Fast Pyrolysis for the Conversion of Biomass Residues to Biofuels and Bioproducts

Transcription

1 Fast Pyrolysis for the Conversion of Biomass Residues to Biofuels and Bioproducts Tim Schulzke, Group Manager Thermochemical Processes and Hydrocarbons Folie 2

2 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

3 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

4 Patron Joseph von Fraunhofer ( ) Scientist Discovery of the»fraunhofer lines«in the Sun s spectrum Inventor New manufacturing methods for reamfree glass and lenses Entrepreneur Director and co-partner of a glass factory Deutsches Museum Fraunhofer-Gesellschaft "Fraunhofer lines" Folie 5

5 The Fraunhofer-Gesellschaft 69 institutes and independent research facilities 2.1 bn research funds 1.9 bn contract research More than employees (m/f) 1 40 facilities in Germany 13 institutes in North Rhine- Westphalia 4 institutes in the Ruhr area more information under: Oberhausen Aachen Duisburg Euskirchen Kaiserslautern St. Ingbert Saarbrücken Karlsruhe Braunschweig Magdeburg Paderborn Dortmund Halle Schmallenberg Schkopau Sankt Augustin Darmstadt Freiburg Bremen Pfinztal Stuttgart Efringen-Kirchen Itzehoe Hannover Wertheim Ilmenau Würzburg Lübeck München Berlin Potsdam Cottbus Leipzig Jena Chemnitz Erlangen Teltow Dresden Sulzbach-Rosenberg Nürnberg Freising Holzkirchen Rostock Institute branch (m/f) as per including fixed-term contracts of less than 18 months. Folie 6

6 Fraunhofer UMSICHT Pioneer of the energy and resource transition Core area: Process engineering Chemical conversion»from raw material to the product«465 employees (3028 permanent staff) in Oberhausen and Sulzbach-Rosenberg Operating budget 2016: 38.8 million Our subjects: Energy I Processes I Products I Environment I Material I Sustainability Site Oberhausen Our guiding themes: - Production without raw materials Site Sulzbach-Rosenberg - Energy with prudence (= English translation of UMSICHT) Folie 7

7 Organisational Chart of Fraunhofer UMSICHT Folie 8

8 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

9 Working areas in bio-based technologies Biogas (anaerobic digestion) former times: plant development, plant erection/delivery, plant operation now: research on repowering of existing biogas plants, Sabatier reaction, project development with industrial partner Loick Bioenergy (also in Brazil) Wood plastic composites several applications Biodegradable plastics Biobased plastics succinic acid, lactic acid, cellulose-acetate, Thermochemical biomass conversion Drying, Torrefaction, Pyrolysis, Gasification, Combustion Folie 10

10 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

11 Past and actual projects with Brazilian partners LCA for several production routes for bio-ethanol and biomass pretreatment Partners involved: CTBE, CTC, UFRJ, USP ASHES recycling of nutrients from bagasse/straw ashes on German side both parts of UMSICHT involved Partners involved: CNPEM/LNNano, IFG, UFG, LANAGRO/MAPA Consulting on setup for certification laboratory for biodegradability of plastics Partner involved: IPT Consultancy during establishment process of ISI Biomassa organizational: Fraunhofer IPK technically: Fraunhofer UMSICHT (Tim Schulzke) Folie 12

12 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

13 Principle of ablative fast pyrolysis Folie 14

14 Ablative fast pyrolysis Experimental facilities Laboratory plant Functional model for mobile plant 10 kg/h 100 kg/h (design capacity) heat supply: electrical resistance heater heat supply: flue gas (propane combustion) wood and straw straw only Folie 15

15 Mass balance Results from pyrolysis of wheat/barley straw 29.6 % 24.3 % 24.5 % 12.6 % 48.8 % 31.6 % 24.8 % 24.8 % 11.6 % 49.6 % 41.2 % 21.7 % 21.2 % 42.7 % 10.1 % Folie 16

16 Ablative fast pyrolysis Quality of pyrolysis biooil aqueous organic Beech wood mass ratio 67.5 % 32.5 % 100 % total Water 61.7 % 25.3 % 28.7 % nonaromatic Acids 7.4 % 5.9 % 10.4 % nonaromatic Alcohols 1.5 % 0.3 % 0.2 % nonaromatic Aldehydes 0.0 % 1.1 % 3.5 % nonaromatic Ketones 5.9 % 7.1 % 5.5 % Phenols 1.2 % 12.0 % 7.7 % Sugars 1.6 % 1.5 % 6.0 % Heterocyclic Sub. 1.4 % 2.9 % 2.7 % not GC-detectable Sub % 42.4 % 34.8 % lower heating value 7.9 MJ/kg 22.3 MJ/kg 15.4 MJ/kg wheat / barley straw at 549 C, beech wood at 550 C Folie 17

17 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

18 Applications for pyrolysis biooil Pyrolysis oil Direct separation Gasification/ Upgrading Thermal utilization Refining Boiler Gas turbine Engine Co-firing Chemicals Fuels Chemicals Heat Power Folie 19

19 Esterification & Acetalization Acid catalyzed reversible reaction Saturation of reactive groups (carboxylic acids, aldehydes, ketones) Higher alcohols (n-butanol) Acetalisation (Aldehydes, Ketones) Esterification (Carboxylic acids) Folie 20

20 Experimental Esterification/Acetalisation 5 g Catalyst 80 ml n-butanol 80 ml Pyrolysis Condensate Variable: Reaction temperature (80 C C) Reaction time Atmosphere (N 2, Air) Biomass: Wood + Straw Alcohol/Condensate - Ratio Set-Up Phase separation Folie 21

21 Catalyst screening Folie 22

22 Pyrolysis Condensate Esterification water content Folie 23

23 Higher Alcohols Production from short chain alcohols Gas phase condensation of alcohols Related to liquid phase aldol condensation Products: linear and branched alcohols Side products: aldehydes Side reaction depending on residence time, temperature and pressure - H2O Folie 24

24 Higher Alcohols Process conditions: 1-80 bar; C Conversion rate: up to 90 % Catalyst Carbon based Commercially available Stable under process conditions Waterproof Folie 25

25 Staged condensation Approach 1. stage 2. stage 3. stage Folie 26

26 Staged Condensation Three stages experiment Folie 27

27 Staged Condensation Three stages experiment Folie 28

28 Staged Condensation Two stages experiment Folie 29

29 Staged Condensation Two stages experiment Folie 30

30 Phenolic resin as wood glue in non-structural timber Duromer 2 2 Novolak, molecular mass g/mol R = -CH 2 OH 2 glue for plywood Resol, molecular mass g/mol Folie 31

31 Phenolic resin as wood glue in non-structural timber Tensile strength measurement according to DIN EN 205 Folie 32

32 Viscosity[mm 2 *0.1/s]; Peakarea [J/g] Free Formaldehyd [%*10]; Tensile strength [N/mm 2 ] Phenolic resin as wood glue in non-structural timber Degree of substitution [%] 0 Viskosität Peakfläche Freies Formaldehyd Bruchlast Folie 33

33 Rigid polyurethane foams small amount of water releases CO 2 Isocyanate Alcohol Urethane Di-isocyanate Polyether-dialcohol / Polyester-dialcohol to be substituted by pyrolysis oil Folie 34

34 Rigid polyurethane foams Structured set of experiments conducted: 3 different types of biomass, varying method of biooil drying Component A concentration Component B Pyrolysis oil PEG 400 Blowing agent (water) Catalyst DABCO Catalyst SnOct Surfactant / Stabilizer 0-80% of active mass rest of active mass 4.1% of component A 0.5% of active mass 1.5% of active mass 2% of active mass Mixing the constituents Mixing two components (A:B = 100 : 145) Mixing time, Rising time PMDI (polymeric methylene diphenylene diisocyanate) Folie 35

35 Rigid polyurethane foams Folie 36

36 Rigid polyurethane foams Thermal Conductivity Straw Birch W/mK W/mK Beech Commercial products : W/mK Sample with comm. A+B : W/mK Benchmark material cut from insulation at Fraunhofer UMSICHT : W/mK Folie 37

37 stress at 10 % compression (kpa) stress at 10 % compression (kpa) stress at 10 % compression (kpa) stress at 10 % compression (kpa) Rigid polyurethane foams Compressive Strength Straw Compressive strength 300 Birch Compressive strength % 10% 20% 30% 40% 50% 60% 70% 80% 0% 10% 20% 30% 40% 50% 60% 70% 80% Oil content Straw Pytec Oil content dried at 80 Straw Pytec dried at at rus Straw Pytec with dried PEG at :20 dried at 120 Straw Pytec dried with PEG with 100:35 PEG 100:20 at 120 dried at 120 Straw Pytec dried with PEG PEG 100:15 100:35 at at Straw Pytec 119 dried with PEG 100:15 at Beech Compressive strength 0 0% 10% 20% 30% 40% 50% 60% 70% 80% Oil content Beech dried with PEG 100:35 at 120 Beech dried with PEG 100:15 at % 10% 20% 30% 40% 50% 60% 70% 80% Commercial products kpa (minimun) Sample with commercial Comp. A kpa Sample with 100 % PEG 16.6 kpa Benchmark material kpa Oil content Birch from Kazan dried with PEG 100:35 at 120 Birch from Kazan dried with PEG 100:15 at 120 Birch from UMSICHT dried with PEG 100:35 at 120 Birch from UMSICHT dried with PEG 100:15 at 120 Folie 38

38 Horizon2020 Project BioMates Fuels from Reliable Bio-based Refinery Intermediates Folie 39

39 Horizon2020 Project BioMates Partners Folie 40

40 Horizon2020 Project BioMates Mild Hydrotreatment at University of Chemistry and Technology Folie 41

41 Outline 1. Fraunhofer-Gesellschaft and Fraunhofer UMSICHT 2. Overview on related working areas of Fraunhofer UMSICHT 3. Past and actual projects with Brazilian partners 4. (Ablative) Fast pyrolysis 5. Upgrading Technologies and final applications for pyrolysis oil 6. Summary Fraunhofer

42 Summary Ablative fast pyrolysis suitable for multiple biomass feedstocks woody biomass like beech, birch, poplar, fir, spruce, especially for herbaceous biomass like straw, miscanthus, Only low value applications for pyrolysis oil directly due to unfavorable properties (acid number, water content, phase sep.) Esterification with higher alcohols one possible upgrade step Staged condensation broadens applicability to Biogas (for aqueous fraction) Acetic acid (from aqueous fraction) Phenol-Formaldehyde resins (wood glue) Polyurethane foams (e.g. building insulation) Fermentable sugars and/or bunker fuel (from high boiling fraction) Mild hydrotreatment after catalytic vapor treatment/staged condensation allows co-processing in conventional petroleum refinery Folie 43

43 Fraunhofer UMSICHT Department Biorefinery & Biofuels Thank You for Your kind attention! Contact: Fraunhofer UMSICHT Osterfelder Strasse 3, Oberhausen, Germany Internet: Фотография: photocase.de Dipl.-Ing. Tim Schulzke Telephone: Folie 44