Jean-Luc Wertz and Prof. Michel Paquot VALEBIO 23 mars 2012 · Liquid hot water (LHW) Pretreatment...
Transcript of Jean-Luc Wertz and Prof. Michel Paquot VALEBIO 23 mars 2012 · Liquid hot water (LHW) Pretreatment...
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Technologies de prétraitement
Jean-Luc Wertz and Prof. Michel Paquot
VALEBIO 23 mars 2012
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PLAN1 Transformation de la biomasse en énergie et produ its
1.1 La bioraffinerie
1.2 Voie biochimique
1.3 Voie thermochimique
2 Prétraitements
2.1 Prétraitements physiques
2.2 Prétraitements chimiques (p. ex. organosolv)
2.3 Prétraitements physico-chimiques (p. ex. steam explosion)
2.4 Prétraitements biologiques
2.5 Résumé
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Définition Bioraffinage
Le bioraffinage est le processus durablede transformation de la biomasse en:1. bioénergie (biocarburants, électricité, chaleur) 2. produits biobasés (alimentation, produits chimiques, matériaux)
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Raffineries de 1ère et 2ème génération
• Première génération: raffinage à partir de biomasse alimentaire (canne à sucre,, grains de maïs, huile végétale…)
• Deuxième génération: raffinage à partir de biomasse non alimentaire (résidus agricoles et forestiers, déchets municipaux…)
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Crude oil refining
Crude oil
Fuels(Energy)
Building blocks(Petrochemistry)
Specialties(e. g. lubricants)
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Biomass refining
Biomass
Biofuels(Bioenergy)
Building blocks(Agro-bio chemistry)
Specialties(e. g. biolubricants)
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Procédés de transformation
• Plateforme biochimique- Hydrolyse acide (dilué ou concentré)- Hydrolyse enzymatique
• Plateforme thermochimique- Combustion- Gazéification- Pyrolyse & traitement hydrothermique
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Dilute acid hydrolysis
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Concentrated acid hydrolysis
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Enzymatic hydrolysis
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Plateforme biochimique Défis
- Prétraitement de la biomasse- Coût et efficacité des enzymes- Fermentation des sucres C5 and C6 - Valorisation de la lignine
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Thermochemical conversion: primary routes
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Gazéification + Fischer-Tropsch
Conversion de la biomasse en gaz de synthèse ou syngas (H2 + CO) suivie de la conversion du syngas par synthèse Fischer-Tropsch en carburants liquides (BtL)
Synthèse Fischer-Tropsch
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Pyrolyse + conversion catalytique
Conversion de la biomasse en bio-huiles, eux-mêmes convertis en carburants liquides
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Schematic of the role of pretreatment
Source: P. Kumar et al., 2009
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Liquid hot water (LHW)Pretreatment with liquid water at high temperature and pressure
Source: N. Mosier et al., 2005
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Liquid hot water
Performance: Strong removal of hemicelluloses but formation of inhibitor
Inbicon’s hydrothermal pretreatment pilot plant Source: Inbicon
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Weak and strong acid hydrolysis
1 Weak acid:
-High-temperature (>160°C), continuous-flow process for low solids loadings
-Low-temperature (<160°C) batch process for high solids l oadings
Performance: Strong removal of hemicelluloses but formation of inhibitors
2. Strong acid:
Powerful agents for cellulose hydrolysis (no enzymes are needed after the strong acid process)
Performance: High monomeric sugar yield but toxic and corrosive
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Alkaline hydrolysis
Well known in the pulp and paper industry as kraft pulping (or sulfate process) where wood chips are treated with a mixture of NaOH and Na2S
Performance: Weak removal of hemicelluloses, strong removal of lignin
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Extraction of lignin from Kraft pulp mill black liquor by the LignoBoost process
Source: Metso, LignoBoost
� Precipitation of lignin from black liquor by lowering the pH with CO2
� Dewatering by filtration� Redispersion of lignin� Dewatering by filtration of the new slurry� Washing to produce lignin cakes
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Organosolv processesSolvolytic cleavage of an alpha-aryl ether linkage by nucleophilic substitution; R=H or CH3; B=OH, OCH3
Performance: Weak removal of hemicelluloses, strong removal of lignin
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Some important organosolv processes
ProcessName
Solvent / Additive
Asam Water + sodium carbonate + hydroxide + sulfide+ methanol / Anthraquinone
Organocell Water + sodium hydroxide + methanol
Alcell (APR) Water+ low aliphatic alcohol (e.g. ethanol)
Milox Water + formic acid + hydrogen peroxide (forming peroxyformic acid)
Acetosolv Water + acetic acid/Hydrochloric acid
Acetocell Water + acetic acid
Formacell Water + acetic acid + formic acid
Formosolv Water + formic acid + hydrochloric acid
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Lignol’s process based on water/ethanol pre-treatment
Source: Lignol
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Oxidative delignification
1. Hydrogen peroxide treatment
2. Ozone treatment
3. Wet oxidation: treatment with oxygen or air in combination with water at high temperature and pressure
Performance: Decrystalisation of cellulose, weak removal of hemicelluloses, strong removal of lignin
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Room temperature ionic liquidsMain cations and anions in ionic liquids
Performance: Partial to complete dissolution of biomass with easy recovery of cellulose upon anti-solvent addition
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Room temperature ionic liquidsDifferent types of interaction present in imidazolinium-based ionic liquids
Source: H. Olivier-Bourbigou, 2010
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Room temperature ionic liquidsProposed mechanism for cellulose dissolution in EmimAc (1-ethyl-
3-methyl imidazolium acetate)
Source: J. ZHANG et al., 2010
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Source: S. Bose et al., 2010
Room temperature ionic liquidsHydrolysis of cellulose in a mixture of cellulases and tris-(2-hydroxyethyl)
methyl ammonium methylsufate (HEMA)
+
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Steam explosionSchematic of the steam explosion process. 1, sample charging valve; 2, steam supply valve; 3, discharge valve; 4, condensate drain valve
Performance: Strong removal of hemicelluloses but formation of inhibitors
Principle:Treatment of biomass with high-pressure saturated steam, followed by a rapid reduction of steam pressure to obtain an explosive decompression
Source: T. Jheo, 1998
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Ammonia pre-treatments
1. Ammonia fiber explosion (AFEX™): biomass is exposed to liquid ammonia at high temperature and pressure and then pressure is reduced
2. Ammonia recycle percolation (ARP): aqueous ammonia passes through biomass at high temperature, after which ammonia is recovered
Performance: Strong decrystallisation of cellulose, weak removal of hemicelluloses
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Ammonia Fiber Expansion Process
– Moist biomass is contacted with ammonia
– Temperature and pressure are increased
– Contents soak for specified time at temperature and ammonia load
– Pressure is released
– Ammonia is recovered and reused
Reactor Explosion
AmmoniaRecoveryRecovered
AmmoniaAmmonia
vapor
Reactor Expansion
Ammonia Recovery
BiomassTreated
Biomass
Heat
What is AFEX™?
AFEX™ is a trademark of MBI
Source: MBI
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Glucan conversion for various AFEX treated Feed sto cks
SwitchgrassSugarcaneBagasse
DDGS
Rice straw
Corn stover
Miscanthus
UT=No PretreatmentAFEX=Ammonia Pretreatment
Biomass Conversion for Different Feedstocks Before and After AFEX
Glucan conversion afterenzymatic hydrolysis
Excellent Biomass Conversion After AFEX Pretreatment
Source: MBI
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Carbon dioxide explosion
High pressure carbon dioxide, and particularly supercritical carbon dioxide is injected into the reactor and then liberated by an explosive decompression
Performance: Strong decrystalisation of cellulose, strong removal of hemicelluloses
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Mechanical/alkaline pre-treatment
Continuous mechanical pre-treatment with the aid of an alkali
Performance: Weak removal of hemicelluloses, strong removal of lignin
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Biological pre-treatmentsWhite-rot fungi are the most efficient in causing lignin degradation
Source: L. Goodeve, 2003
Source: R.A. Blanchette, 2006
Performance: strong removal of hemicelluloses and lignin
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XX: Major effect; X: Minor effect;; *: increases crystallinity; 1) alters lignin structureInhibitors: furfural from hemicelluloses and hydroxymethylfurfural from cellulose and hemicelluloses
Pretreatment Decrystallization of cellulose Removal o f hemicelluloses Removal of lignin Inhibitor formati on
Liquid hot water 1) XX XX
Weak acid 1) XX XX
Alkaline X XX
Organosolv X XX
Wet oxidation XX X XX
Steam explosion* 1) XX XX
Ammonia fiber explosion (AFEX)
XX X
CO2 explosion XX XX
Mechanical/alkaline X XX
Biological XX XX
Performance summary
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Performance summary
1. All pretreatments partially or totally remove hemicelluloses
2. Wet oxidation, AFEX and CO2 explosion reduce cellulose crystallinity
3. Alkaline, organosolv, wet oxidation, mechanical/alkaline and biological partially or totally remove lignin
4. High amounts of fermentation inhibitors are formed with liquid hot water, weak acid and steam explosion
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Thank you for your attention