Organosolv- based integrated bioreﬁnery of the (ligno) cellulosic biomass an evolu)on from pretreatment to frac)ona)on processes

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$evolu)on from pretreatment to frac)ona)on processes Paul Christakopoulos,$ Leonidas Matsakas, Christos Nichos, Ulrika Rova Biochemical and Chemical Process

Leonidas Matsakas, Christos Nichos, Ulrika Rova Biochemical and Chemical Process

1 Organosolv- based integrated bioreﬁnery of the (ligno) cellulosic biomass an evolu)on from pretreatment to frac)ona)on processes Paul Christakopoulos, Leonidas Matsakas, Christos Nichos, Ulrika Rova Biochemical and Chemical Process Engineering, Luleå University of Technology, Bio4Energy Researchers Meeting 8-9 June Skellefteå

2 The Chemical and Biochemical Process Engineering group CO2 reﬁning processes Chemicals Fuels Materials Bioreﬁnery (Biomass route) Biological and Cataly.c conversion Electro- reﬁnery (Non- Biomass route)

4 The default opera6on of lignocellulosic conversion processes has become almost dogma6c: The raw material is ﬁrst subjected to a pretreatment designed to improve access to the polysaccharides present in the biomass Separa.on has not been a goal

5 Pre- treatment and frac6ona6on, by deﬁni6on

6 Routes for the conversion of biomass into liquid fuels! Serrano-Ruiz and Dumesic, 2010 Red arrows refer to thermal routes, green arrows refer to biological routes, and blue arrows refer to catalytic routes

7 Pre- treatment and fracbonabon Pretreatment of lignocellulosic biomass is mainly associated with biochemical enzyma6c hydrolysis. It improves the eﬃciency of the following enzyma6c hydrolysis step. Pretreatment for thermochemical processes is limited to size reduc6on and drying Pre- treatment vs FracBonaBon Pretreatment focuses on access to carbohydrates Frac6ona6on focuses on separa6on of lignocellulosic components Pre- treatment is ethanol- centric Frac6ona6on is mul6product- centric, i.e.high vol.- low value and low vol.- high value products Bozell, BioResources5(3), 1326 (2010 Although these deﬁni6ons are given, the border between frac6ona6on and pre- treatment is some6mes unclear

8 The petrochemical industry gives a good example Carbon from coal, crude oil or natural gas is used for: ü Transforma6on into fuel for combus6on reac6ons, genera6ng energy (the large majority) (high vol.- low value ) ü Reﬁnement to form the standard building blocks of the chemical industry (much smaller por6on) (low vol.- high value products) Synergis)c interac)on between energy from fuels and proﬁts from chemicals has been a key component of the petrochemical industry for decades

9 Key characteris)cs of biomass frac)ona)on technology designed for mul)product opera)on will include selec)ve separa)on of each component of a biomass feedstock, easy access to and isola)on of the components a@er separa)on, and recovery of each component in high yield.

10 Well- known biomass pretreatment methods: Dilute acid, steam explosion, hot water, AFEX Biomass frac6ona6on technologies: Organosolv processes, processes based on ionic liquids, mul6stage acid hydrolysis

11 Steam explosion pretreatment High dry- ma[er content C, 1-20 min. Rapid release of the pressure Works well for many materials in general, also so^wood Addi6on of an acid, e.g., H2SO4 H3PO4, SO2, Hac, etc. Usually < 2%; commonly %

12 ü The explosion had a high inﬂuence on diges6bility improving it by up to 90 % compared to a steam pretreatment without explosion. ü A Δp of around 20 bar is necessary to reach the maximum improvement in diges6bility Pielhop et al. Biotechnol Biofuels (2016) 9:152

13 Organosolv Pretreatment q Organosolv pretreatment: Pretreatment of lignocellulosic biomas with an aqueous / organic solvent mixture used as the pretreatment medium q Typical solvents : methanol, ethanol, acetone due to low cost, low boiling point, ease of recovery, good lignin solubility q Process temperatures: T ( C) q Achieves frac6ona6on of the major biomass components (cellulose, lignin, and hemicellulose) into three process streams Solvent recycling Lignocellulose Water/Solvent Catalyst Organosolv Lignin separa6on Solvent separa6on Cellulose Lignin Hemicellulose

14 Lignin- free carbohydrate frac6ons ü The enzyme cost accounts for more than 15 % of the minimum bioconversion product (e.g. ethanol) selling price ü The GHG emission associated with produc6on of cellulases accounts for more than 40 % of the GHG emissions from the bioconversion product (e.g. ethanol) ü 50-90%, of the cellulases will be adsorbed onto lignin present in the material

15 Hybrid / Organosolv Solvent- Steam explosion pretreatment Aim: Combine component fractionation achieved by operating the reactor in organosolv mode with the defibration/physical size reduction of the biomass achieved at the final stage by the rapid decompression of the biomass. Steam Reactor SE Valve Cyclone Biomass collection Control panel

16 Hybrid / Organosolv Solvent- Steam explosion pretreatment Ethanol Biomass Steam Slurry

17 Spruce No Explosion Steam Organosolv Explosion

18 Birch No Explosion Steam Organosolv Explosion

19 Organosolv Biomass Pretreatment for Flexible Fuel ProducBon (Solvefuels) (Swedish Energy Agency) ü reducing enzyme consump6on by combining a novel organosolv pretreatment process with advanced frac6ona6on of lignocellulosic biomass into lignin- free carbohydrate frac6ons ü implemen6ng high gravity fermenta6on resul6ng in an increased ethanol yield Period

20 Integrated conversion of forest residues into methane and carbonised materials INFORMAT FORMAS call: Forest raw m aterial and Biomass: Research for a transi6on to a bio- based economy. ü Demonstra6on of an integrated produc6on of methane and carbonized biomaterials (biochar, charcoal and carbon ﬁber) through an eﬀec6ve frac6ona6on of forest biomass. Project partners are Sveaskog, Bothnia Bioindustries Cluster Piteå Science Park, Erebia, Blatraden and Environmental Technical Center Umeå. Period:

21 Conclusions ü The hybrid organosolv pretreatment/frac6ona6on allows the frac6ona6on of spruce biomass with eﬃcient lignin and hemicellulose removal ü High cellulose content solids, up to 72% can be obtained ü High lignin recovery yields up to 70% are possible ü Compa6ble with ethanol- centric and mul6product- centric processes.

Does densification (pelletisation) restrict the biochemical conversion of biomass?

Does densification (pelletisation) restrict the biochemical conversion of biomass? Linoj Kumar, Zahra Tooyserkani Shahab Sokhansanj, Richard Chandra Jack Saddler* Forest Products Biotechnology/Bioenergy