Biorefinery scenarios for the future BOKU network Bioconversion of Renewables

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Biorefinery scenarios for the future BKU network Bioconversion of Renewables Thomas Rosenau, Antje Potthast, Falk Liebner, Stefan Böhmdorfer,

1 Biorefinery scenarios for the future BKU network Bioconversion of Renewables Thomas Rosenau, Antje Potthast, Falk Liebner, Stefan Böhmdorfer, Axel Russler University of Natural Resources and Life Sciences Vienna (BKU), Department of Chemistry, Chair of Wood, Pulp and Fiber Chemistry

Definition: Biorefinery Fractionation (separation and

further to produce an optimum of balanced products 1)

Bioenergy If possible: preserving the unique properties of the

2 Definition: Biorefinery Fractionation (separation and purification) of biomass in its main components that are used further to produce an optimum of balanced products 1) Biopolymers (Biomaterials) 2) Biochemicals 3) Biofuel 4) Bioenergy If possible: preserving the unique properties of the raw material not destroying it! Acknowledge and utilize the synthesis effort of nature!

3 Creating value added products?! WD Polymers Composites Fibers Bagasse Cost of the raw material Value created Chemicals Biofuels Ethanol Energy Straw

4 Biorefinery looking into (far) future Where do the resources come from? Renewable resources Biorefineries Time Fossil resources Petrochemistry (Energy and chemicals) We need CARBN to produce materials and chemicals. We don t necessarily need CARBN for energy production (there are other and better alternatives)!

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

5 Biorefinery looking into (far) future The basis of the chemical industries, present and future Renewable resources Biorefineries Chemical Industries Fossil resources Petrochemistry In (far) future, fossil fuels 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 research.

6 What about Green Chemistry? Example: chemical from cellulose Green way from cellulose (waste) 1 step yield 82% solvent water or ethanol microwave heating catalyst: clay 92% of atoms used 3 hours R H H H H Classical way (Synthese) from furfuryl alcohol 13 steps yield 8% six different (chlorinated) solvents heating, cooling (-78 C) Extensive purification 3% of atoms used approx. 5 days Selection from the 12 Principles of Green Chemistry : Avoid waste Design direct syntheses Use renewables as starting materials Use catalysts Maximize atom economy Boost energy efficiency Use innocent solvents The Green in Green chemistry has to cover the whole reaction system, not just the starting material. This includes reagents, solvents, auxiliaries, experimental setup and technology, purification and separation steps, as well as energy aspects. Important: development of new, direct syntheses, minimizing the use of dangerous solvents and reagents, utilization of the synthesis effort of nature

7 Biorefinery looking into (far) future General future developments Material / chemical utilization Energetic utilization Food / feed if possible Energy / chemicals from food-/feedstock Cascade utilization Direct (one-step) utilization

8 Distribution of wood constituents in beech (Fagus sylvatica) 25% 29% Cellulose Lignin Hemicellulose Extractives Residue 40% 1% 5%

25% LIGNIN 29% HEMI- CELLULSE CELLULSE 1% 5% 40% Me --4-5 Cellulose Me DPM ' Me H Me -1 Me --4 H From other natural starting materials:

9 25% LIGNIN 29% HEMI- CELLULSE CELLULSE 1% 5% 40% Me Cellulose Me DPM ' Me H Me -1 Me --4 H From other natural starting materials: Extractives (fats, oils, isoprenoids) Proteins Carbohydrates in general Lignin 4--5 H Me 5-5 H Me R H H H H H H H H R Hemicelluloses H Me CH H H

$weight fraction 1,4 1,2 1,0 0,8 0,6 0,4 0,2 Cotton Linters 5 min 20 min 1 hour 2 hours 4 hours 8 hours 24 hours 15000000 10000000 5000000 Renewable resources Biorefineries 0,0 3 4 5 6 log Mw 0 10 20$

10 Biorefinery analytics Carbohydrate (cellulose) analysis Lignin analysis Diff. weight fraction 1,4 1,2 1,0 0,8 0,6 0,4 0,2 Cotton Linters 5 min 20 min 1 hour 2 hours 4 hours 8 hours 24 hours Renewable resources Biorefineries 0, log Mw Time, min Analysis of products 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 Fossil resources Petrochemistry Development of new products and technologies based on renewables must go hand in hand with the development of robust and reliable accompanying analytics.

11 Biorefinery looking into (far) future Renewable resources Biorefineries ~400 kg Fossil resources Petrochemistry ~1000 kg ~400 kg The amounts of cellulose and lignin produced are roughly the same. Utilization of the bulk lignin has been the bottleneck in all recent biorefinery approaches (irregular structure and recalcitrance of lignin).

3 rd Generation biorefinery: ~100% use-up of biomass 25% Cellulose, Hemicelluloses Pulp,

CELLULSE Lignin 1% 5% NH 3 / 2 Fertilizer / humic matter: N-Lignin by ammonoxidation, urea

according to biomass (straw, wood, foliage, stalks) complete use-up of biomass including

12 3 rd Generation biorefinery: ~100% use-up of biomass 25% Cellulose, Hemicelluloses Pulp, materials Chemicals Biofuels Biogas Solid / gaseous residues LIGNIN CELLULSE 40% 29% HEMI- CELLULSE Lignin 1% 5% NH 3 / 2 Fertilizer / humic matter: N-Lignin by ammonoxidation, urea (C 2 -sequestration) novel separation technologies (e.g. supercritical C 2 ) modular setup small, cheap units for on-site use usage adjustable according to biomass (straw, wood, foliage, stalks) complete use-up of biomass including lignin including residues from fermentation (biofuel / biogas) including C 2 (up to 15%) and NH 3 return of organic matter to soil fertilizer / soil improver artificial humic matter International scientific leadership of BKU

13 Ammonoxidation of ligneous matter is the best option for bulk lignin utilization - artificial humic substances Complex of dead organic matter Lignin containing raw / waste materials Topsoil natural humification Required chemicals 2, NH 3, H 2 (T, p) Reactor 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

Biorefeneries BKU network: Bioconversion of renewables Developing biorefineries of the future Renewable resources Biorefineries Starting materials of the future Fractionation into main (pure)

14 Biorefeneries BKU network: Bioconversion of renewables Developing biorefineries of the future Renewable resources Biorefineries Starting materials of the future Fractionation into main (pure) components Analytics Cascade utilization and sustainability Biotechnology and further conversion into chemicals Fossil resources Petrochemistry nly BKU covers the whole chain in (biorefinery) research from primary production and fractionation of biomaterials over biotechnological and chemical conversions to the final products, including analytics, technology and socio economic aspects.

15 BKU Network for Bioconversion of Renewables Bundle expertise at BKU Initiate cooperations with industry, academic partners, agriculture and forestry, public partners Join our initiative!

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

Biorefineries. What do we know? Where are the problems? Thomas Rosenau Thomas Rosenau University of Natural Resources and Life Sciences Vienna Department of Chemistry Biorefineries What do we know? Where are the problems? thomas.rosenau@boku.ac.at Bioeconomy a contradiction