Woody Biomass Conversion:
Process Improvements at ESF
Shijie Liu
Biorefinery Research Institute
Department of Paper and Bioprocess Engineering
SUNY College of Environmental Science and Forestry
Outline
Introduction
Hot-Water Extraction
Wood Extract Hydrolysis
Membrane Separation
Fermentation
Conclusion
Woody Biomass
Chemical components of wood
wood
21% hardwoods
Lignin
extractives
2-8%
25% softwoods
carbohydrates
35% hardwoods
hemicellulose
25% softwoods
cellulose
45%
Incremental Deconstruction
„
„
„
„
Maximize value achievable
Minimize energy loss
Minimize waste byproducts generation
Multiple product mix
Wood Components:
„
Inorganic Components
K & Ca (400 ~ 1000 ppm);
Mg & P (100 ~ 400 ppm) ; and 70 others
„
Extractives
Aliphatic and alicyclic: Terpenes; terpenoids; esters; fatty acids;
alcohols; …
Phenolic: phenols; stilbenes; lignans; isoflavones; …
Others: sugars; cyclitols; tropolones; amino acids, …
„
„
„
Hemicellulose
Lignin
Cellulose
Lignin
„
Three precursors
a. trans-Coniferyl
alcohol
Guaiacyl
b. trans-Sinapyl
alcohol
Syringyl
c. trans-p-Coumaryl
alcohol
p-Hydroxyphenyl
Hemicellulose
„
Common among angiosperm woody biomass:
Hemicellulose
Type
1
2
3
Soft
wood
Hard
wood
5 ~ 8%
0
10~15%
0
0
2~5
7 ~ 10%
Trace
Trace
15~30%
4
5
Cellulose
Woody
Biomass
Residual
Woody biomass
Hot-Water
Extraction
Co-Gen
or CHP
Gasification
Feedstock
Extraction
Liquor
Alkaline
Puling
Electricity
and Steam
Reconstituted
Wood Products
Separation
or Co-Gen
Plastics
Adhesives
Solvent
Surface agents
Carbohydrates
Aromatics
…
…
…
Sugars
Food additives:
sugar oligomers
Black
Liquor
Paper products or
Cellulose products
Hydrolysis /
Separation
Acetic
Acid
Fuel
Pellets
Unbleached
Pulp
Bleached Pulp
Methanol
Pulping
Chemicals
Xylitol
Ethanol
Butanol
Acetone
Hydrogen
Lactic Acid
PHA
Hot-Water Extraction
Maple Wood Extract
„
100
150
200
Acetyl
Aromatics
Furfurals
10
1
0.1
40
Starting conditions:
369.20 g OD Maple Woodchips
3024.04 g water, 28°C
20
HAc
30
20
MeOH
10
10
Sugars
0
0
50
100
time, min.
150
200
0
Acetic Acid, mM
„
50
100
Concentration, mM
„
Acetic Acid,
Methanol
Acetyl,
Polysaccharides
Aromatics,
Furfurals
Monomeric
Sugars
Methanol, mM
„
time, min.
0
Autocatalytic Extraction
„
„
Dissolution of acetyl groups produces Acetic acid
(HAc)
Acetic acid ionizes in Water
+
⎯
⎯→
HAc ←
⎯⎯ H + Ac
„
+
−
[H ][Ac ]
Ka =
[HAc]
Acidity or proton catalyzes extraction
L-OXn + H+ == L-OXn●H+
L-OXn●H+ + H2O == L-OH + XnOH●H+
XnOH●H+ == XnOH + H+
pH in Extract liquor
5.0
(10,50)
(5,50)
4.5
(5,100)
(5,200)
pH
4.0
(10,1000)
3.5
(5,1000)
(C+0, CHOAc)
3.0
2.5
0
50
100
150
T, °C
200
250
Mass Balance
Residual Woodchips: 77.00 g
Glucan: 38.57 g
Xylan:
4.14 g
Mannan: 1.10 g
Galactan: 0.92 g
Arabinan: 0.04 g
Rhamnan: 0.12 g
Acetyl:
0.89 g
Woodchips: 100 g
Glucan: 40.77 g
Xylan:
15.42 g
Mannan: 2.13 g
Galactan: 0.80 g
Arabinan: 0.58 g
Rhamnan: 0.42 g
Acetyl:
2.17 g
= Glucose: 45.30 g
= Xylose:
17.52 g
= Mannose: 2.37 g
= Galactose: 0.89 g
= Arabinose: 0.66 g
= Rhamnose: 0.47 g
= Acetic acid: 3.57 g
Klason Lignin:
22.30 g
Acid Soluble Lignin: 2.94 g
Unidentified:
12.46 g
Hot-Water
Extraction at 160°C
for 2 hours with
Water to Solid
ratio of 4:1
= Glucose: 42.86 g
= Xylose:
4.70 g
= Mannose: 1.22 g
= Galactose: 1.02 g
= Arabinose: 0.04 g
= Rhamnose: 0.14 g
= Acetic acid: 1.46 g
Klason Lignin:
20.0 g
Acid Soluble Lignin: 0.89 g
Unidentified:
10.33 g
Extract: 23.00 g
Glucan: 0.88 g
Xylan:
8.94 g
Mannan: 0.94 g
Galactan: 1.31 g
Arabinan: 0.55 g
Rhamnan: 0.82 g
Acetyl:
1.07 g
Degredated Lignin:
Unidentified:
= Glucose: 0.98 g
= Xylose:
10.16 g
= Mannose: 1.04 g
= Galactose: 1.46 g
= Arabinose: 0.62 g
= Rhamnose: 0.92 g
= Acetic acid: 1.76 g
3.27 g
5.22 g
ESF Biorefinery:
„
„
„
Hot-Water Extraction
Hydrolysis
Fractionation
„
„
„
„
„
„
Acetic Acid
Methanol
Reducing Sugars
Aromatics, Furfurals
Xylan
Fermentation to Ethanol, Plastics, …
Theoretical Considerations:
DP of the Extractable Polymers
200
k E = kH
DP in extract liquor
DP in solid phase
150
100
50
0
0
20
40
60
Time
80
100
120
Hydrolysis
„
Extract or Dissolved woody biomass solution
„
„
„
Hydrolyzate
„
„
Dissolved carbohydrates and lignin in liquid
Monomeric sugars (~1/3) and polysaccharides
Monomeric sugars (> 80% of all carbohydrates)
Hydrolysis
Hydrolysis
„
„
Depolymerize macromolecules (of
carbohydrates) by inserting water
molecules between the monomeric units
Enzymatic hydrolysis
„
„
Using a hydrolytic enzyme as catalyst
Acid Hydrolysis
„
Using acid (proton) as catalyst
Enzymatic Hydrolysis
„
Substrate specific
„
„
„
Cellulase, xylanase, …
Endo, exo,
Inhibition
„
„
Acid
phenolics
„
Reducing Sugar Concentration, g/L
No pH adjustment
Enzymatic Hydrolysis
pH = 3.26
60
50
40
B
C
D
30
0
1
2
3
Hydrolysis Time, Days
4
Reducing Sugar Concentration, g/L
Enzymatic Hydrolysis
pH = 5.5
60
50
40
B
C
D
30
0
1
2
3
Hydrolysis Time, Days
4
Acid Hydrolysis
„
Glycosidic bonds
„
„
„
Proton is the active catalyst
No preference on first, second, or any bond
Dehydration
„
„
Undesirable dehydration reactions with
monomeric sugars as initial reactants
Acid recover / reuse
Acid Hydrolysis
Reaction Rate
Dehydration reaction
Hydrolysis Reaction
[H+]
Acid Hydrolysis
„
Dilute acid
„
„
„
„
Lower pH, but not high concentration
HCl, H2SO4, HNO3, …
Furfural, HMF and further dehydration
products
Lignin / aromatics - deposition
Xylose Concentration, g/L
Acid Hydrolysis: 95°C
70
60
50
0.0% H2SO4
1.5% H2SO4
3.0% H2SO4
6.0% H2SO4
40
30
20
10
0
0
60
120
Time at temperature, minutes
180
Acid Hydrolysis: 105°C
Free Acetic Acid Concentration, g/L
10
8
0.0% H2SO4
1.5% H2SO4
3.0% H2SO4
6.0% H2SO4
6
4
2
0
0
20
40
60
80
100
Time at temperature, minutes
120
Hydrolysis: 105°C
Precipitates, g/L
10
0.0% H2SO4
1.5% H2SO4
8
3.0% H2SO4
6.0% H2SO4
6
4
2
0
0
20
40
60
80
100
Time at temperature, minutes
120
Fractionation
„
Solid-liquid separations
„
„
„
„
Aromatics and/or degraded lignin recovery
Xylan or xylo-oligomer recovery
Catalyst recovery
Liquid-liquid separations
„
„
„
Membrane separations for
Sugar stream purification
Recovery of chemicals
Nano-Filtration Membrane System
Experimental Set-up: Membrane Separation
Schematic Diagram
P
Permeate
Holding
Tank
Feed and
Concentrate
Tank
Samples of fractionation
Membrane Separation
„
„
Resistances:
„ Osmotic Pressure
„ Friction – Porous Solids
Model:
μ ⎛⎜
⎞
U
⎟
Δp = π + U ⎜1 +
bU
2
⎟
k ⎝ a +U
⎠
2
Osmotic pressure
1800
Apple Juice
Orange Juice
Osmotic Pressure, psi
1600
Glucose
1400
1200
1000
Sucrose
800
600
400
200
0
0
10
20
30
Solids, %
40
50
Flux versus Pressure
Permeate Rate, mL/min
500
400
300
200
100
0
40
60
80
100
Pressure, PSI
120
140
160
First pass: 3-14-06
Permeate Rate, mL/min
500
„
„
400
„
„
300
„
V0 = 66L
Vf = 28L
[HAc]0: 4.62 g/L
[HAc]f: 5.19 g/L
P = 150 psi
200
100
0
1.0
1.2
1.4
1.6
1.8
V0/V
2.0
2.2
2.4
Second pass: 3-14-06
Permeate Rate, mL/min
300
200
„
„
„
100
„
„
V0 = 66 L
Vf = 28 L
[HAc]0: 2.20 g/L
[HAc]f: 3.3 g/L
P = 150 psi
0
1.0
1.2
1.4
1.6
V0/V
1.8
2.0
2.2
Third Pass: 3-14-06
400
Permeate Rate, mL/min
„
„
300
„
„
200
„
V0 = 66 L
Vf = 22.23 L
[HAc]0: 1.40 g/L
[HAc]f: 2.64 g/L
P = 150 psi
100
0
1.0
1.2
1.4
1.6
1.8
V0/V
2.0
2.2
2.4
2.6
Osmotic Pressure Change
160
140
120
π, psi
100
80
60
40
20
0
1.0
1.2
1.4
1.6
1.8
V0/V
2.0
2.2
2.4
Fractionation of wood extracts
Time, minutes
0
60
120
180
240
300
360
10
5
Concentrate Stream
0
0.00
0.02
Permeate Stream
0.04
0.06
0.08
0.10
0
60
120
180
Time, Minutes
240
300
360
C, g/L
C, g/L
15
Reducing sugars as xylose:
200
Starting point
First pass 23.4 g/L
Second pass –
18.2 g/L
Third pass –
16.0 g/L
Reducing Sugars, g/L
1
2
150
3
100
50
0
1
2
3
4
5
6
7
8
V0/V
9
10
11
12
13
14
Acetyl
40
Free Acetic Acid
Bond Acetyl, as acetic acid
C, g/L
30
20
10
0
1
2
3
4
5
6
V0/V
7
8
9
10
Acetic acid concentrations
0.18
0.16
0.14
C, mol/L
0.12
0.10
Concentrate Stream
0.08
0.06
Permeate Stream
0.04
0.02
0.00
0
60
120
180
Time, minutes
240
300
360
Minors
1.6
1.4
C, g/L
1.2
Methanol
HMF
Furfural
Formic Acid
1.0
0.8
0.6
0.4
0.2
0.0
1
2
3
4
5
6
V0/V
7
8
9
10
Separation Efficiency
1.05
Xylose
1.00
Rs
0.95
0.90
Aromatic Compounds
0.85
0.80
0
60
120
180
Time, minutes
240
300
360
Separation Efficiency
0.5
Acetate
Methanol
Furfural
HMF
0.4
Rs
0.3
0.2
0.1
0.0
-0.1
0
60
120
180
Time, minutes
240
300
360
Fermentation
„
Ethanol
„
„
„
Butanol
„
„
E. Coli
Pichia Stipitis
Clostridium acetobutylicum
PHA
Conclusions
Wood Extracts contain more oligmers
than monomeric sugars
Acid hydrolysis is currently preferred
NF-Membrane can be employed to
purify sugar stream;
Osmotic pressure plays an important
role;
Acknowledgements
„
Thomas E. Amidon￭ Christopher D. Wood
„
Raymond Appleby ￭Zhijie (Jeff) Sun
„
Jennifer Putnam ￭ Kathryn Gratien
Alan Shupe
￭ Mitchell Graves
Tingjun Liu
￭ Ruofei Hu
„
Dave Kiemle
„
„
￭ Yang Wang
Thanks!