrolysis;TGA pyrolysis, 25oC/min. in nitrogen
> Problems:
Bio-oil (liquid products) analysis:RTX 1701 column(14% cyanopropylphenyl, 86%
dimethylpolysiloxane; 60 m, 0.25 mm id.)
TGA is not working(will be repaired within two weeks)
CH•
N
cyanopropylphenyl
dimethylpolysiloxane
SiH
O
H3Si
*n
> In situ studies of monomeric phenols production
(HCl pre-treatment, (CH3COO)2Ca, ZnCl2)
Thank you for your attention
