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Transformation of lignocellulose into aromatic building blocks
Rainer Schweppe, Gerd Unkelbach, Ulrich Fehrenbacher
Fraunhofer ICT, Pfinztal
Thomas Hirth
Fraunhofer IGB, Stuttgart
Biorefinica 2009, Osnabrück
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Contents
1. Introduction
2. Sugar based aromatics
3. Lignin separation and transformation
4. Summary and conclusions
Introduction
- Potential of
Lignocellulose-Feedstock's (LCF) -
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Vision
Exploration of new synthesis strategies and development of new production sites for the partial substitution of fossil to renewable resources within the middle of the 21 century.
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
From feedstock to product
Raw materialRaw material
Processing-
Grinding-
Extraction-
Digestion
Processing-
Grinding-
Extraction-
Digestion
Biotechnological
Transformation
Biotechnological
TransformationChemical
Transformation
Chemical Transformation
Building Block Material
Building Block Material
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Cellulose
Glucose
Hydroxymethyl-Furfural (5-HMF)
O CHOCH2HO
Hemicellulose
Xylose
Furfural
O C
H
O
Lignin
“Oligo-phenol“
Monophenol
CHCHCH2OH
OHOH
CHCHCH2OH
OHOHHO
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Source: DOW
Ligno-Cellulosic Feedstock (LCF)
Technical Lignin Hemicellulose / Polyoses Cellulose
Fractionation (e.g. “Organosolv- Process)
Lignin Polymers and Resins for:
Bonding MaterialArtificial ResinResinous Exchanger
Alkaline HydrolysisOxidation
Vaniline and Deriv.Vanilin and Deriv.Vanilic AcidSyringa aldehyde
ReductiveHydrothermolysis
Phenols and Deriv.Phenols, BenzeneResins, Oil
HydrolysisAcid Treatment
FurfuralFuran and Deriv.
THF -ButanediolTHF- PolyurethaneFuran Resins
Hydrolysis / Ferm.
Ethanol and Deriv.
Hydrothermolysis
Polyalcohols
Reductive Amination
Diamins, Diisocyanates
( Polyurethanes )
Acid Treatment
HMFand Derivatives
Levulinic Acid (LEVA)(+ Formic Acid)
LEVA-EstersEthyl levulinatehigher esters(Fuel additive, Solvents)
Angelica lactones(Solvents)
Poly-(α-angelicalactone) (Polymers , Plasticizers)
Polycarbonate
Cellulose Oligomersa. Polymerisation
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Sugar based aromatics
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Glucose, Fructose
Hydrothermolysisreductive
Hydrothermolysis
5-HMF5-Hydroxymethylfurfural
DHD2,5-Dihydroxydioxan Polyalcohols
O
O
OH
OH
O CHOHO-CH2
OH
OHOH
OHOH
OH
Mannit
OH
OH
OHOH
OHOH
Sorbit
Compressive strength _|_ rise for reference #1 and formulation #3
0.00
20.00
40.00
60.00
80.00
100.00
120.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
% compression
Com
p. s
tres
s (k
Pa)
Reference #1 Formulation #3
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Purification of 5-Hydroxymethylfurfural via distillation
HMF residue(raw material)
5-HMF 5-HMF residue(raw) (purified)
DBU-Vorhaben
„Synthesebausteine aus nachwachsenden
Rohstoffen„
Aktenzeichen: 24621
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
ICT Synthesis of 2,5-Furanedicarboxylic acid (FDCA)
Pt auf C
O2OH
O
OHO
OH
OO
OH
Oxidation of 5-Hydroxymethylfurfural in water
Batch size max. 2,5 kg 5-HMF
Yield FDCA > 98 %
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
2,5-Dihydroxymethylfurane
5-Hydroxymethylfurfural
Furandicarboxylic Acid 2,5-Diaminomethylfurane
Polyesters,Polyamides,Thermoplastic Elastomers
Polyesters,Polyurethanes
Polyamides,Polyurethanes
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Biopolymers based on Furanedicarboxylic acid
Polyamides OO
OO
OR RO
N
OO
N* CH2 *n
x NH2 CH2 NH2x
+
OO
OO
OR RO
O
OO
O* CH2 *n
x OH CH2 OHx
+Polyesters
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Tm = 250 °C
Tm = 175 °C
Fibres
Tm = 125 °C
OO
NH
ONH ** n
OO
NH
ONH* *n
OO
NH
ONH* *n
Thermal properties polyamides of glucose based polyamides
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Tm = 205-210 °C
Fibres from melt
Tm = 120 °C
Tm = 163 – 165 °C
Tm = 143 – 146 °C
OO
O
OO*
O
n
OO
O*
OO *n
OO O
OO **n
OO O
OO* *n
Thermal properties of glucose based polyesters
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
OO
O
O
*O
*
O
n
O
O
OH
OH
PolyglykolideGlykolide
Polyester Tm
(°C)
Poly(3HB) 178
Poly(3HV) 110
Poly(L-lactid) 185
Poly(glycolid) 223-228
DHD
OH
O
OHOH
OHOH
Glucose
sc. H2 O Oxid.
Lignin separation
and transformation
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Lignin
1/2
(C6H10O5)nHO
O
(OCH3)
OCH3
CH2
CO
H2C OH
OH
HC
CH
H2C OH
OHC
CH
H2C OH
O
H3CO
OHH2C
CH
HC
O
OHH2C
HC
HC
H3CO
OH
O
OCH2
CH
CH
OCH3
HC
HC
H2C
O
HC
HC
H2C OH
OH
OCH3
H3CO
OH
O
OHH2C
CH
HC
O
OCH3
H3CO
OH
OHH2C
CH
HC
H3CO
O
OHH2C
HC
HC OH
OCH3
CH2
CO
H2C OH
O
OCH3
HC
HC
H2COH
OH
O
OHH2C
CH
HC
OCH3
H3CO OCH3
OH
O
OHH2C
HC
HC
HC
CH
O
OH
CH2
OCH3OCH3
OOC
HC
OH
HCOCH3
HCO
HC
HC
H2C
HC
CO
OH
1
2
3
4
5
6
7
8
9
10
11 12
13a 14a
15
16
17
18
1/2 1/2
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Sulfate or sulfite process
Acid wood digestion
Ionic liquids
Hydrothermal Treatment (Aquasolv-Process)
Organosolv-process (Ethanol, …)
Enzymatic cleavage (+ Fraunhofer IGB)
Lignin release from wood
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Temperature: 150 – 250°CExraction time: 1 hourSolvens: Ethanol/Water
Autoclave (13 L)
SeparationSolvent Regeneration
Beech wood
Lignin production:
The ORGANOSOLV-Process
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Nanosized
Organosolv-Lignin
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Process parameter
max. temperature: 400°C max. pressure: 250 barmax. flow rate: 7,3 L/hReactor length: 8- 12 mReactor diameter: 9 mmResidence time: 15 min
Lignin Transformation: Hydrothermolysis
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
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
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
6000000
6500000
7000000
7500000
8000000
8500000
9000000
9500000
1e+07
1.05e+07
1.1e+07
1.15e+07
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
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
750000
800000
850000
900000
950000
Time [min]
Ab
un
dan
ceM
ass
sele
ctiv
e d
etec
tor
Flam
ion
izat
ion
det
ecto
r
OH
OH
OH
OH
OH
O
O
O
OH
O
OH
O
OH
O H
OH
O
OH
O
OH
OOOH
O H
OH
O
O H
OH
O
OH
OH
O
OO
O H
OO
O H
O
O
O H
O
O H
O H
OH
O
O
O
OO
OH
OO
OH
O H
O
O
OO
O H
O
O O H
OO
OH
O
O
O
O
O
OH
OOH
O
OH
O O
OH
O
OH
OH O
O
O
OH
OH
OH
OH
O
O
O
OH
O
O
O
O H
O
O
O H
OH
O
O
O
OH
O
O
OH
O H
OO
O
= ISTD
OH
O
CH3
O O
O
OH
OCH3
O
CH3
O
O
OH
OCH3
OH
O
CH3
O
OH
OCH3
OHO
CH3
O
O
CH3
CH3
OH
O
CH3
OH
O
CH3
OHO
OH
OCH3
O
O
OCH3
O
OH
OH
OH
O
CH3
OH
OH
CH3
OCH3
CH3
OH
O
OCH3
OH
OCH3
CH3 O
O
CH3
OCH3
Fraction of monomers
Fraction of oligomersChemical composition of the products
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Oil composition after hydrothermal treatment
phenol
guajacol & monomethoxyphenols
syringol & dimethoxyphenols
o-hydroxyphenol derivatives
m-hydroxyphenol derivatives
benzene; 1,2,3- triol derivatives
alkylphenols
di.- and trimethoxy-alkylbenzenes;alkylbenzenesunknown compounds
Poplar lignin Beech wood lignin
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Lignin in composites
Summary and conclusions
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Cellulose, Hemicellulose und Lignin are already used in industrial scales
Increasing use of Lignocellulose is detectable
There exist several ways for the production of lignocellulosic products .
Lignin based products could partially substitute fossil resources. Technical feasibility studies are still running.
High grade of functionality needs special conversion technologies.
Biorefinica 2009Transformation of Lignocellulose into aromatic building blocks
Acknowledgment:
Deutsche Bundesstiftung Umwelt (DBU)
Fachagentur Nachwachsende Rohstoffe (FNR)
Thank you for your attention !