Aromatic compounds by hydrothermal degradation
of lignins from biorefineries
Gerd Unkelbach1, Daniela Pufky-Heinrich1, Detlef Schmiedl2, Thomas Hirth3
1 Fraunhofer
Center for Chemical - Biotechnological processes
Institute for Chemical Technology
3 Fraunhofer Institute of Interfacial Engineering and Biotechnology & University Stuttgart
2 Fraunhofer
R
O
CH3
CH3
O
H2C OH
CH2
CH
H2C OH
CH
HC
OMe
OH
H2C OH
CH
O
CH H2C
OH
HC
H2C OH
OH
HC
HC OH
OMe
HC
OMe
HC O (C5H10O5)nH
H2C
CH
HC
CH
HC
O
CH
HC
CH
O
CO
CH2
HC
CH
OH
R
HC OH
MeO
R
O
OMe
OMe
OH
H2C OH
HC OH
OMe
O
CH
O
O
OMe
HC
H2C OH
O
O
OH
OH
MeO
H2C OH
O
CO
HC
(OCH3)0,5
O
CH
CH
CH
O
HC
O
O
HO
OMe
HC
OMe H2C OH
MeO
CH
HC
CH3
OH
H2C OH
CH2
H2C OH
HC
MeO
HC OH
CO
H2C OH
O
CO
H2C OH
H3C
O
OH
O
MeO
H2C OH
MeO
OMe
OH
© Fraunhofer CBP
CH3 H3C
OH
OH
HO
HC
O
OMe
O
HC
HO
OH
OH
H3C
O
OH
CH3
Biomass - A new feedstock for the 21. century ?
coal
crude oil / natural gas (> 1950)
From coal to crude oil new efficient
techniques have been developed for an
economic production of chemicals
© Fraunhofer CBP
biomass ?
For the shift from oil / gas to
biomass it has to be the same
Biomass - A new feedstock for the 21. century ?
coal
crude oil / natural gas (> 1950)
From coal to crude oil new efficient
techniques have been developed for an
economic production of chemicals
© Fraunhofer CBP
biomass ?
For the shift from oil / gas to
biomass it has to be the same
Biomass - A new feedstock for the 21. century ?
coal
crude oil / natural gas (> 1950)
From coal to crude oil new efficient
techniques have been developed for an
economic production of chemicals
© Fraunhofer CBP
biomass ?
For the shift from oil / gas to
biomass it has to be the same
ethylene
110 Mio. t/a
890 €/t
1035 €/t C
propylene
75 Mio. t/a
850 €/t
988 €/t C
benzene
45 Mio. t/a
830 €/t
902 €/t C
cellulose
320 Mio. t/a
500 €/t
1250 €/t C
starch
55 Mio. t/a
250 €/t
625 €/t C
sugar
143 Mio. t/a
300 €/t
750 €/t C
ethanol
36 Mio. t/a
365 €/t
700 €/t C
lignin
??????????????????????????
Products out of Benzene
Ref.: H.-J. Arpe, Industrielle Organische Chemie, Wiley-VCH
© Fraunhofer CBP
Products out of Xylene
Ref.: H.-J. Arpe, Industrielle Organische Chemie, Wiley-VCH
© Fraunhofer CBP
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Ref.: Edward M. Rubin, Nature 454, 841-845
© Fraunhofer CBP
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Ref.: Edward M. Rubin, Nature 454, 841-845
© Fraunhofer CBP
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
ethanol/water
ethanol/
water
Digester
400 L
200°C
mother
liquor
wood chips
xylose fraction
tank farm
pulping
lignin
fiber
fraction
lignin precipitation/
solvent recovery
organosolv lignin
lignin washing
dewatering
hydrolysis lignin
lignin
drying
hydrolysis
residue
glucose
solution
dewatering
fiber washing
© Fraunhofer CBP
enzymatic
hydrolysis
conc. glucose solution
concentration
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
ethanol/water
Digester
hydrothermal
400 L
mother
200°C
ethanol/
reactive liquor
water
extraction of
wood chips
C5/C6tank farm
components
and
Lignin
pulping
xylose fraction
lignin
fiber
fraction
lignin precipitation/
solvent recovery
organosolv lignin
lignin washing
dewatering
hydrolysis lignin
lignin
drying
hydrolysis
residue
glucose
solution
dewatering
fiber washing
© Fraunhofer CBP
enzymatic
hydrolysis
conc. glucose solution
concentration
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Cellulose
Hemicellulose
Lignin
40-55%
15-35%
28-41% (sw);
18-25% (hw)
© Fraunhofer CBP
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Cellulose
Hemicellulose
Lignin
40-55%
15-35%
28-41% (sw);
18-25% (hw)
hydrolysis results in C6- and C5-sugars as
feedstock for fermentation or chemical
reactions
© Fraunhofer CBP
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Cellulose
Hemicellulose
Lignin
40-55%
15-35%
28-41% (sw);
18-25% (hw)
hydrolysis results in C6- and C5-sugars as
feedstock for fermentation or chemical
reactions
© Fraunhofer CBP
structure strongly addicted to
the method of preparation and
the raw material
 wide range of molecular
characteristics and functionality
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Cellulose
Hemicellulose
40-55%
15-35%
Lignin
28-41%
Estimated Response
Surface(sw);
w EtOH=65,0
18-25% (hw)
Mw Lignin
(X 1000,0)
3,4
3
2,6
2,2
1,8
1,4
1
160 170
hydrolysis results in C6- and C5-sugars as
feedstock for fermentation or chemical
reactions
© Fraunhofer CBP
180 190
Temperatur
200 210
220 2
2,5
3
3,5
4
Verweilzeit
Mw Lignin
800,0
1040,0
1280,0
1520,0
1760,0
2000,0
2240,0
2480,0
2720,0
2960,0
3200,0
3440,0
structure strongly addicted to
the method of preparation and
the raw material
 wide range of molecular
characteristics and functionality
Utilizing lignocellulosic biomass
by pulp mills (Kraft, Sulfide, Soda, … -pulping)
or in “Biorefineries” by fractionation of hardwood by
e.g. a modified Organosolv-process
Cellulose
Hemicellulose
Lignin
40-55%
15-35%
28-41% (sw);
18-25% (hw)
hydrolysis results in C6- and C5-sugars as
feedstock for fermentation or chemical
reactions
no “easy” degradation of the
macromolecule possible!
only material applications
(e.g. phenolic resins)
© Fraunhofer CBP
Structural properties of lignin
bond type
dimer structure
softwood (spruce)
C9 units of 100
hardwood (beech)
C9 units of 100
β-O-4
arylglyceryl-β-arylether
48
65
α-O-4
benzyl-arylether
6–8
β-5
phenylcoumaran
9 – 12
6
5-5
biphenyl
10 – 11
2
diarylether
4
2
β-1
1,2-diarylpropane
7
15
β-β
THF or resinol type
2
2+5
4-O-5
Ref.: ERICKSON, M.; LARSSON, S.; MISCHKE, G.E. (1973)
NIMZ, H.; LÜDEMANN, H.D. (1974)
© Fraunhofer CBP
Structural properties of lignin
bond type
dimer structure
OH
softwood (spruce)
C9 units of 100
hardwood (beech)
C9 units of 100
48
65
β-O-4
arylglyceryl-β-arylether
α-O-4
benzyl-arylether
6–8
β-5
phenylcoumaran
9 – 12
6
5-5
biphenyl
10 – 11
2
diarylether
4
2
β-1
1,2-diarylpropane
7
15
β-β
THF or resinol type
2
2+5
4-O-5
H3C
O
O
O
H3C
CH3
OH
O
H3C
OH
H3C
O
O
OH
O
CH3
Ref.: ERICKSON, M.; LARSSON, S.; MISCHKE, G.E. (1973)
NIMZ, H.; LÜDEMANN, H.D. (1974)
HO
© Fraunhofer CBP
CH3
O
Structural properties of lignin
bond type
dimer structure
OH
softwood (spruce)
C9 units of 100
hardwood (beech)
C9 units of 100
48
65
β-O-4
arylglyceryl-β-arylether
α-O-4
benzyl-arylether
6–8
β-5
phenylcoumaran
9 – 12
6
5-5
biphenyl
10 – 11
2
diarylether
4
2
β-1
1,2-diarylpropane
7
15
β-β
THF or resinol type
2
2+5
4-O-5
H3C
O
O
O
H3C
OH
H3C
OH
H3C
O
O
OH
O
CH3
HO
© Fraunhofer CBP
CH3
O
Ref.: ERICKSON, M.; LARSSON, S.; MISCHKE, G.E. (1973)
NIMZ, H.; LÜDEMANN, H.D. (1974)
reduction: max phenolics: about 20%
oxidation (vanilla type aldehydes): 20+%
pyrolysis: 10+% phenolics
CH3
O
Every attack leads to a
structural change
Structural properties of lignin
bond type
dimer structure
OH
softwood (spruce)
C9 units of 100
hardwood (beech)
C9 units of 100
48
65
β-O-4
arylglyceryl-β-arylether
α-O-4
benzyl-arylether
6–8
β-5
phenylcoumaran
9 – 12
6
5-5
biphenyl
10 – 11
2
diarylether
4
2
β-1
1,2-diarylpropane
7
15
β-β
THF or resinol type
2
2+5
4-O-5
H3C
O
CH3
O
O
O
H3C
CH3
OH
O
H3C
OH
H3C
O
O
OH
O
CH3
Ref.: ERICKSON, M.; LARSSON, S.; MISCHKE, G.E. (1973)
NIMZ, H.; LÜDEMANN, H.D. (1974)
HO
reduction: max phenolics: about 20%
oxidation (vanilla type aldehydes): 20+%
pyrolysis: 10+% phenolics
Every attack leads to a
structural change
hardwood lignins (e.g. beech) are good raw materials for the production of
aromatic compounds by BCD (base catalyzed depolymerisation)
© Fraunhofer CBP
Principle of the BCD-process
BCD procedure
H2O + lignin + catalyst
pH ~ 13
flow diagram of the miniplant
TI
H2O
reactor
cooler
reactor
PI
TI
TIC
emergency valve
H2O + phenolics + tar
pH ~ 8-10
rupture disc
acidification
Pressure
regulator
preheater
TIC
waste
TI
H2O + phenolics + tar
pH ~3-4
product
PI
PI
filtration
H2O + phenolics
pH ~3-4
tar
H 2O
lignin
solution
extraktion
org. solvent +
phenolics
distillation
oligomer
phenolics
© Fraunhofer CBP
monomer & oligomer
phenolics
H2O + not extractable
pH ~ 3-4
NF / RO
not extractable
+
salts
temperature
250-350°C,
pressure max
250 bar,
residence time
<15 min,
10 % Lignin (Organosolv-Lignin),
NaOH / NaHCOO
Principle of the BCD-process
R
monomer
R
R
R
R
H3C
H2C OH
H2C OH
CH
CH
CH2
HC OH
HC
CH
HC
OMe
OH
H2C OH
CH
O
OH
H2C OH
OH
HC
HC OH
OMe
HC O
(C5H10O5)nH
H2C
CH
HC
CH
HC
CH
O
CH
HC
CH
HC OH
CO
CH2
HC
CH
HC
OMe
O
O
OH
O
5-5
HO
O
CH3
OH
ß- ß
O
HO
O
H3C
CH3
MeO
OH
OH
O
O
CH3
pH:12-14; c: OHLi, Na, K, Ca, Mg, Cs
p:200-250bars
T:200-350°C
O
CH3
O
H3C
OH
O
CH3
O
CH3
OH
OMe
O
oligomer
CH3
OH
O
© Fraunhofer CBP
O
H3C
O
OH
CH3
HO
O
HC
O
ß- ß
O
OH
HO
OMe
CH3
ß-1
H3C
H3C
MeO
H2C OH
ß-5
O
O
O
O
CH3
CH3
MeO
OH
OH
OH
O
O
CH3
HC OH
OMe
O
H2C OH
O
O
CH3
OH
O
O
HC
H2C OH
O
O
OMe
CH3
CH3
O
OMe
HC
OMe
OH
MeO
H2C OH
dimer
O
CO
HC
OH
HO
OH
CH3
O
HC
CH
CH
(OCH3)0,5
HC
CH H2C
OH
OH
OH
CH
O
O
O
CH3
O
OH
OMe
HC
OMe H2C OH
H3C
O
OH
OH
HC
MeO
O
R
H2C OH
CH2
H2C OH
O
CO
CO
H2C OH
MeO
H2C OH
CH3
O
O
O
OH
O
CH3
O
OH
O
CH3
OH
O
O
HO
O
OH
O
O
O
O
O
CH3
HO
CH3
O
O
HO
H3C
O
O
O
CH3
OH
O
CH3 H3C
O
CH3
OH
CH3
H3C
O
OH
HO
HO
CH3
H3C
O
CH3
O
OH
CH3
Principle of the BCD-process
R
R
R
R
R
H3C
H2C OH
H2C OH
CH
CH
CH2
HC OH
HC
CH
HC
OMe
OH
H2C OH
CH
O
OH
H2C OH
OH
HC
HC OH
HC O
(C5H10O5)nH
H2C
CH
HC
CH
HC
CH
O
CH
HC
O
CH
HC OH
CH3
CH3
CH
HC
CH3
O
H3C
O
OH
O
O
HC OH
OH
H3C
MeO
O
O
O
CH3
OH
HO
OH
OMe
CH3
HO
O
H3C
HO
OMe
O
O
HO
O
H3C
O
CH3
OH
O
CH3
HC
O
MeO
OH
OH
O
O
OMe
OH
© Fraunhofer CBP
CH3
pH:12-14; c: OHLi, Na, K, Ca, Mg, Cs
p:200-250bars
T:200-350°C
O
CH3
O
H3C
OH
O
CH3
O
CH3
OH
O
O
O
O
CH2
MeO
H2C OH
OH
O
CH3
OMe
O
H2C OH
OH
O
O
CO
HC
H2C OH
O
OMe
O
HC
OMe
O
CH3
CH3
O
OMe
HC
CH3
O
OMe
OH
MeO
H2C OH
OH
CH3
CO
HC
OH
HO
OH
O
HC
CH
CH
(OCH3)0,5
HC
CH H2C
OH
OH
OH
CH
O
O
O
CH3
O
OH
OMe
HC
OMe H2C OH
H3C
O
OH
OH
HC
MeO
O
R
H2C OH
CH2
H2C OH
O
CO
CO
H2C OH
MeO
H2C OH
CH3
O
O
O
OH
O
CH3
O
OH
O
CH3
OH
O
O
HO
O
OH
O
O
O
O
O
CH3
HO
CH3
O
O
HO
H3C
O
O
O
CH3
OH
O
CH3 H3C
O
CH3
OH
CH3
H3C
O
OH
HO
HO
CH3
H3C
O
CH3
O
OH
CH3
Analytical methods
 reactor water, extracts and filter-cakes were characterized by
gravimetric analysis
 elemental analysis was done on the oil and tar fractions
 monomers were identified and quantified by GC-MSD/FID
 reactor water was analyzed by HPLC MS/RID/DAD
(formic acid, acetic acid, methanol)
 oligomeric oxyaromatics were analyzed on a LC MSD Ion Trap XCT plus
OH
OH
O O
O
O
O
O
O
O
O
O
O
OH
O
O
O
HO
OH
O
O
H
O
O
OH
O
OH
O
O
O
OH
OH
O
OH
OH
O
O
H
OH
O
OH
OH
OH
OH
O
OH
HO
OH
O
OH
OH
O
O
O
O
O
OH
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
20.00
22.00
24.00
26.00
28.00
30.00
32.00
950000
900000
= ISTD
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
100000
4.00
© Fraunhofer CBP
O
O
O
O
O
O
OH
850000
800000
750000
Flam ionization detector
O
O
OH
OH
OH
OH
O
O
OH
O
O
O
O
OH
O
OH
O
Mass selective detector
O
OH
O
OH
OH
O
OH
O
Abundance
OH
HO
O
O
OH
1.15e+07
1.1e+07
1.05e+07
1e+07
9500000
9000000
8500000
8000000
7500000
7000000
6500000
6000000
5500000
5000000
4500000
4000000
3500000
3000000
2500000
2000000
1500000
1000000
500000
O
OH
O
O
OH
OH
O
OH
O
O
OH
OH
OH
O
O
O
OH
O
OH
6.00
8.00
10.00
12.00
14.00
16.00
18.00
Time [min]
20.00
22.00
24.00
26.00
28.00
30.00
32.00
GC-MSD/FID of an extracted oil
Analytical methods
 reactor water, extracts and filter-cakes were characterized by
gravimetric analysis
 elemental analysis was done on the oil and tar fractions
 monomers were identified and quantified by GC-MSD/FID
 reactor water was analyzed by HPLC MS/RID/DAD
(formic acid, acetic acid, methanol)
 oligomeric oxyaromatics were analyzed on a LC MSD Ion Trap XCT plus
Intens.
x108
78
6
1.5
Possible structures of the molecule ions:
9
10
1.0
5
4
11
12 13
3
0.5
2
14
O
15
16
-
O
HO
1
OH
-
O
HO
-
HO
OH
OH
0.0
2
4
6
8
10
12
14
16
18
Time [min]
Intens.
x107
H3C
H3C
2.0
1.5
HO
1.0
OH
OH
0.5
0.0
2
4
6
8
10
12
14
16
18
black: TIC: scan:100-2200 amu; green: EIC: m/z=305.5 z=1;
blue: EIC: m/z= 291.4 z=1; brown: EIC: m/z= 277.3 z=1
© Fraunhofer CBP
Time [min]
HO
OH
OH
H3C
O
OH
OH
Effect of temperature / residence time on oil yield
oil or tar
– yield
[%]
Ausbeute
[%]
60
50
40
30
20
10
0
L 54
300 / 300
L 91
300 / 450
L 55
300 / 600
L 92
325 / 300
L 56
325 / 450
L 93 Mw
325 / 450
L 94
325 / 600
L 57
350 / 300
L 95
350 / 450
L 58
350 / 600
Tem peratur
/ Verw eilzeit [s]time [sec]
temperature
[°C] /[°C]
residence
- with increasing temperature a decomposition of the tar-fraction occurs
- oil-yield always stays at around 20-25 wt%
© Fraunhofer CBP
600
Effect of temperature / residence time on oil composition
residence time [sec]
phenol
guajacol & monomethoxyp.
syringol & dimethoxyphenols
o-hydroxyphenol derivatives
m-hydroxyphenol derivatives
benzene; 1,2,3- triol derivatives
alkylphenols
300
alkylbenzenes
oligomers
300
temperature [°C]
350
- strong effect of temperature on cleavage of methyl-aryl-ether bonds
- medium effect of residence time on cleavage of methyl-aryl-ether bonds
© Fraunhofer CBP
Effect of temperature / residence time on tar yield
const. p=250bar, cNaOH=0,5%; MIBK extracted
residence time [s]
yield tar [%]
temperature [°C]
R2= 99,7 %
- with increasing temperature a decomposition of the tar-fraction occurs
- oil-yield always stays at around 20-25 wt%
© Fraunhofer CBP
Effect of temperature / residence time on molecular characteristics
of the tar-fraction
Mn [g/mol]
Mw [g/mol]
Mz [g/mol]
molecular
weight
[g/mol]
Molekulargewicht
[g/mol]
600
500
400
300
200
100
0
L 54
300 / 300
L 91
300 / 450
L 55
300 / 600
L 92
325 / 300
L 56
325 / 450
L 93 Mw
325 / 450
L 94
325 / 600
L 57
350 / 300
[°C] / Verweilzeit [s]
temperatureTemperatur
[°C] / residence
time [sec]
starting material: Mn= 800 g/mol; Mw = 1575 g/mol ; Mz = 3035 g/mol
© Fraunhofer CBP
L 95
350 / 450
L 58
350 / 600
BCD on different Lignins – Organosolv-Lignins
T=300°C, p=250bar, τ=600s; ethyl acetate extracted
perennial plant
annual plant
phenol
guajacol & monomethoxyphenols
syringol & dimethoxyphenols
o-hydroxyphenol derivatives
m-hydroxyphenol derivatives
benzene; 1,2,3- triol derivatives
alkylphenols
di- & trimethoxy-alkylbenzenes; alkylbenzenes
oligomers
the type of lignin / annual plant (HGS) or perennial plant (G / GS) determine
the product distribution in the oil-phase
© Fraunhofer CBP
BCD on different Lignins – Kraft–Lignin (sofwood)
[NaOH]
Y oil
Low
(1%)
Estimated Response Surface
c NaOH=1,0
20
18
16
14
12
10
8
6
4
300
310
320 330
temperature
340
Y oil
8,7
9,5
10,3
11,1
11,9
12,7
13,5
14,3
15,1
15
13
15,9
11
9
7 residence time 16,7
5
17,5
Effect of c(NaOH) on the oil-yield
Main Effects Plot for Y oil
15,9
14,9
Medium
(3%)
Y oil
Estimated Response Surface
c NaOH=3,0
20
18
16
14
12
10
8
6
4
300
310
320 330
temperature
340
Y oil
8,7
9,5
10,3
11,1
11,9
12,7
13,5
14,3
15,1
15
13
15,9
11
9
7 residence time 16,7
5
17,5
Y oil
13,9
12,9
11,9
10,9
9,9
300,0 340,0 5,0
15,0 1,0
5,0
temperature residence time c NaOH
High
(5%)
© Fraunhofer CBP
Y oil
Estimated Response Surface
c NaOH=5,0
20
18
16
14
12
10
8
6
4
300
310
320 330
temperature
340
Y oil
8,7
9,5
10,3
11,1
11,9
12,7
13,5
14,3
15,1
15
13
15,9
11
9
7 residence time 16,7
5
17,5
- very strong effect of temperature on oilyield (not like OS-Lignin)
- medium effect of residence time and
base concentration on oil-yield
Forthcoming activities
 Investigations & comparisation of process parameters and the type of
lignin on the cleavage of aryl-aryl-ether and aryl-methyl-ether bonds
R
process parameters:
H
R: H or alkyl
T, τ, p, catalyst
OH
OH
R
R
presence of active H2
R
G
or
O
OH
CH3
OH
OH
R
O
OH
CH3
R
CH3
O
OH
CH3
HO
OH
OH
type of subtsrate:
HGS-Lignin (annual plants)
S
O
OH
GS-Lignin (hard wood)
G-Lignin (soft wood)
© Fraunhofer CBP
Forthcoming activities
 Upgrading of analytical methods especially SEC-MS and NMR
Intens.
[mAU]
100
80
60
Organosolv lignin
40
20
0
0
2
4
6
8
10
12
14
16
18
Time [min]
Intens.
[mAU]
800
600
T=300°C, 35sec.
400
200
0
0
2
4
6
8
10
12
14
16
18
Time [min]
Intens.
[mAU]
1250
1000
750
T=350°C, 35sec.
500
250
0
0
2
4
6
8
10
12
14
16
18
Time [min]
SEC of lignin (red), oil L38(blue), oil L39(green), DAD λ: 280nm
 Improvement of the downstream processing by membrane separation
 Scale-up and further process development at Fraunhofer CBP
© Fraunhofer CBP
Forthcoming activities
multi purpose reactor and continuous liquid/liquid-extraction
(100L, 200°C // < 80 kg/h)
continuous operating high pressure plant
(350°C, 300bar, 20 kg/h)
 Scale-up and further process development at Fraunhofer CBP
© Fraunhofer CBP
Forthcoming activities
 Investigations on subsequent bond splitting together with partners
OH
O
OH
HO
lignin
OH
OMe
MeO
BCD
O
HO
OH
phenolics
OMe
MeO
OMe
OH
OH
OH
HO
downstream
processing 1
OH
HO
O
O
HO
OMe
O
O
HO
HO
O
OH
method 2
OMe
HO
O
downstream
processing 2
OMe
HO
O
phenolics
MeO
char
© Fraunhofer CBP
OH
O
OMe
OH
O
OMe
OH
OH
HO
OMe
OMe
O
Forthcoming activities
 Investigations on subsequent bond splitting together with partners
OH
O
OH
HO
OH
HO
OH
OMe
MeO
O
HO
OH
OH
OH
OH
HO
~ 30% (C9) of alkyl-bridges are binding
~ 65 wt% of the lignin
O
HO
O
HO
O
OH
OMe
HO
HO
O
O
MeO
O
OMe
O
OMe
OH
OH
OMe
OMe
O
OH
OH
HO
© Fraunhofer CBP
O
HO
OMe
O
OMe
 Only by using different methods
yields > 30 wt% on aromatics
are possible !
OMe
MeO
OMe
Summary
 oil yields are around 25 wt% in short residence times by BCD
 the yield of water insoluble (pH=3) oligomeric compounds (tar) is approx.
50wt% of Lignin
 depending on the process parameters (T, p, residence time, catalyst) and
the downstream processing a defined product distribution can be reached
 the downstream processing / extraction has to be optimized
 only combined processes / subsequent bond splitting will be successful for
high aromatic yields, but…
© Fraunhofer CBP
Summary
 oil yields are around 25 wt% in short residence times by BCD
 the yield of water insoluble (pH=3) oligomeric compounds (tar) is approx.
50wt% of Lignin
 depending on the process parameters (T, p, residence time, catalyst) and
the downstream processing a defined product distribution can be reached
 the downstream processing / extraction has to be optimized
 only combined processes / subsequent bond splitting will be successful for
high aromatic yields, but…
© Fraunhofer CBP
Contact
Gerd Unkelbach
Fraunhofer Center for Chemical-Biotechnological Processes CBP
Am Haupttor (Bau 1251), 06237 Leuna
Phone +49 3461 43 9101
[email protected]
© Fraunhofer CBP