school of engineering mohammad. taherzadeh @ hb. se mohammad. taherzadeh @ hb. se tel :...
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![Page 1: School of Engineering Mohammad. Taherzadeh @ hb. se Mohammad. Taherzadeh @ hb. se Tel : +46-70-7171032 Tel : +46-70-7171032 www. hb. se / ih / resourcerecovery](https://reader035.vdocuments.site/reader035/viewer/2022062322/56649e535503460f94b48f46/html5/thumbnails/1.jpg)
School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Pretreatment of different materials: An international perspective
Mohammad J. TaherzadehSchool of Engineering
University of Borås
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
A variety of lignocelluloses are attractive in different reagions!
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Complex plants cell walls
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
A challenge by lignin and hemicellulose!
Lignin
Hemicellulose
Cellulose chains
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Challenge of crystallinity!
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Alternative patterns of aggregation
A. The fibrils were twisted individually and then the assembly also twisted.
B. The individual fibrils were twisted of 90°over 300 nm and then packed as closely as possible
C. The fibrils were collectively subjected to twist.
Helical form of a 6 by 6 nm nanofibrils is compared with that of nine 2 by 2 helical nanofibrils packed as close as possible, with the same period.
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Alternative patterns of aggregation
Would not be mechanically stable
Cellulose is deposited alone
The most efficient load-bearing structure
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Changes during Isolation
• Two stages in isolation will influence the final pattern of aggregation:
1.Elevation of temperature2.Effect of drying
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Cellulose is hydrated in its native state at the level of elementary nanofibril
Effects of elevated temperature
Temperature elevation changes the state of aggregation of native
cellulose.
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Drying results in distortion of nanofibrils by:Removing too much of the water needed to lubricate the motion of the nanofibrils relative to each other.
Drying?
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Linear parallel segments, which are artifacts of isolation processes are easily mistaken for naturally accuring crystalline domains.
Changes during Isolation
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Pretreatment in order to:
Release cellulose from the structure:Remove or hydrolyze hemicellulosesRemove lignin
Reduce cellulose crystallinity Provide enough accessible surface area to
absorb the enzymes Adsorption/desorption rates of the enzymes Remove inhibitory compounds following the
substrate
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Pretreatment methods (various efficiency on different factors)
Physical methods Chemical & Physicochemicals
Biological
milling:- Ball milling- Two-roll milling- Hammer milling- Colloid milling- Vibro energy millingirradiation:- Gamma-ray irradiation- Electron-beam irradiation- Microwave irradiationOthers:- Hydrothermal- High pressure steaming- Expansion- Extrusion- Pyrolysis
Explosion:- Steam, Ammonia, CO2, SO2 , AcidsAlkali:- NaOH, NH3, (NH4)2SO3Acid:- Sulfuric, Hydrochloric & Phosphoric acidsGas:- ClO2, NO2, SO2 Oxidizing agents:- Hydrogen peroxide- Wet oxidation- OzoneSolvent extraction of lignin:- Ethanol-water extraction- Benzene-water extraction- Ethylene glycol extraction- Butanol-water extraction- Swelling agentsOrganosolvs/ Ionic liquids
Fungi and actinomycetes(lignin peroxidase, manganese peroxidase, laccase…)
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Cellulose solvents effective for crystallinity
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Possible non-aqueuous cellulose solvents
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Low-temperature Ionic Liquids (80-130 C)
1-Ethyl-3-methylimidazolium acetate [EMIM]OAc
1-Ethyl-3-methylimidazolium chloride [EMIM]Cl
1-Allyl-3-methylimidazolium chloride [AMIM]Cl
1-Butyl-3-methylimidazolium chloride [BMIM]Cl
1-Butyl-3-methylimidazolium bromide [BMIM]Br
1-Butyl-3-methylimidazolium acetate [BMIM]OAc
1-Butyl-3-methylimidazolium tetrafluoroborate [BMIM]BF4
1-Butyl-3-methylimidazolium hexafluorophophate [BMIM]PF6
1-Butyl-3-methylimidazolium methylsulfate [BMIM]MeSO4
1-Octyl-3-methylimidazolium chloride [OMIM]Cl
Imidazole salts
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Milling: Usually part of the process!
Milling: Ball milling Two-roll milling Hammer milling Colloid milling Vibro energy milling
Functions: Size reduction Degree of crystallinity
High energy costs!
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Irradiations
Irradiation:– Gamma-ray irradiation– Electron-beam irradiation– Microwave irradiation
Usually good results Expensive! Ultrasound might have a good
a chance for commercialization (already in the market)
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Hydrothermal process
Cooking in liquid hot water generally at 150-210 °C Water under high pressure can:
– Penetrate into the biomass, – Hydrate cellulose, – Remove hemicellulose (a major function),– Remove part of lignin (but not so effective),
Autohydrolysis occur due to releasing some carboxylic acids such as acetic acid,
Advantages:– No addition of chemicals,– No neutralization afterward,– No corrosion-resistant materials for reactor,– Could be combined with e.g. a delignification process
Industrial application such as by Danish Inbicon
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
High-pressure steaming (+explosion)
Cooking with steam generally at 150-220 °C & 0.5-20 min If followed by explosive releasing of the pressure = Steam
explosion Steam explosion is one of the most popular pretreatments Explosion has important function pH reduces due to autohydrolysis
Industrtial applications by e.g.– Cambi (Norway)– Chemtex (Italy)– Greenfield (Canada)
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Dilute-acid processes!
Similar methods in pulp industries Similar temperature/Pressure as steam explosion! Improvement by addition of:
– Dilute-acid (0.1-1% acids: H2SO4, HCl, etc.)– Carboxylic acids (e.g. acetic acid)– 1-4% SO2– CO2
Functions:– Open up the polymers– Hydrolysis of hemicellulose
Potential commercialization by e.g :– POET (USA)– SEKAB (Sweden)– ABENGOA (USA)
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Alkaline cooking! Treatment with alkaline solutions:
– NaOH,
– Ca(OH)2 (lime) or
– Ammonia (AFEX)
Popular in pulp industries (kraft process) To remove lignin effectively (+ sometimes a part
of the hemicellulose) To reduce crystallinity of cellulose Generally at about 90-130 C for a few minutes to
hours High pH (e.g. 11-12) or alkali concentrations 1-
20% High amount of NH3 is needed (e.g. 1:1 kg/kg
NH3/biomass) Can also be used with explosion
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Oxygen treatments (wet oxidation)!
Wet oxidation = treatment with water and air or O2 at 140-200 C for e.g. 30 min.
It is exothermic process (because of oxidations) It is a combination of solubilization and
degradation reactions Hydrolytic reactions organic acids The hemicelluloses are extensively cleaved to
monomeric sugars; The lignins undergo both cleavage and oxidation; Cellulose is partly degraded.
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Organosolves/Ionic liquids!
Lignocelluloses are mixed with organic liquid (and water?) and heated to dissolve:– Ligning– And/or cellulose
Temperatures of 80-200 °C can be used:– Depends on the solvent used!
Simple solvents such as ethanol or acetone can be used!
Low Temperature Ionic Liquids are hot research topic today!
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Our latest results for high crystalline cellulose!
N-Methylmorpholine-N-oxide (NMO or NMMO) No toxicity Solvent of cellulose Industrial solvent 80-130 C
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Conclusion Lignocelluloses are diffent:
Type, Age, Crystallinity Dryness, Type of the cell wall ….
Pretreatments have different effectivities on various lignocelluloses,
Great developments in pretreatments, but still long way to go…
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School of School of EngineeringEngineering
[email protected]@hb.se.se Tel: +46-70-7171032Tel: +46-70-7171032www.hb.se/ih/www.hb.se/ih/resourcerecoveryresourcerecovery
Thank you!
Question?