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Biomass Pretreatment PDF
Biomass Pretreatment PDF
Mats Galbe
Dept. Chemical Engineering
Lund University
Research @ Chem Eng – Lund
Examples
Biogas
SSF
Lignin
Biorefinery concept
CH2OH
Cellulose glucose
glucose
O OH
OH (42%)
HO Hemicellulose
(20%)
OH
CH2OH
mannose
O OH
OH OH
HO
CH2OH
galactose
HO O
OH
OH
Extractives
OH
Lignin
rhamnose
HO O OH
CH3
(21%)
OH OH
O OH
OH xylose
HO ETHANOL
PHENOLICS
OH
FURALDEHYDES R
O OH ALIPHATIC ACIDS
OH arabinose HO
CH2 O CHO
HOH2C CH3COOH R R
OH
acetic acid OH
HMF
COOH O HCOOH
glucurono-
CHO
O
formic acid
OH pyranose
OH EXTRACTIVES
furfural
H3CO
CH3COCH2CH2COOH
OH
Terpenoids etc.
COOH levulinic acid
O
galacturono
HO
OH
OH -pyranose FERMENTATION INHIBITORS
OH
Pretreatment – desired features for fermentation
Hydrolysis of hemicellulose
• Modification of the
structure
• Increased surface area
• Increased pore sizes
• Partial hydrolysis of
hemicellulose
Rough classification in
terms of pH
Alkaline methods
Leaves a part of the HC in the solid fraction
(For ammonia fibre explosion, AFEX, almost all HC)
Requires hemicellulases acting both on solid and dissolved HC
Classification of pretreatment methods
Irradiation:
• Gamma-ray irradiation
• Electron-beam irradiation
• Microwave irradiation (short penetration)
requires a liquid (or a wet mtrl), dilute
solutions resulting
• Expensive!
• Ultrasound?
Ionic liquids (IL)
Examples
• ILs are salts 1-Ethyl-3-methylimidazolium chloride [EMIM]Cl
• A large organic cation
1-Butyl-3-methylimidazolium bromide [BMIM]Br
• A small anion, usually inorganic
• Liquids at room temperature 1-Butyl-3-methylimidazolium acetate [BMIM]Oac
• Typically range 80 – 130°C
• Chemically stable
• Disrupts bonds between cellulose,
hemicellulose and lignin
• Low degradation to by-products
• A variation of hydrothermolysis
is the wet-oxidation procedure ,
where air or oxygen is added
• Lignin is oxidized causing loss
Alkali
Time
Flash-
vapour
Boiler
Computer
Pretreated
material
Steam pretreatment unit
10 litre reactor
160 - 230 °C
Impregnation with
H2SO4, SO2 or alkali
Main purposes
Improve the enzymatic
hydrolysis of cellulose
Hydrolysis of hemicellulose
Soaking
Steam
pretreated
spruce
Reactor
Solids
Filter
Liquid
Conditions? Depend on purpose
Biomass
Pulping Pulp
Reactor
Heat & Electricity
Power
Solids
Heat
Ethanol
Enzymatic Butanol
Filter Fermentation
hydrolysis Lactic acid
Other
Liquid
Conditions? Depend on purpose
Biomass
Pulping Pulp
Reactor
Heat & Electricity
Power
Solids
Heat
Ethanol
Enzymatic Butanol
Filter Fermentation
hydrolysis Lactic acid
Other
Liquid
Fermentation
Reaction Furfural
Acids (levulinic, Formic etc)
Separation Oligomers
(Building blocks
for polymers)
Assessment? Depends on purpose
Biomass
Example: Reactor
Fermentation of all carbohydrates
Yield of sugars
Concentration of sugars/product
Fermentability
Requires subsequent steps
Enzymatic hydrolysis
Example:
Fermentation
Oligomers as building blocks
SSF
Molecular weight distribution
Structure (side groups etc)
Separation steps
Purity
etc
Severity factor
Time
Consolidated two-step hydrolysis: Profile
OR step-wise temperature change
Time
Improvement of temperature control in steam
pretreatment
T
e
Control by pressure: Fast, requires pT-data m
p
Time
30
Glucose [g/100g]
Mannose [g/100g]
25 Xylose [g/100g]
Total C6 Sugars
Glucose [g/100g]2
20 Mannose [g/100g]2
Xylose [g/100g]
Total C6 Sugars
15
[g/100g DM]
10
0
2.6 2.8 3 3.2Combined Severity3.4 3.6 3.8 4
By-products after dilute-acid hydrolysis
Combined pretreatment and enzymatic
hydrolysis of Barley Husk
Sugar yield (g/100 g Barley Husk)
35
Arabinose
30 Xylose
Glucose
25
20
15
10
0
215 220 210 215 220 210 215 190 200 205 210 215 190 195 200 205 210 215 200 205 Temp. (°C)
5 10 15 5 10 15 Time (min)
0 0.5 Acid conc. (%)
Combined pretreatment and enzymatic
hydrolysis of Barley Husk
4 Acetic Acid
0
215 220 210 215 220 210 215 190 200 205 210 215 190 195 200 205 210 215 200 205 Temp. (°C)
5 10 15 5 10 15 Time (min)
0 0.5 Acid conc. (%)
Microwave
oven
Rotor
Control unit
Shell
Treatment
vessel
Continuous pretreatment reactor
Sekab E-technology
Extraction of hemicellulose from
barley husks
Steam
Filtration - LAROX Concentration
explosion filter press using UF
Extraction of Arabinoxylan from Barley husks
Screening with microwave oven
60 40000
35000
50
Yield (% oligo- and
polysaccharides)
40
30000
Impregnation with
25000
Yield water (pH 6,5)
Mw
30 20000
Mw
15000
20
10000 Res. time: 5 min
10
5000
0 0
100 120 140 160 180 200 220
Temperature
45 60000
40
50000
Yield (% oligo- and
35
polysaccharides)
25
40 40
0 0 0
2.0 2.5 3.0 3.5 4.0 3.0 3.2 3.4 3.6 3.8 4.0 4.2
40
Barley straw 20
50
0.5 wt%
10 1.0 wt%
40
Xylan yield (%)
0
30 3.6 3.7 3.8 3.9 4.0 4.1 4.2 4.3
Severity factor
20
Wheat straw
1 wt% 50
10
1.5 wt%
2 wt% 40
0 Xylan yield (%)
3.6 3.7 3.8 3.9 4.0 4.1 4.2
30
Severity factor a
20
Severity factor
If pH decreases, the molceular
mass decreases
Percentage of arabinoxylan > 5 kDa
100
80
60
40
20 Barley
Wheat
0
4 5 6 7 8 9 10 11 12
180-190°C 210°C
Low severity High severity
Pretreatment Pretreatment
step 1 step 2
High enzymatic
digestibility
Hemi
in liquid
Two-step pretreatment of spruce
(Yields of some sugars)
Improved One-step pretreatment of spruce
Two-step dilute acid pretreatment
Step-wise increase between two temperatures
Ta
time
20
15
10
0
2 5 10 2 5 10 2 5 10 min
190 200 210 ºC
Pretreatment conditions
Linde et al (2006)
Pretreatment of straw
(Glucose yield)
50
Enzymatic hydrolysis
Pretreatment
40 Maximum theoretical
Overall yield of glucose
(g/100g dry straw)
30
20
10
0
2 5 10 2 5 10 2 5 10 min
190 200 210 ºC
Pretreatment conditions
Linde et al (2006)
Finally…
Bottom of reactor
Research/pilot plant
- Two-steps dilute acid- and enzymatic hydrolysis
- Capacity: 2 tons of dry substance per 24 hours
- Complete plant with recirculation of process stream
- Investment 22 million Euro
- Inauguration: May 26 2004
Plan
Demo plant 2010/11
Industrial scale 2014
Problems in pilot plant (deposits)
Problems in pilot plant (leakage)