Biorefineries. What do we know? Where are the problems? Thomas Rosenau

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1 Thomas Rosenau University of Natural Resources and Life Sciences Vienna Department of Chemistry Biorefineries What do we know? Where are the problems?

2 Bioeconomy a contradiction per se? CHEMISTRY NATURE BIECNMY & GREEN CHEMISTRY?

3 Biorefineries Biorefineries some background The problems of today s biorefineries (the sixpack ) Three examples (for a more optimistic ending)

Chemistry - Refinery Green Chemistry - Biorefinery Products from bio-refineries 1) Bio-polymers (Bio-materials) 2) Bio-chemicals 3) Bio-fuel 4) Bio-energy Definition: refinery

4 Chemistry - Refinery Green Chemistry - Biorefinery Products from bio-refineries 1) Bio-polymers (Bio-materials) 2) Bio-chemicals 3) Bio-fuel 4) Bio-energy Definition: refinery / biorefinery Fractionation (separation and purification) of fossil resources / biomass into its main components that are used further to produce an optimum of balanced products

Looking into the (far) future The basis of the chemical industries, present and future Renewable resources Biorefineries Chemical Industries Fossil resources Petrochemistry In (far) future, fossil

5 Looking into the (far) future The basis of the chemical industries, present and future Renewable resources Biorefineries Chemical Industries Fossil resources Petrochemistry In (far) future, fossil resources WILL be used up. If mankind is not to fall back into a rudimental, pre-industrial state, the whole production and all flows of the chemical industries will have to be changed from a petrochemical basis to a renewable basis. This requires long-term efforts and fundamental research.

6 Either r

7 Product classes of today s classical chemical industry Products from petrochemistry Polymers Industrial chemicals Solvents Elastomers Paint Pharmaceuticals Agrochemicals leochemicals Products from industrial biorefineries Alcohols Amino acids rganic acids Vitamins

8 Product classes of the chemical industry in the far future Polymers (Bio)chemical technologies producing all materials from renewables, which are nowadays mainly based on fossil resources Industrial chemicals Solvents Elastomers Paint Pharmaceuticals Change of the basis of chemical industries and all related production lines Fossil Renewables Agrochemicals leochemicals Alcohols Amino acids rganic acids Vitamins

9 Green starting materials for biorefineries today Mass balance - current situation Plants for biodiesel Plants for biogas Starch for bioethanol Starch for food/feed il plants Sugar 29% Medical plants Fiber plants thers 11.2% 5.8% Wood (pulp, paper, textile, derivatives) thers 91% 44.6% 5.36% 0.446% 1.34% 0.893% 1.34% 9% Wood is - and will remain - the most important renewable starting material for future chemical industries ( biorefineries ).

10 25% LIGNIN 29% HEMI- CELLULSE CELLULSE 5% 1% 40% Anaximenes (ca. 550 v. Chr.): sind viele Dinge aus einem reinen Element [Feuer Wasser Erde Luft] geformt, andere aus zweien oder dreien, nur das Holz jedoch bedarf aller vier. υλη Holz, Materie Methyl, Cellulose Ethyl, ( 1-D ) Propyl Me α--4 β-5 Me DPM β β' Me H Me β-1 Me β--4 H ther natural starting materials: Extractives (fats, oils, isoprenoids) Proteins Starch ther carbohydrates Lignin ( 3-D ) H 4--5 Me 5-5 H Me R H H Hemicelluloses ( 2-D ) H Me H H H H H H CH H H R

11 Biorefineries Biorefineries some background The problems of today s biorefineries (the sixpack ) Three examples (for a more optimistic ending)

12 The time problem Time to grow: refinery 130+ years, biorefinery 25+ years only?! Renewable resources Biorefineries Time Fossil resources Petrochemistry (Energy and chemicals) Today Biorefinery is not an old science There are minimum time requirements for technological and socioeconomic developments.

13 Development time Time to grow: refinery 130+ years, biorefinery 25+ years only?!? Renewable resources Biorefineries Fossil resources Petrochemistry Development of polymers based on building blocks (McKinsey & Comp: Industrial Biotechnology, 2014)

14 The energy vs. matter problem Use as matter : chemicals, materials, food, feed We need CARBN to produce materials and chemicals. We don t necessarily need CARBN for energy production (there are other and better alternatives)! Renewable resources Biorefineries Fossil resources Petrochemistry

15 The energy vs. matter problem Cascade utilization as the logical consequence Extractives Polymers 1) Chemical utilization 2) Energy utilization Value created Biotechnology (fermentation) Chemistry (reactions) Burning Do something with it first! If nothing works you can still burn it! (George A. lah, Nobel Prize Chemisty 1994) Energy usage modes (biogas, pyrolysis oils, direct burning) should be operated only after value-added chemical utilization. A major hindrance in cascade utilization is the insufficient advancement of separation technology and analytical capability today.

16 The separation / analysis problem Natural products Extremely complex mixtures Natural variability Hard to process (consistency) Unknown components Mostly aqueous mixtures ften low concentration (fermentation) Unstable upon storage Demand for new biorefinery-specific separation / purification / analysis techniques!!!

17 We need powerful biorefinery analytics Carbohydrate (cellulose) analysis Lignin analysis Diff. weight fraction 1,4 1,2 1,0 0,8 0,6 0,4 Cotton Linters 5 min 20 min 1 hour 2 hours 4 hours 8 hours 24 hours Renewable resources Biorefineries 0,2 0, log Mw Time, min Analysis of byproducts Fossil resources Petrochemistry 8,0 20,0 22,0 24,0 26,0 28,0 5 - p-methoxyphenacylbromid - 23,728 - GC-MS - CE-MS - NMR - LC-MS - DESI-MS - GPC Development of new products and technologies based on renewables must go hand in hand with the development of robust and reliable analytical methodology.

The lignin problem Example: utilization of

Cellulose (and hemicellulose) can be nicely used

18 The lignin problem Example: utilization of spruce wood Bleaching Ethanol plant Thanks to: Borregaard, Norway / Finland Cellulose (and hemicellulose) can be nicely used today, lignin cannot. Meaningful uses of lignin as general C-source for chemical industries are needed!!!

19 The alpha beta problem α-1-4-link α-1-6-bridge STARCH β-1-4-link H H H H H (Hemi)CELLULSES Glucose from starch is easy, glucose from cellulose is not. n the long run, energy and chemicals / materials will be derived from natural resources that have no competitive utilization in the food / feed market. This requires long-term research efforts (and might require some improved ethical thinking).

20 The breakdown problem Drop-in strategy vs. use-as-is strategy (Bio) Refinery Gas il Coal Future renewable chemistry ( biorefineries ): C, H 2, CH 4, CH 2 =CH 2, Providing C 2 H 5 H necessary chemicals (what (Syn the gas, fossil biofuels, do pyrolysis) today) PLUS Biogas Multiple by cascade bond cleavage utilization PLUS Breakdown to C 1 /C 2 -units Providing special and novel materials Simply by feeding better the use old of the intrinsic chemical properties industries Chemical industries Platform chemicals (commodities) Fine chemicals (specialties) Synth. polymers, fibers, paints, pharmaceutics Value created Is it wise to disregard the synthesis and optimization effort of nature? Acknowledge the uniqueness of the raw materials not just destroying them!

21 biomass Example: poly(lactic acid) (PLA) biorefinery Made from renewable recources Biologically degradable Detour : polymer monomer polymer sugar fermentation lactic acid destillation polymerisation lactide Polylactic acid (PLA)

22 Biorefineries Biorefineries some background The problems of today s biorefineries (the sixpack ) Three examples (for a more optimistic ending)

5-2 h: artificial humification Demethoxylation Demethylation Formation of quinones xidation of aliphatic

23 Ammonoxidation of ligneous matter: N-lignins Complex of dead organic matter Lignin containing raw / waste materials Topsoil 1-3 years: natural humification Required chemicals 2, NH 3, H 2 (T, p) Reactor h: artificial humification Demethoxylation Demethylation Formation of quinones xidation of aliphatic side chains Cleavage of aromatic ring systems Nitrogen enrichment Natural humus Artificial humus, N-lignins

N-Lignins as multifunctional, artificial humic matter and soil improver Chemistry largely identical to natural humic matter C- and N-source, analogous to natural humic matter Short-term, mid-term and

24 N-Lignins as multifunctional, artificial humic matter and soil improver Chemistry largely identical to natural humic matter C- and N-source, analogous to natural humic matter Short-term, mid-term and long-term fertilizing effect Matrix effect (water and nutrient reservoir) Able to utilize bulk lignin amounts Return of lignin into natural cycles (C, N) rather than burning it to C 2 Additional C 2 sequestration / mineralization (carbamate / urea)

25 Whole plant cell wall NMR BKU Universitäts- und Forschungszentrum Tulln (UFT) Analysis of: Celluloses Pulps Lignin Biopolymers Biomaterials Paper Historic celluloses Novel analysis methods specific for green applications

Cellulose aerogels: Functional materials

029 0.030 sound propagation [km s -1 ] 0.

26 Cellulose aerogels: Functional materials with fascinating properties Selected properties cellulose aerogel silica aerogel density [mg cm - ³] > > specific surface [m² g -1 ] α (lin) [1/K 10-6 ] at RT sound propagation [km s -1 ] Ultra-leightweight cellulosic bodies for heat, sound and impact insulation and for medicine (cell scaffolds, bone replacement).

Summary: General trends in future biorefineries

utilization Food / feed: starch Cellulose &

food-/feedstock Cascade utilization Direct

nature s ingenuity in synthesis and material

27 Summary: General trends in future biorefineries Material / chemical utilization Energetic utilization Food / feed: starch Cellulose & lignin: chemistry Energy / chemicals from food-/feedstock Cascade utilization Direct (one-step) utilization by burning Better use of nature s ingenuity in synthesis and material production Extensive breakdown of renewables green-to-oil C, H 2, CH 4, C 2 H 5 H

28 Financial $upport Alma mater viridis

29 Thanks to the people who are actually doing the work

30 Thomas Rosenau University of Natural Resources and Life Sciences Vienna Department of Chemistry Biorefineries What do we know? Where are the problems?

The chemicalbasisof bioeconomies

The chemicalbasisof bioeconomies Chemistry, biorefineries and renewables Green chemistry and biorefineries Let s look at bioeconomy - through the chemist s eyes Chemistry - Refinery Green Chemistry - Biorefinery