, snabrück Transformation of lignocellulose into aromatic building blocks Rainer Schweppe, Gerd Unkelbach, Ulrich Fehrenbacher Fraunhofer ICT, Pfinztal Thomas Hirth Fraunhofer IGB, Stuttgart
Contents 1. Introduction 2. Sugar based aromatics 3. Lignin separation and transformation 4. Summary and conclusions
Introduction - Potential of Lignocellulose-Feedstock's (LCF) -
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.
Raw material Processing - Grinding - Extraction - Digestion Biotechnological Transformation Chemical Transformation Building Block Material From feedstock to product
Cellulose Hemicellulose Lignin Glucose Xylose ligo-phenol Hydroxymethyl- Furfural (5-HMF) Furfural Monophenol H CH 2 CH H C CH 2 H CH CH CH 2 H CH CH H H H H H
Ligno-Cellulosic Feedstock (LCF) Fractionation (e.g. rganosolv- Process) Cellulose ligomers a. Polymerisation Technical Lignin Hemicellulose / Polyoses Cellulose Alkaline Hydrolysis xidation Vaniline and Deriv. Vanilin and Deriv. Vanilic Acid Syringa aldehyde Reductive Hydrothermolysis Phenols and Deriv. Phenols, Benzene Resins, il Lignin Polymers and Resins for: Bonding Material Artificial Resin Resinous Exchanger Hydrolysis Acid Treatment Furfural Furan and Deriv. THF -Butanediol THF- Polyurethane Furan Resins Hydrolysis / Ferm. Ethanol and Deriv. Hydrothermolysis Polyalcohols Reductive Amination Diamins, Diisocyanates ( Polyurethanes ) Acid Treatment HMF and Derivatives Levulinic Acid (LEVA) (+ Formic Acid) LEVA-Esters Ethyl levulinate higher esters (Fuel additive, Solvents) Angelica lactones (Solvents) Poly-(α-angelica lactone)(polymers, Plasticizers) Polycarbonate Source: DW
Sugar based aromatics Biorefinica 2009
Glucose, Fructose Hydrothermolysis reductive Hydrothermolysis H H H-CH 2 CH H H H H H H 120.00 Compressive strength _ _ rise for reference #1 and formulation #3 5-HMF 5-Hydroxymethylfurfural H H DHD 2,5-Dihydroxydioxan H H Mannit H H Sorbit Polyalcohols Comp. stress (kpa) 100.00 80.00 60.00 40.00 20.00 0.00 0.00 2.00 4.00 6.00 8.00 10.00 12.00 % compression Reference #1 Formulation #3
Purification of 5-Hydroxymethylfurfural via distillation 5-HMF 5-HMF residue (raw) (purified) DBU-Vorhaben Synthesebausteine aus nachwachsenden Rohstoffen Aktenzeichen: 24621 HMF residue (raw material)
ICT Synthesis of 2,5-Furanedicarboxylic acid (FDCA) H H 2 Pt auf C H H xidation of 5-Hydroxymethylfurfural in water Batch size max. 2,5 kg 5-HMF Yield FDCA > 98 %
5-Hydroxymethylfurfural Furandicarboxylic Acid 2,5-Dihydroxymethylfurane 2,5-Diaminomethylfurane Polyesters, Polyamides, Thermoplastic Elastomers Polyesters, Polyurethanes Polyamides, Polyurethanes
Biopolymers based on Furanedicarboxylic acid Polyamides R R + H 2 N CH 2 x NH 2 * N N CH 2 * x n Polyesters R R + H CH 2 H x * CH 2 * x n
Thermal properties polyamides of glucose based polyamides N H N H * n * Tm = 250 C * N N n H H * Tm = 175 C Fibres * N N n H H * Tm = 125 C
Thermal properties of glucose based polyesters * n Tm = 205-210 C Fibres from melt * * n Tm = 120 C * * n Tm = 163 165 C * * n Tm = 143 146 C
Glucose DHD Glykolide Polyglykolide H H H H sc. H 2 H H xid. * n * H Polyester T m ( C) Poly(3HB) 178 Poly(3HV) 110 Poly(L-lactid) 185 Poly(glycolid) 223-228
Lignin separation and transformation
Lignin 18 H 2C H 16 H 2C H C HC CH 2 2 17 H 2C H HC H H 2CH 1 H 2C H 3 C HC CH H CH 2C H 2 15 H 3C CH 3 H 2C H HC CH 3 HC CH CH HC 1/2 1/2 CH 3 HC 4 HC H 2C H CH 3 H 3C H 2C H H HC HC H CH (CH 3) 1/2 HC C H 2C H CH 3 HC H HC 10 H 3C HC H C CH 2 5 HC CH CH H 2C H CH 3 3 9 H 2C H HC HC H HC H 2C CH CH H 3C HC (C 6H 10 5) nh HC CH 11 HC 12 CH 3 CH 3 HC 6 CH2 H H 2C H 13a H 3C 14a CH 7 H 2C H CH 3 H HC H HC 8 HC H 3C H CH 3
Lignin release from wood Sulfate or sulfite process Acid wood digestion Ionic liquids Hydrothermal Treatment (Aquasolv-Process) rganosolv-process (Ethanol, ) Enzymatic cleavage (+ Fraunhofer IGB)
Lignin production: The RGANSLV-Process Temperature: 150 250 C Exraction time: 1 hour Solvens: Ethanol/Water Separation Solvent Regeneration Autoclave (13 L) Beech wood
Nanosized rganosolv-lignin
Lignin Transformation: Hydrothermolysis Process parameter max. temperature: 400 C max. pressure: 250 bar max. flow rate: 7,3 L/h Reactor length: 8-12 m Reactor diameter: 9 mm Residence time: 15 min
Chemical composition of the products Fraction of oligomers Fraction of monomers CH 3 H CH 3 H CH 3 H 3C H CH 3 H H CH 3 CH 3 CH 3 1.15e+07 1.1e+07 1.05e+07 1e+07 9500000 9000000 8500000 8000000 7500000 7000000 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH3 H CH 3 H CH 3 CH 3 H CH 3 CH 3 H H H H 3C CH 3 H 3C H H 3 C CH 3 H H 3C H H H CH 3 CH 3 6500000 H 6000000 H H H Abundance Mass selective detector 5500000 5000000 4500000 4000000 3500000 3000000 2500000 2000000 1500000 1000000 500000 950000 H 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 900000 H 850000 800000 750000 700000 650000 600000 = ISTD 550000 500000 Flam ionization detector 450000 400000 350000 300000 250000 200000 150000 100000 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 Time [min]
Poplar lignin phenol guajacol & monomethoxyphenols syringol & dimethoxyphenols o-hydroxyphenol derivatives m-hydroxyphenol derivatives benzene; 1,2,3- triol derivatives alkylphenols di.- and trimethoxy-alkylbenzenes; alkylbenzenes unknown compounds Beech wood lignin il composition after hydrothermal treatment
Lignin in composites
Summary and conclusions Biorefinica 2009
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.
Acknowledgment: Deutsche Bundesstiftung Umwelt (DBU) Fachagentur Nachwachsende Rohstoffe (FNR) Thank you for your attention!