J.Y. Zhu
US Forest Service, Forest Products Laboratory, Madison, WI
2011 TAPPI IBBC
Atlanta, GA, March 14-16, 2011
Why is so unique about
woody biomass ?
Strong structure and large physical size
High energy for size reduction Strong recalcitrance to deconstruction: Most pretreatment not efficient Especially for softwoods Supply of Biomass
~180 softwood
Forest Biorefinery
Energy for wood size reduction
Remove recalcitrance - Pretreatment
Enzyme adsorption to lignocellulose
nonproductive adsorption by lignin
washing
Feedstock Comparison
500‐1000 Wh/kg
50 Wh/kg
1.3 cents/liter
~50 Wh/kg
Cornstover
Energy Consumption for
Size Reduction
Size reduction
Nonwoody:
Woody:
50 Wh/kg = 0.18 GJ/ton
200‐600 Wh/kg = 0.72‐2.16 GJ/ton Biomass ethanol Energy ~80 gallon/ton of biomass (OD) Ethanol HHV = 90 MJ/gallon
Biomass ethanol energy = 7.2 GJ/ton
Thermo to electric energy conversion: 30%
Nonwoody: 8% of total ethanol energy
Woody: 30‐90% of total ethanol energy
Sulfite, SPORL Technology
Applied Microbiology Biotechnology (2010) 86:1355
Lodgepole pine
Wood chips
Water
SPORL
pretreatment Separation
Substrate
Size
reduction
Steam
Spent
liquor
Press
Filtration water
Filtration
Chemicals
XAD column
detoxification
Hydrolysate
Fermentation
Ethanol
SPORL Chemistry
Hemi. degradation
Cellulose depolym.
Lignin condensation
Low delignification
Low degradation hemi.
Low depolym. cellulose
Avoid excessive lignin condensation Sulfonated lignin
Hemicellulose degradation
Cellulose depolymerization
Energy Savings by
Post-Pretreatment Size-Reduction
Bioresource Technology (2010) 101:2782
Pretreatment
@180oC for
30 mina
Untreated
Hot-water
Acid
SPORL
SPORL
Initial
liquor
pH
5.0
1.1
4.2
1.9
Disk milling
energy
(kWh/ton wood)
699
680
412
594
153
Size-reduction
energy savings
(%)
2.7
41.0
15.0
78.1
SED (%)
12.7
16.0
41.6
75.1
91.6
Effect of Milling Disk-Plate Gap
Bioresource Technology (2010) 101:2782
Disk-milling energy
(Wh/kg od untreated wood)
512
256
128
64
Pretreatment pH(t=0)
Hot water
5.0
Dilute acid 1.1
SPORL
4.2
SPORL
1.9
32
16
8
0.5
1.0
1.5
2.0
2.5
3.0
Disk-plate gap (mm)
3.5
4.0
Effect of Milling Disk-Plate Gap
SED (wt% of substrate glucan)
100
Bioresource Technology (2010) 101:2782
90
80
70
60
Pretreatment pH(t=0)
Dilute acid 1.1
SPORL
1.9
2
y = 42.6 - 1.52x, r = 0.72
2
y = 97.2 - 1.68x, r = 0.61
50
40
30
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Disk plate gap (mm)
3.5
4.0
Woody Species Studied
Softwood Lodgepole pine
Red pine
Spruce
Hardwoods Aspen
Eucalyptus Poplar: NE222, NM6, DN5
Decayed Tree
Ethanol concentration (g/L)
High Solids
Saccharification and Fermentation
60
Solids @ 18%
50
40
30
20
Fermentation Experiments
I
II-1 II-2 II-3 III
10
SPORL
DA
0
0
20
40
60
80 100 120 140 160 180
Fermentation duration (h)
High Solids
Saccharification and Fermentation
SSF efficiency @ 96 h (%)
90
80
Solids @ 18%
70
60
50
40
30
SPORL
DA
20
6
8
10
12
14
Cellulase dosage (FPU/g glucan)
16
Washing of Solubles
Enzyme adsorption to lignocellulose
nonproductive adsorption by lignin
washing
Unwashed SPORL Substrate:
Comparing washing with MgSO4
Substrate enzymatic digestibility, SED (%)
Bioresource Technology (2010) 101:9120
100
90
80
70
60
Unwashed
o
Washed @ 25 C
Unwashed + Mg(II)
50
40
5
10
15
20
25
30
Cellulase loading (FPU/g cellulose)
Material and Energy Analysis
Applied Microbiology Biotechnology (2010) 86:1355
Hydrolysis (H) lignin from solid substrate
0.41
(113 Wh/kg)
NA
A
0.18
(50 wh/kg)
1.33
Glucan: 385
Mannan: 4
Xylan: 8
H Lignin: 195
603
C
NA
NA
NA
Ethanol
276 Liters
1000
Glucan: 426
Mannan: 110
Xylan: 69
Lignin: 271
Ethanol: 209
H Lignin: 195
B
Dissolved (D) Lignin
in spent liquor
397
Glucan: 32
Mannan: 86
Xylan: 27
D Lignin: 76
Ethanol: 67
D Lignin: 76
4.55
GJ/ton wood
SPORL – Without detoxification
Bioresource Technology (2010) 101:8678
Ethanol
Lignosulfonate
Spent
Liquor
Chemicals
SPORL
pretreatment
Separation
Steam
Combined
Fermentation
Filtration
water
Size
reduction
Water
Press
Mass Energy Balance
Bioresource Technology (2010) 101:8678
0.76
(212 Wh/kg)
0.18
(50 wh/kg)
1.33
606
603
NA
Glucan: 367
Mannan: 3
Xylan: 3
Lignin: 213
NA
Ethanol
NA
270 Liters
1000
Glucan: 419
Mannan: 117
Xylan: 55
Lignin: 286
Ethanol: 213
Lignin: 286
394
Glucan: 27
Mannan: 60
Xylan: 22
Lignin: 73
4.05
NA
Pilot Scale Study
CD‐300 Disk refiner with Impregnation Semi‐continuous
20 – 40 kg per run
Future Plans
Partner with industry for Jet fuel Production Lignin co‐products
SPORL Publications
Zhu, J.Y., Pan, X.J., Wang, G.S, Gleisner, R., (2009), “Sulfite Pretreatment (SPORL)
for Robust Enzymatic Saccharification of Spruce and Red Pine“ Bioresource Technology,
100(8):2411-2418.
Wang, G.S., Pan, X.J., Zhu, J.Y., Gleisner, R., Rockwood, D.R., (2009), “Sulfite
Pretreatment to Overcome Recalcitrance of Lignocellulose (SPORL) for Robust Enzymatic
Saccharification of Hardwoods“ Biotechnology Progress, 25(4):1086-1093
Zhu, W., Zhu, J.Y., Glesiner, R., Pan, X.J., (2010), “On Energy Consumption for SizeReduction and Yield from Subsequent Enzymatic Hydrolysis of Lodgepole Pine,” Bioresource
Technology ,101:2782-2792
Zhu, J.Y., Zhu, W. OBryan, P., Dien, B.S.,Tian, S., Gleisner, R., Pan, X.J., (2010),
“Ethanol Production from SPORL-Pretreated Lodgepole Pine: Preliminary Evaluation of Mass
Balance and Process Energy Efficiency”. Applied Microbiology and Biotechnology
86:1355-1365
Tian, S., Luo, X., Yang, X.S., Zhu, J.Y., (2010) “Robust Cellulosic Ethanol Production
from SPORL-Pretreated Lodgepole Pine using an Adapted s. cerevisiae without Detoxification”,
Bioresource Technology 101:8678-8685
Liu, H., Zhu, J.Y., Fu, S.Y., (2010), “Effects of Lignin-Metal Complexation on Enzymatic
Hydrolysis of Cellulose”. J. Agricultural and Food Chemistry, 58:7233-7238
Liu, H., Zhu, J.Y., (2010) “Eliminating Inhibition of Cellulase by Unbound Lignin in
Unwashed SPORL-Pretreated Lignocellulose Using Lignin-Metal Complexation“ Bioresource
Technology, 101:9120-9127
SPORL Publications
Luo, X.L., Gleisner, R., Tian, S., Zhu, W.Y., Negron, J., Horn, E., Pan, X.J, Zhu, J.Y., (2010), “Evaluation of Mountain Beetle Killed Lodgepole Pine for Cellulosic Ethanol Production by SPORL” Ind. Eng. Chem. Res. 49(17):8258‐8266
Ind. Eng. Chem. Res. Zhu, J.Y., Pan, X.J., Zalesny, R.S. Jr., (2010), “Pretreatment of Woody Biomass for Biofuel Production: Energy Efficiency, Technologies and Recalcitrance” Applied Microbiology and Biotechnology, 87:847‐857
Tian, S. , Zhu, W., Gleisner, R., Pan, X.J., Zhu, J.Y., (2010) ”Comparisons of SPORL and Dilute Acid Pretreatments for Sugar and Ethanol Productions from Aspen” Biotechnology Progress (accepted)
Zhu, J.Y., Wang, G.S., Gleisner, R., Pan, X., (2009), “Specific Surface for Evaluating Wood Size Reduction and Pretreatment Efficiencies” Chemical Engineering Science, 64(3):474‐
485. Zhu, J.Y. and Pan, X.J., (2010), “Woody Biomass Pretreatment for Cellulosic Ethanol Production: Technology and Energy Consumption Evaluation” Bioresource Technology 101:4992‐5002
FL: 0.68
FL
1000
Glucose: 277
FDD:
Glucose: 264
FDD: 0.46
Glucan: 380
Mannan: 7
Xylan: 7
Lignin: 207
FL:
630
FDD
Glucan: 420
Mannan: 95
Xylan: 46
K. Lignin: 282
NA
FDD:
1000
Glucan: 391
Mannan: 100
Xylan: 60
K. Lignin: 286
634
Glucan: 351
Mannan: 9
Xylan: 9
Lignin: 241
1.33
0.18
NA
FL:
Ethanol
FL: 206 L/ton
FDD: 222 L/ton
FL: 366
Glucan: 20
Mannan: 46
Xylan: 26
Lignin: 51
Acetic acid: 9
HMF as hexsan: 4
Furfural as pentosan: 6
FDD: 370
Glucan: 21
Mannan: 45
Xylan: 20
Lignin: 75
Acetic acid: 8
HMF as hexsan: 4
Furfural as pentosan: 5
FL:
Ethanol: 162
Lignin: 241
FDD:
Ethanol: 175
Lignin: 207
FL: 2.62
FDD: 3.21
SPORL - Dilute Acid Comparisons
SPORL: 0.07
SPORL/DA:
1.25
0.18
SPORL:
627
NA
SPORL:
Glucan: 432
Mannan: 0
Xylan: 12
Lignin: 161
Ethanol: 188
Lignin: 161
DA:
DA:
627
664
664
SPORL:
H2 S04: 11
NaHS03 : 30
DA: 0.17
DA:
1000
Glucan: 438
Mannan: 16
Xylan: 164
K. Lignin: 208
Ethanol: 169
Lignin: 194
Glucan: 418
Mannan: 1
Xylan: 13
Lignin: 194
DA:
H2 S04: 11
336
Glucan: 13
Mannan: 12
Xylan: 97
Lignin: 14
NA
Ethanol
SPORL: 238 L/ton
DA: 214 L/ton
Acetic acid: 50
HMF as hexsan: 2
Furfural as pentosan: 16
SPORL:
373
Glucan: 11
Mannan: 12
Xylan: 108
Lignin: 47
Acetic acid: 68
HMF as hexsan: 2
Furfural as pentosan: 13
SPORL: 4.09
DA:
3.40