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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
CO2 refining processes
Biorefinery (Biomass route)
Electro-‐refinery (Non-‐Biomass
route)
Chemicals Fuels Materials
The Chemical and Biochemical Process Engineering group
Biological and
Cataly.c conversion
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
Pre-‐treatment and frac6ona6on, by defini6on
Routes for the conversion of biomass into liquid fuels
Red arrows refer to thermal routes, green arrows refer to biological routes, and blue arrows refer to catalytic routes
!
Serrano-Ruiz and Dumesic, 2010
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
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
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.
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
Steam explosion pretreatment
• High dry-‐ma[er content • 160-‐240°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 0.2-‐ 0.5%
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
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 (185–210 °C)
q Achieves frac6ona6on of the major biomass components (cellulose, lignin, and
hemicellulose) into three process streams
Organosolv Lignocellulose Water/Solvent Catalyst
Lignin separa6on
Solvent separa6on
Solvent recycling
Cellulose Lignin Hemicellulose
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
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
Cyclone
Biomass collection
Control panel
SE Valve
Hybrid / Organosolv Solvent-‐Steam explosion pretreatment
Biomass
Steam
Ethanol
Slurry
Spruce
No Explosion Explosion
Steam
Organosolv
Birch
No Explosion Explosion
Steam
Organosolv
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 2016-‐2018
Integrated conversion of forest residues into methane and carbonised materials
INFORMAT
FORMAS call: “Forest raw material 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: 2017-2020
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.
