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Pre-treatment Technologies
Jean-Luc Wertz and Prof. Michel Paquot
Lignofuels 2011 - 29 September 2011
PLAN
1. Introduction
2. Physical pre-treatments
3. Chemical pre-treatments (e.g. organosolv)
4. Physicochemical pre-treatments (e.g. steam explosion; AFEX)
5. Biological pre-treatments
6. Economic analysis (OPEX, CAPEX)
7. Performance summary
Average composition of lignocellulosic biomass
Cellulose: molecular structure
• Glucose units linked by β 1-4 glycosidic bonds• One reducing end and one non-reducing end• Linear straight polysaccharide
Hemicelluloses• High structural diversity• Monomers: pentoses and hexoses• Branched polysaccharides• Example: xyloglucans as shown below
Lignin
• Monomers : 3 different monolignols (H, hydroxyphenyl; G, guaïacyl; S, syringyl)
H
G
S
Lignin
Cross-linked polymers of monolignols
Schematic of the role of pre-treatment
Source: P. Kumar et al., 2009
Liquid hot water (LHW)Biomass pretreatment with water at high temperature and pressure
Inbicon’s hydrothermal pre-treatment pilot plant
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 loadings
2. Strong acid:
Powerful agents for cellulose hydrolysis and no enzymes are needed after the concentrated acid process
Alkaline hydrolysis
Well known in the pulp and paper industry as kraft pulping
Extraction of lignin from Kraft pulp mill black liquor by the LignoBoost process
Source: Metso, LignoBoost
Schematic of the MixAlco® process (Terrabon, Inc.)
Source: Holtzapple et al., Terrabon
Organosolv processesSolvolytic cleavage of an alpha-aryl ether linkage by nucleophilic substitution; R=H or CH3; B=OH, OCH3
Some important organosolv processes
Process Name
Solvent / Additive
Asam Water + sodium carbonate + hydroxide + sulfide + methanol / Anthraquinone
Organocell
Water + sodium hydroxide + methanol
Alcell (APR)
Water+ low aliphatic alcohol
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
Lignol’s process based on water/ethanol pre-treatment
Source: Lignol
lignocellulosic materials
heating
filtration
rinsing
washing
water precipitation
centrifugation
washing
Formic Ac./Acetic Ac./Water
Formic Ac./Acetic Ac./Water
Water
pulp
black liquors
Acidified water
pulp
pulp
black liquors
lignins
lignins
Water solubles
Water
CIMV process: formic acid / acetic acid / H2O
Source: C. Vanderghem et al., ULg-GxABT
,
CIMV process using acetic acid/formic acid/waterSource: C. Vanderghem et al., ULg-GxABT
Time
Tem
pera
ture
1,00,50,0-0,5-1,0
1,0
0,5
0,0
-0,5
-1,0
FA/AA/W 1Hold Values
> – – – < 60
60 7070 8080 90
90
YieldPulp
Contour Plot of Pulp Yield vs Temperature; Time
Time: 1h (-1), 2h (0), 3h(1). Temperature: 80°C (-1), 90°C (0), 107°C (1)
CIMV process using acetic acid/formic acid/waterSource: C. Vanderghem et al., ULg-GxABT
Temperature
FA/A
A/W
1,00,50,0-0,5-1,0
1,0
0,5
0,0
-0,5
-1,0
Time 1Hold Values
> – – – < 20
20 4040 6060 80
80
delignification% Of
Contour Plot of % Of delignification vs FA/ AA/ W; Temperature
Temperature: 80°C (-1), 90°C (0), 107°C (1).
FA/AA/W: 20/60/20 (-1) 30/50/20(0); 40/40/20 (1)
CIMV process using acetic acid/formic acid/waterSource: C. Vanderghem et al., ULg-GxABT
Time
Tem
pera
ture
1,00,50,0-0,5-1,0
1,0
0,5
0,0
-0,5
-1,0
FA/AA/W 1Hold Values
> – – – – – < 0
0 1010 2020 3030 4040 50
50
(ppm)Furfural
Contour Plot of Furfural (ppm) vs Temperature; Time
Time: 1h (-1), 2h (0), 3h(1). Temperature: 80°C (-1), 90°C (0), 107°C (1)
CIMV process using acetic acid/formic acid/waterSource: C. Vanderghem et al., ULg-GxABT
Temperature
FA/A
A/W
1,00,50,0-0,5-1,0
1,0
0,5
0,0
-0,5
-1,0
Time 1Hold Values
> – – – – < 30
30 4040 5050 6060 70
70
(%)digestibilityEnzymatic
Contour Plot of Enzymatic digestibility (% ) vs FA/ AA/ W; Temperature
Temperature: 80°C (-1), 90°C (0), 107°C (1).
FA/AA/W: 20/60/20 (-1) 30/50/20(0); 40/40/20 (1)
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
Room temperature ionic liquidsMain cations and anions in ionic liquids
Room temperature ionic liquidsDifferent types of interaction present in imidazolinium-based ionic liquids
Room temperature ionic liquidsProposed mechanism for cellulose dissolution in EmimAc
Room temperature ionic liquids
Hydrolysis of cellulose in a mixture of cellulases and an ionic liquid (HEMA)
+
Steam explosionSchematic of the steam explosion process. 1, sample charging valve; 2, steam supply valve; 3, discharge valve; 4, condensate drain valve
ULg-Gembloux Agro-Bio Tech steam explosion pilot plant (Source: N. Jacquet et al.)
ULg-Gembloux Agro-Bio Tech steam explosion pilot plant (Source: N. Jacquet et al.)
Ulg-GxABT steam explosion pilot plant (Source: N. Jacquet et al.)
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
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
BiomassTreatedBiomass
Heat
What is AFEX™?
AFEX™ is a trademark of MBI
Glucan conversion for various AFEX treated Feed stocks
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
Carbon dioxide explosion
High pressure carbon dioxide, and particularly supercritical carbon dioxide is injected into the reactor and then liberated by an explosive decompression
Mechanical/alkaline pre-treatment
Continuous mechanical pre-treatment with the aid of an alkali
Biological pre-treatmentsWhite-rot fungi are the most efficient in causing lignin degradation
Source: L. Goodeve, 2003
Source: R.A. Blanchette, 2006
XX: Major effect; X: Minor effect;; *: increases crystallinity; 1) alters lignin structureInhibitors: furfural from hemicelluloses and hydroxymethylfurfural from cellulose and hemicelluloses
PretreatmentDecrystallization of
celluloseRemoval of
hemicellulosesRemoval of
ligninInhibitor
formation
Liquid hot water1) XX XX
Weak acid1) XX XX
Alkaline X XX
Organosolv X3 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
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
PretreatmentOPEX ($/gal EtOH)
CAPEX($/gal annual
capacity)
Liquid hot water 1.65 4.57
Weak acid 1.35 3.72
Alkaline 1.60 3.35
Organosolv
Wet oxidation
Steam explosion
Ammonia fiber explosion (AFEX)
1.40 3.72
Ammonia recycle percolation (ARP)
1.65 4.56
Ideal 1.00 2.51
ECONOMIC ANALYSIS: OPEX (Minimum Ethanol Selling Price), CAPEX
Source: Eggeman et al., 2005NB Enzyme cost: EUR 3/kg of produced cellobiose
Thank you for your attention